Photosensitive resin for printing matrix engraved by laser

FIELD: physics.

SUBSTANCE: invention pertains to a printing matrix engraved by a laser, used for obtaining a relief image using known methods. Description is given of the printing matrix engraved by a laser, obtained through photocuring a compound on a photosensitive resin base (a), consisting of a polymerised unsaturated group and which has an average molecular mass between 1000 to 20 x 104, an organic compound (b), with a polymerised unsaturated group and average molecular mass less than 1000 and an organic silicon compound (c), with at least, one Si-O bond and not containing a polymerised unsaturated group. Content of the organic silicon compound (c), lies in the range from 0.1 to 10 % of the mass of the compound on the photosensitive resin base. Description is given of obtaining the printing matrix engraved by a laser, through formation of the given compound on a canvas or cylinder with subsequent linking and solidification under exposure to light.

EFFECT: increased resistance of the printing matrix to abrasion and to adhesion on its surface.

19 cl, 2 tbl, 12 ex

 

The technical FIELD TO WHICH the INVENTION RELATES.

This invention relates to a composition based photosensitive resin printing matrix and laser engraving of the printing matrix, which is used to obtain a relief image for flexographic printing plates, high-quality printing plates or screen printing, laser engraving, education stereotype for surface treatment such as embossing, the formation of a relief image for printing tiles or similar, get the stereotype of a conductor, semiconductor or dielectric for electronic device, receiving the stereotype of a functional material such as an antireflection film in the optical device, a color filter or a filter, near-infrared, and, further, education covering film or stereotype for orienting layer, ground layer, luminescent layer, electron transport layer, or layer of sealing material in the production of components of liquid crystal display, an organic electroluminescent display or the like, or a roller for normalization of the amount of ink that is in contact with the fabric, transferring the ink, or with anilox roller, not forming a stereotype.

PRIOR art

Among other methods is Catania gradually increasing the share of flexographic printing, which is used for packing materials such as corrugated cardboard, paper bags, paper bags, flexible packing film, building and decorative materials, such as Wallpaper and decorative prints, printing labels and such. Photosensitive resin often used for the production of printing plates for the printing process. For example, uses a method in which a liquid photosensitive resin or solid form photosensitive resin in the form of a sheet. Photomask is placed on the photosensitive resin, the light through photomask carries out the crosslinking reaction and then not sewn parts are washed away using a developing solution. In recent years, developing and increasing the volumes used in connection with increased efficiency in the production of printing forms the so-called flexographic P-technology (computer form); this technology, providing a thin layer of light absorption, called the black layer on the surface of the photosensitive resin, applies the effect to the layer of laser light, forming an image mask directly on the form from a photosensitive resin, followed by exposure to light through a mask, causing the crosslinking reaction with subsequent leaching is not sewn parts that are not operated light. However, this technology is limited to the military capabilities to improve efficiency. The problem is that stage of development can be reduced, and therefore, highly desirable technology in which a relief image is formed directly on the source of the printed form and is not required stage of manifestation.

To solve this problem, a method in which an original printing plate is directly exposed to the laser engraving. The production of forms for letterpress and die by this method has previously been performed. In this method, previously used materials obtained by heating and curing synthetic rubber, such as EPDM and silicone. However, these materials require not only a lot of time to produce, because they take a lot of time for heating and curing to achieve the required mechanical properties, artificial ageing, it is additionally necessary to stabilize their properties, and, further, the first of the above-mentioned materials, using as the original, synthetic resin and the like, have the disadvantage that the fragments formed by engraving, glued to the surface of the form when the form is engraved by laser, and these pieces are very difficult to remove. The second of these materials, using as starting materials silicones, have the disadvantage that the speed of laser engraving so low that it requires a lot of time for the production of shaped and sustained the motion to dissolve the ink is low and so on

As a way to overcome the disadvantages of the materials described above, a method for production of laser engraving flexographic printing plates, in which laser light is effective in curing a photosensitive resin obtained by vodootvedenie composition based photosensitive resin, with the formation of irregular stereotype on the surface.

For example, the patent is 1 (Japanese Patent No.2846954(U.S.Patent No.5798202)) and patent 2 (Japanese Patent No.2846955 (U.S.Patent No.5804353)) for the first time describe the use of the material obtained by mechanical, photochemical or thermochemical consolidation of thermoplastic elastomers, such as SBS, SIS or SEBS.

Patent 3 (JP-A-56-64823) first described the use of the material of the roller obtained by photographing images of the liquid photosensitive resin. In the future, the authors of this invention have proposed in the patent 4 (WO 03-022594) laser-engraving original printing plate using a liquid composition on the basis of a photosensitive resin containing a polymeric material that is plastomer at 20°and suggested a way to make improvements, in which the inorganic porous material is added to prevent formation of liquid fragments under the action of the laser, which reduces build-up on mold surfaces, and the optical system is protected from contamination.

In recent years, felicilda demand on stereotypes for permanent printing, and for this application it became necessary to develop a cylindrical printing matrices, such as seamless cushions, without joints, easily processed laser engraving and suitable for printing high quality.

As described previously, the engraving laser source based form utverzhdenii photosensitive resin has good features laser engraving in comparison with embedded synthetic rubbers and silicone rubbers, and it is expected that the edge of the image is so sharp, that will be fine stereotypes, providing, thus, a high, and not only satisfactory print quality. As a precondition for this, it is extremely important to ensure the accuracy of the thickness of the printing plate and the print quality is highly dependent on the accuracy of thickness form to the stage of laser engraving. In the case of the engraving laser printed matrix high precision film thickness can be guaranteed by the surface treatment utverzhdenii photosensitive resin obtained through a stage photograph with the following processing methods of cutting, grinding and polishing. In particular, in the case of a cylindrical printing matrices, such as seamless cushions that can be placed in the printer, providing print immediately after the gender stereotype is Chen laser engraving, confidence in the accuracy of the thickness is critical in the production method of the engraving laser printed matrix. Of course, the accuracy of the thickness of the stereotype is also important when printed flat shape twisted in the printer cylinder to provide printing, and the same is true for the sheet original form for engraving with a laser.

Patent 1 (Japanese Patent No.2846954(U.S.Patent No.5798202)) and patent 2 (Japanese Patent No.2846955 (U.S.Patent No.5804353)) describe the way in which the composition is based on the photosensitive resin is formed in the shape of a leaf, then cylindrically curved, and the joint is welded by fusion to achieve bestowest. These documents describe that these surfaces can be polished. The authors of this invention have proposed in patent 5 (PCT/JP2004/005839) method to obtain a cylindrical seamless matrix using a liquid photosensitive resin and has also proposed that a surface treatment such as cutting, grinding and polishing, is performed after curing under the action of light.

The authors present invention also investigated in detail the methods of surface treatment such as cutting, grinding and polishing, as applied to conventional compositions based photosensitive resin, previously described, and as a result, it was found that the adhesive fragments formed inthese processes, deposited on the surface and that these fragments are difficult to remove and traces of cutting and polishing may remain on the surface, and the production accuracy of the resulting surface becomes so poor that there is a problem with the print quality, especially if you are high press. The above sticky debris deposited on the surface of the cutting head or polishing wheel, and, in some cases, hard stick. It was found that for treatment of these problems, when the adhesive fragments adhere to the surface of the cutting head or polishing of the circle, you want a neat process, such as stopping work for cleanup and removal of the adhered debris, and thus, the process takes a considerable amount of time.

The authors of this invention in the aforementioned patents 3 and 5 has been proposed a method in which a liquid photosensitive resin is applied at 20°that is an excellent way due to the liquid form of the composition based on the photosensitive resin, which is easily molded and can accept or leaf shape, or form roller in such a simple way as a floor cloth; now found that due to the restrictions on the shape of the resin blend to facilitate curing of the resin, the printed form, laser engraving, after a hole is Denia has the undesirable tendency to the phenomenon of "carrying ink" in which the ink remains in the areas between the elements formed relief stereotype, which reduces the print quality.

There are several variants of the usual ways of improving the surface properties of the printing form-based photosensitive resin, although it is not the means, with respect to the engraving laser printed matrix. For example, patent 6 (JP-A-6-186740) describes the print matrix, suitable for water manifestations for the formation on the surface of the irregular patterns using fotografiruemyj technology, and describes that the photosensitive resin is added to the silicon compound with the polymerized unsaturated group, which is lightly copolymerized with the resin. As the effect of adding the above-mentioned silicone compound described the inhibition of the deposition of dried ink and paper traces between elements formed of relief stereotype. However, the patent 6 (JP-A-6-186740) relates to the production of printing forms using fotografirovalas technology, but not for laser engraving of the printing matrix. If applied in that patent, a silicon compound, is added to control the wetting ability of the surface of the printing plate has a large number of the polymerized unsaturated groups, there is interest in that the density of a point is to the stitching was increased to increase the rigidity utverzhdenii photosensitive resin or increase the compression ratio when the photograph. The authors of the present invention, in a study of "carrying ink after applying silicon compounds described in patent 6, the result found that the silicon compound can be easily transferred to the surface of the cured photosensitive resin and is fixed on the surface for a photograph, and the surface becomes excessively hydrophobic and, as a consequence, is not wetted by a solvent such as alcohol, is widely used as a solvent in the ink and the like; the authors of this invention have recognized this as a problem in ensuring a high quality print.

Also, a method in which the processed surface of the flexographic printing form-based photosensitive resin. Conducted research with the aim of preventing a phenomenon in which the ink deposited on the surface of the printing plate in the printing process, remain and cannot be deleted if they are captured inside small elements of the stereotype, such as points, small letters and fine lines, and these remaining ink transferred to the printing material, leaving spots of ink out of the print area. This trend is particularly amplified in the case of printing for a long period of time or if the pressure during the transfer of ink on the plate surface between the anilox roller and form large, and ink stains in n the printed areas are a serious problem in terms of print quality. If such spots are found, the printer must be stopped to clean the plate surface and, thus, performance is markedly reduced. In patent 7 (JP-A-2002-292985) method, which is applied to the mixture of aqueous emulsion resin and silicon or fluorine compounds, however, this method is not sufficiently effective against the retention of the ink, because covering the aqueous solution has a low wetting ability. There is also the problem of the stability of the effect.

Patent 8 (JP-A-60-191238) describes the material to be copied image, which has a layer of a photosensitive resin layer, scratch resistant, and protective layer, and also describes that the silicone oil is included in the layer of photosensitive resin and silicone oil is transferred to the surface of the photosensitive resin, forming a rough layer. Patent 8 describes as one of the applications of photosensitive resin form of letterpress printing, in which irregular stereotype is formed through the exposure and the stage of manifestation, but it is not the engraving laser form, where the stereotype is formed using the method of laser engraving. For added silicone oil compound, which can be easily transferred from the internal parts of resin to the surface, it is assumed therefore that silicone is aslo not fixed in the resin. Therefore, when the above-described material for the formation of image is used as a printing plate, there is the problem of extraction of silicone oil used ink and, thus, it is difficult to maintain the effect of scratch resistance for a long time.

The authors of the present invention realized as two permanent problem removing sticky debris generated during the stage surface treatment such as cutting, polishing and grinding in the preparation of the engraving laser printed matrix formed from utverzhdenii photosensitive resin, and the problem of "transferring ink between the volume elements of the stereotype of the engraving laser printed matrix. Not described technology, in which the method is able to solve both of these problems simultaneously.

Patent 1 (Japanese Patent No.2846954)

Patent 2 (Japanese Patent No.2846955)

Patent 3 (JP-A-56-64823)

Patent 4 (WO 03/022594 A)

Patent 5 (PCT/JP2004/005839)

Patent 6 (JP-A-6-186740)

Patent 7 (JP-A-2002-292985)

Patent 8 (JP-A-60-191238)

PROBLEM SOLVED IN the INVENTION

The purpose of this invention was to propose a composition based photosensitive resin, suitable for the production of the engraving laser printed matrix prepared from utverzhdenii photosensitive resin, for which the removal of sticky debris generated during the stud and the surface treatment, such as cutting, polishing and grinding is easy, and a printing matrix prevents ink stains on its surface, has a high resistance to abrasion and resistance to adhesion to the surface.

WAYS TO SOLVE

As a result of intensive studies to solve the above problems, the authors of this invention have found that, when the organosilicon compound (C)having in a molecule at least one Si-O bond and not having the polymerized unsaturated group, is added to the composition based on the photosensitive resin in amounts of 0.1-10% of the total weight of the composition, is achieved unexpected effect, in which the cured material obtained by cross-linking and curing of the composition based on the photosensitive resin buildup on the surface and resistance to surface abrasion, cut, and abrasion resistance is dramatically increased and, further, provided saving ink on the surface during printing. These effects developed in this invention.

The INVENTION

1. Composition based photosensitive resin for laser engraving of the printing matrix, which contains the resin (a)whose average molecular weight is in the range of 1000 or less or 200000 or less, with the polymerized unsaturated group is at, as well as the organic compound (b) with an average molecular weight less than 1000, with the polymerized unsaturated group, and the organosilicon compound (c)having in a molecule at least one Si-O bond and not containing the polymerized unsaturated group, where the content of the organosilicon compound (c) is 0.1 wt.% or more, or 10 wt.% or less of the total weight of the composition based on the photosensitive resin.

2. Composition based photosensitive resin according to claim 1 in which the organosilicon compound (c) has an average molecular weight of 100 or less or 100,000 or more and which is liquid at 20°C.

3. Composition based photosensitive resin according to claim 1 in which the organosilicon compound (C) is a silicon compound represented by the average gross formula (1)

RpQrXsSiO(4-p-r-s)/2,

where R is one or more hydrocarbon group selected from the following: a linear or branched alkyl group(s)which has from 1 to 30 carbon atoms; cycloalkyl group(s), which has from 5 to 20 carbon atoms; CNS group(s)which has from 1 to 20 carbon atoms; aryl-substituted alkyl group(s)which has from 1 to 30 carbon atoms (the number of carbon atoms in the alkyl group substitution); halogen-substituted aryl is owned by the group(s), which has from 6 to 20 carbon atoms; alkoxycarbonyl group(s), which has from 2 to 30 carbon atoms; monovalent group(s)containing a carboxyl group or a salt thereof; monovalent group(s)containing alphagroup or a salt thereof; and polyoxyalkylene group(s);

Q and X may be the same or different and each of them is the same hydrocarbon group or more selected from the following: a hydrogen atom, a linear or branched alkyl group(s)which has from 1 to 30 carbon atoms; cycloalkyl group(s), which has from 5 to 20 carbon atoms; CNS group(s)which has from 1 to 20 carbon atoms; aryl-substituted alkyl group(s)which has from 1 to 30 carbon atoms (the number of carbon atoms in the alkyl group substitution); halogen-substituted aryl group(s), which has from 6 to 20 carbon atoms; alkoxycarbonyl group(s), which has from 2 to 30 carbon atoms; monovalent group(s)containing a carboxyl group or a salt thereof; monovalent group(s)containing alphagroup or a salt thereof; and polyoxyalkylene group(s);

p is a Prime number in the range from 1 to 4;

r is a Prime number in the range from 0 to 4;

s is a Prime number in the range from 0 to 4;

and is the sum of p+r+s is a Prime number lower than 4.

4. The composition OS is ove photosensitive resin according to claim 3, in which the silicon compound is a compound having at least one organic group selected from the following: aryl group, a linear or branched alkyl group containing as a substituent at least one aryl group; alkoxycarbonyl group, CNS group and polyoxyalkylene group and a hydrogen atom attached to a carbon atom that is attached organic group (hydrogen α-position).

5. Composition based photosensitive resin according to claim 4, in which the silicon compound has at least one group selected from the following: methylstyrene group, sterelny group and carbinol group.

6. Composition based photosensitive resin according to claim 1 in which the organosilicon compound (c) is a compound containing at least one group selected from the following: aryl group, a linear or branched alkyl group containing as a substituent at least one aryl group; alkoxycarbonyl group, CNS group and polyoxyalkylene group and a hydrogen atom attached to a carbon atom that is attached organic group (hydrogen α-position).

7. Composition based photosensitive resin according to claim 1, additionally containing initiator polopoly is erinacei, in which the initiator of photopolymerization contains at least one initiator of photopolymerization, exciting the hydrogen atom (d).

8. Composition based photosensitive resin according to claim 7, in which the initiator of photopolymerization contains at least one initiator of photopolymerization, exciting the hydrogen atom (d) and at least one degradable initiator of photopolymerization (e).

9. Composition based photosensitive resin of claim 8, in which the initiator of photopolymerization, exciting the hydrogen atom (d)comprises at least one compound selected from the following: benzophenone, xanthene and anthrachinone and degradable initiator of photopolymerization (e) contains at least one compound selected from the following: alkyl esters Bessonov, 2,2-dialkoxy-2-phenylacetophenone, acylated esters Asimov, azo-compounds, organic sulfur compounds and diketones.

10. Composition based photosensitive resin according to claim 7 or claim 8, in which the initiator of photopolymerization is a compound having in the same molecule as an initiator of photopolymerization, exciting the hydrogen atom as a functional substituent, and degradable initiator of photopolymerization as a functional substitute.

11. Composition based photosensitive resin according to claim 1, in which the MES is a (a) is liquid at 20° With the resin (a) and/or the organic compound (b) are compounds bearing element, which has at least one connection selected from the following: carbonate bond, a tie simple ether linkage of ester, and/or which is at least one molecular level, which is a saturated aliphatic hydrocarbon link or unsaturated aliphatic hydrocarbon chain having a urethane bond.

12. Composition based photosensitive resin according to claim 1, in which the covering layer of a composition based on the photosensitive resin has a thickness of 1 mm and has a degree of light absorption 0% or more and 70% or less.

13. Composition based photosensitive resin according to claim 1, which is liquid at 20°C.

14. The engraving laser printing matrix, obtained by photographic compositions on the basis of a photosensitive resin, where the printed matrix contains the organosilicon compound in its inner part or on the surface, and the silicon atoms derived from organosilicon have relative content of 0.01% or more or 10% or less, when the organosilicon compound is recorded and quantitatively determined by a combination of solid-state methods29Si-NMR (spectroscopy solid-state nuclear resonance, which is logged by the kernel is the isotope is Rennie atomic weight 29), and a flame ionization spectroscopy.

15. The engraving laser printing matrix, which can be obtained by molding composition based photosensitive resin according to claim 1 into a sheet or cylinder and then the crosslinking and curing of a cloth or cylinder under the action of light.

16. The engraving laser printed matrix 14 or 15, having the surface treated with at least one method selected from the following: cutting, grinding, polishing, blast after crosslinking and curing under the action of light.

17. The engraving laser printed matrix clause 16, in which the elastomer layer is formed by curing the composition on the basis of a photosensitive resin which is liquid at normal temperature.

18. The engraving laser printed matrix clause 16, in which the surface layer of the multilayer material is a layer that can be engraved by laser near-infrared light.

19. The engraving laser printing matrix containing the composition based photosensitive resin, where the engraving laser printing matrix has a surface with that of the wetting ability that when 20 μl of the indicator fluid with a surface energy of 30 mn (trademark "Wetting Tension Test Mixture No.30,0", produced by Wako Pure Chemical Industries, Ltd.), quantitatively selected what micropipettes of a particular type, was bury on the surface and within 30 seconds was measured, the maximum size of the area, on which was spread a drop, the size of the region in diameter was 4 mm or more and 20 mm or less.

20. The engraving laser printing matrix according to any one of PP-19, which is the original flexographic printing form, or the original form of letterpress printing, or the original form of stencil printing, in which the stereotype is made by way of laser engraving, or roller standard amount of ink that is in contact with the fabric, transferring the ink, or with anilox roller, on which is formed the template.

Advantages of the INVENTION

This invention provides a composition based photosensitive resin, suitable for the production of the engraving laser printed matrix formed from utverzhdenii photosensitive resin, which makes light surface treatment such as cutting, grinding and polishing, and a printing matrix prevents the formation of spots of ink on it, increasing abrasion resistance and preventing buildup on the surface.

BRIEF DESCRIPTION of DRAWINGS

Figure 1 is a photograph of the surface of the printing form after the trial printing in example 1 of the present invention, and

Figure 2 is a photograph of the surface of the PE atoi form after trial printing in comparative example 1 of the present invention.

A DETAILED DESCRIPTION of the PREFERRED OPTION IMPLEMENTATION

A detailed description of the preferred alternative implementation of the present invention will be given hereinafter in detail.

The organosilicon compound (C)used in this invention is defined as a compound having at least one functional group on the silicon atom. Used organosilicon compound should preferably have at least one Si-O bond in the molecule. The organosilicon compound having a siloxane structure or a polysiloxane structure with Si-O-Si bond, particularly preferably from the viewpoint of atmospheric stability, structural stability and stability during storage.

The organosilicon compound (C) of the present invention preferably is a compound not having the polymerized unsaturated group in the molecule. In this invention, "the polymerized unsaturated group" is defined as the polymerized unsaturated group that is involved in a radical or polyprionidae reactions of polymerization. Preferred examples of the polymerized unsaturated groups involved in free-radical polymerization are vinyl group, an acetylene group, acrylic group and metakrila group.

Preferred examples of the polymerized not asimenos group, participating in polyprionidae polymerization, are cannamela group, Tolna group, asiagraph, epoxypropan, which is undergoing the open loop response of accession, oxetanone group, a group of cyclic ether, dioxooleana group, spiroergometry group, spiroergometry group, bicicleta-ester group and a cyclic group of aminoether.

In this invention the preferred organosilicon compound contains at least one silicon compound with at least a portion of the silicon linkages, represented, for example, General formula(2), (3), (4), (5).where in the formula, R1each independently may be one or more hydrocarbon group selected from the following: a linear or branched alkyl group(s)which has from 1 to 30 carbon atoms; cycloalkyl group(s), which has from 5 to 20 carbon atoms; CNS group(s)which has from 1 to 20 carbon atoms; aryl-substituted alkyl group(s)which has from 1 to 30 carbon atoms (the number of carbon atoms in the alkyl group substitution); halogen-substituted aryl group(s), which has from 6 to 20 carbon atoms; alkoxycarbonyl group(s), which has from 2 to 30 carbon atoms; monovalent group(s)containing to roxylenol group or a salt thereof; monovalent group(s)containing alphagroup or a salt thereof; and polyoxyalkylene group(s).

The above-mentioned organosilicon compound represented by the average gross formula (1)

RpQrXsSiO(4-p-r-s)/2,

where R is one or more hydrocarbon group selected from the following: a linear or branched alkyl group(s)which has from 1 to 30 carbon atoms; cycloalkyl group(s), which has from 5 to 20 carbon atoms; CNS group(s)which has from 1 to 20 carbon atoms; aryl-substituted alkyl group(s)which has from 1 to 30 carbon atoms (the number of carbon atoms in the alkyl group substitution); halogen-substituted aryl group(s), which has from 6 to 20 carbon atoms; alkoxycarbonyl group(s), which has from 2 to 30 carbon atoms; monovalent group(s)containing a carboxyl group or a salt thereof; monovalent group(s)containing alphagroup or a salt thereof; and polyoxyalkylene group(s);

Q and X may be the same or different and each of them is the same hydrocarbon group or more selected from the following: a hydrogen atom, a linear or branched alkyl group(s)which has from 1 to 30 carbon atoms; cycloalkyl group(s), which has from 5 to 20 carbon atoms; CNS group(s), to ora has from 1 to 20 carbon atoms; aryl-substituted alkyl group(s)which has from 1 to 30 carbon atoms (the number of carbon atoms in the alkyl group substitution); halogen-substituted aryl group(s), which has from 6 to 20 carbon atoms; alkoxycarbonyl group(s), which has from 2 to 30 carbon atoms; monovalent group(s)containing a carboxyl group or a salt thereof; monovalent group(s)containing alphagroup or a salt thereof; and polyoxyalkylene group(s);

p is a Prime number in the range from 0 to 4;

r is a Prime number in the range from 0 to 4;

s is a Prime number in the range from 0 to 4;

and is the sum of p+r+s is a Prime number lower than 4.

The molecular structure of the above-mentioned organosilicon compound is not specifically limited, but preferred compounds may be compounds with polyalkyleneglycol structure in the main chain, such as polydimethylsiloxane and polydimethylsiloxane. It can also be a compound having a polysiloxane structure as part of the molecule. Hereinafter, may be used in connection with a specific organic group introduced into the polysiloxane structure. Especially, there may be used a compound having an organic group introduced into the side chain polysiloxane, a compound having an organic group introduced into the anti-Christ. alonya the ends of the polysiloxane, the compound having an organic group introduced into one end of the polysiloxane, a compound having an organic group introduced into the side link and the ends of the polysiloxane, or similar connection. Specific examples of organic groups that can be introduced into the polysiloxane structure are amino group, a carboxyl group, a carbinol group, aryl group, alkyl group, alkoxycarbonyl group, CNS group, a linear or branched alkyl group, substituted by at least one aryl Deputy, and polyalkylene group. In this invention, preferred examples of the aryl group may be phenyl group, Tomilina group, xylella group, biphenylene group, naftalina group, antanella group, pelinalina group, phenanthroline group. Preferred linear or branched alkyl group, substituted aryl group, such as methylstyrene or stiralnaya. Further, there may be used an organic group in which a hydrogen atom in the aromatic carbon aryl group substituted by other functional groups. Can also be used a compound in which some or all of the associated hydrogen atoms substituted with fluorine atom, a chlorine atom or a bromine atom.

As the organosilicon compound(C) in this invention particularly preferred compounds, having at least one organic group selected from the following: phenyl group, methylstyrene group, sterelny group, alkoxycarbonyl group, CNS group and polyoxyalkylene group containing compound in which the hydrogen atom directly attached to the carbon atom that is attached organic group, i.e. the hydrogen atom is α-the position of a linear connection (hereinafter referred to as the hydrogen in α-position). These compounds are added to the resin as an additive. If photoslive and curing are performed with the use of these compounds, very few number of components extracted in the ink during the printing of the obtained cured material, and stability effects prevent delays ink on the plate surface and increased stability to reduced friction are extremely high. The phenomenon, when containing these compounds material obtained from the composition based on the photosensitive resin cured in the reaction of the photopolymerization, is immersed in the solvent, the weight change before and after the immersion a little, although the nature of this phenomenon has not been explained. This means that the number of components that have ink during printing, a little, and when printing is carried out continuously, the change in mehanicheskij properties and printing properties can be reduced, and this is extremely important in terms of practical value. The authors of the present invention assume that the reason for the appearance of this phenomenon is that compound with hydrogen in α-position promotes a certain reaction in photopolimerization process is captured in the cured material through a chemical reaction.

As the organosilicon compound (C) in this invention it is desirable to have the connection that does not become opaque or low, when mixed with a photosensitive resin. There is absorption, measured by the counter uptake as an index to determine the degree of opacity. The range of absorption is in the range from 0 to 70%, more preferably in the range from 0 to 50%, even more preferably in the range from 0 to 40%.

As the organosilicon compound (C) in this invention have been used in commercial products that are typically available, for example, various grades of silicone oil, replaced by organic groups produced by Shin-Etsu Chemical Co., Ltd., Wacker Asahikasei Silicone Co., Ltd., GE Toshiba Silicones Co., Ltd. and Dow Corning Toray Silicone Co., Ltd. Examples of compounds used may be, for example, methylstyryl-modified silicone oil (trademark "KF-410"), carbinol-modified silicone oil (tor the brand new "X-22-160AS"), ether-modified silicone oil (trademark "X-22-715"), alkyl-modified silicone oil (trademark "KF-412), produced by Shin-Etsu Chemical Co., Ltd.

The amount of added silicon compound (C) in this invention, preferably, should be in the range from 0.1 to 10%, more preferably in the range from 0.3 to 5%, even more preferably in the range from 0.5 to 3%, counting from the total number of compositions on the basis of a photosensitive resin. If the added amount is 0.1% or more, the adhesiveness of the surface of the product fototerapia composition based photosensitive resin and the stability of the surface to friction can be maintained at a low level and, further, inhibited the migration of ink during printing. If the added amount is 10% or less, the phenomenon of exclusion ink is not observed and can be obtained satisfactorily printed material. Characteristics of cut can be greatly improved, for example the wear of the cutting edges of the knife is exceptionally low, and the service life of the knife may be extended if the composition is based on the photosensitive resin is formed in a cylindrical form and then photoallergen, the surface has been processed to remove subtle irregularities to obtain a smooth surface. Further, if the added amount of extending t is 10% or less, the stereotype can be formed on the plate surface without reducing the engraving speed, when the engraving laser printing matrix is obtained as the product of fototerapia composition based photosensitive resin by laser engraving.

The average molecular weight of organosilicon compound (C) in this invention is in the range from 100 to 100,000, more preferably in the range from 300 to 10,000, more preferably in the range from 500 to 5000. If the average molecular weight is 100 or more, the degree of extraction in ink on the inside of the product fototerapia compositions on the basis of a photosensitive resin or the degree of extraction in the solvent during the washing of the form can be located at a low level. If the average molecular weight is 100,000 or less, the characteristics of mixing with other components forming composition based on the photosensitive resin are satisfactory. Especially preferably, the compound was liquid at 20°C.

Next will be described a method for measuring the average molecular weight (Mn) of organosilicon compounds (C). The organosilicon compound (C) was dissolved in the solvent and analyzed by gel-distribution chromatography (GPC method), average molecular weight (Mn) was calculated in relation to the standard floor is styrene, for which the molecular weight is known. To connect with a wide range of molecular weight, average molecular weight was measured by this method. As a measure for the distribution of molecular weight was used indicator of polydispersity (Mw/Mn), namely the ratio of the average molecular weight (Mn) weighted average molecular weight (Mw), measured at the same time. If the polydispersity is 1.1 or more, this means that the distribution of molecular weight is used, the average molecular weight, determined by GPC method. For connection, the polydispersity is less than 1.1, the molecular structure can be analyzed, since the distribution is extremely narrow, and as the average molecular weight is used, the molecular weight calculated by using the nuclear magnetic resonance or mass spectrometry.

The refractive index of silicone compound (C) in this invention should be in the range of from 1,400 to 1,590, more preferably in the range from 1,430 to 1,490, when measuring diffractometer Abbe at 25°C. If the refractive index is within this range, the organosilicon compound may be mixed with other components forming composition based on the photosensitive resin is ez education strong opacity, that guarantees the ability to potootvedeniya and, further, the mechanical properties vodootvedenija material. In the production method of the engraving laser printed matrix there is no need to form a clear stereotypes, in contrast to the shape of the photosensitive resin, on which a clear stereotypes are formed by way of photolithography using light and manifestations. Clear stereotypes are formed at the stage of laser engraving. It is usually assumed that in case of a photosensitive resin for the formation of a clear standard stereotypes composition having reduced scattering of light due to turbidity, is preferred. For laser engraving of the printing matrix only characteristic of curing at a fixed thickness is important, and even if the song is more or less noticeable turbidity that causes scattering of light, the matrix can be made by curing. Therefore, there is a very significant advantage in the freedom of choice of connections that can be applied when the engraving laser printing matrix is prepared using a composition based on the photosensitive resin as the starting material. In this invention, if the refractive index of organosilicon much different from indicators predominately components of the composition based on the photosensitive resin, different from the organosilicon compound (C), the printed matrix can become visibly turbid. Thus, the approximate difference between the refractive index of silicon compounds (C) and refractive index of the other components is preferably from ± 0.1 or less, more preferably ± 0.05 or less.

The organosilicon compound (C) in this invention preferably has in the molecule of the polymerized unsaturated group. However, for applications in which liquid ink is not coming to the surface, for example as applied to Tanasescu cloth or roller, which can be engraved by laser, compounds which are polymerized unsaturated group may be used, as those compounds that have a small amount of the polymerized unsaturated groups in the molecule, especially 2 or less, and whose average molecular weight is relatively high, especially 1,000 or more, rend alcohol or similar solvents, compression vodootvedenie does not create permanent problems.

In this invention, the curable resin contains an unsaturated group having an average molecular weight preferably in the range of from 1,000 to 200,000 and more and less. The preferred range of the average molecular weight is in the range of from 2,000 or more to 00000 and less even more preferred is the range from 5000 or more to 50,000 or less. If the average molecular weight of resin (a) is 1,000 or more, the original printing plate, which is made by polymerization of the resin, it retains its strength and the relief image derived from this original form, is durable and can ensure reuse, when applied as a printed form or similar. If the average molecular weight of resin (a) is 200,000 or less, a sheet or cylindrical twisted the original of the engraving laser printing form can be made, if prevented excessive increase in viscosity during the pressing of the composition based on the photosensitive resin. Mentioned here, the average molecular weight refers to a value measured by gel-distribution chromatography and calibrated against standard polystyrene whose molecular weight is known.

The term "polymerized unsaturated group in this invention is defined as the polymerized unsaturated group that is involved in a radical or polyprionidae the polymerization reaction, as described in the section on organosilicon compound (C). Particularly preferred resins containing an average of 0.7 or more polymerized unsaturated groups on m is lukulu. If the number of the polymerized unsaturated groups per molecule an average of 0.7 or more, the original printing plate excellent in mechanical properties, the relief image is resistant to compression by laser engraving. Further, the service life is satisfactory, reuse, which is desirable, guaranteed. When discussing the mechanical strength of the original printed form, the number of the polymerized unsaturated groups should be more than 0.7, and more preferably more than 1 such group in the molecule of the resin (a). The present invention in the resin (a) is the preferred position of the polymerized unsaturated group is a position in which the polymerized unsaturated group directly attached to the end of the main segment of the polymer, or by the end of the lateral segment of the polymer, or is located in the main segment of the polymer or in a side chain. The average number of the polymerized unsaturated groups per one molecule of the resin (a)may be determined through analysis of the molecular weight by the method of nuclear magnetic resonance (NMR method).

As a way to obtain a resin (a) polymerized unsaturated group can be introduced, for example, right at the end of the molecule. A suitable method may be a method in which a compound having multiple reactive groups, such to the to the hydroxyl group, amino group, epoxypropyl, carboxyl group, anhydrite group, ketone group, a hydrazine group, an isocyanate group, isothiocyanate groups, cyclic carbonates, alkoxycarbonyl groups and having a molecular weight of several thousand, is introduced into reaction with a linking agent with many groups, the ability to communicate with reactive groups of the resin (for example, polyisocyanate, if the reactive group is a hydroxyl group or amino group). The conversion of the linking group in the end is reached with regard to molecular weight, and a group that reacts with a linking group, at the end leads to reactions of organic substances with the polymerized unsaturated group, which eventually joins the polymerized unsaturated group in the molecule end.

The applied resin (a) preferably is a resin which is easily oijala, or resin, which is easily decomposed. For resin, which is easily decomposed, it is preferable to have as Monomeric segment, which is easily decomposed, styrene, α-methylsterol, α-mitoxantron, acrylic esters, methacrylic esters, esters, ethers, nitro compounds, carbonates, carboline connection hemiacetal, oxyethylene compounds, aliphatic cyclic compounds and the like, which before occhialino contained in the molecular chain as leggerissimo unit link. In particular, typical examples of resins that are easily decomposed, are polyesters, such as polyethylene glycol, polypropyleneglycol, polytetramethylene, aliphatic polycarbonates, aliphatic carbamates, poly (methyl methacrylate), polystyrene, nitrocellulose, polyoxyethylene, polynorbornene, hydrogenated polycyclohexylene, or polymers having dendrimer molecular structure with a large number of branches. From the point of view of decomposing the preferred polymers with a large number of oxygen atoms in the molecular chain. Among them, compounds having a carbonate group, a urethane group and methacryloyl group, easily decomposed when heated and preferred. For example, polymers having satisfactory thermal degradation may constitute polyesters and polyurethanes synthesized from polycarbonatediol and polycarbonatediol acids as starting materials, and polyamides synthesized from polycarbonatediol as the original. These polymers may contain polymerized unsaturated group in the main chain or side chain. In particular, if the reactive functional groups such as hydroxyl group, amino group, carboxyl group, are in the end, it is easy to enter the polymerized unsaturated group at the end of main is th segment.

Examples of the resin (a) may be a compound having the polymerized unsaturated group in the main segment or in the lateral segment of the molecule polydienes, such as polybutadiene or polyisoprene. Examples of the resin (a) can also be polymeric compounds in which the polymerized unsaturated group has been introduced by chemical reactions, such as substitution, elimination, condensation or accession, using as the initial polymer compounds without the polymerized unsaturated groups. Examples of polymer compounds without the polymerized unsaturated groups may be polymers of C-C link, such as polyethylene, polypropylene, polyalkalene, such as polyvinyl chloride and grades, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyvinyl acetate, polyvinylacetate, polyacrylic acid, poly(meth)acrylates, poly(meth)acrylamide, and polyvinyl esters, as well as polyesters, such as polyfamily ether, polythioether, such as polyethylene terephthalate, polycarbonate, Polyacetal, polyurethane, polyamide, polyurea, polyimide and polydiorganosiloxane, or polymers, containing a heteroatom in the main chain of these polymer compounds, or aperiodic or block copolymers, synthesized from various types of Monomeric compounds. Further, the manifold is of IPA polymer compounds, having polymerized unsaturated group in the molecule, can be mixed and applied.

In particular, if a flexible relief image you want to use as a flexographic printing form, it is desirable to apply a liquid resin with a glass transition temperature of 20°s or less and more preferably to apply a liquid resin with a glass transition temperature 0°or less. As such liquid resins may be used, for example, compounds synthesized from hydrocarbons, such as polyethylene, polybutadiene, hydrogenated polybutadiene, polyisoprene and hydrogenated polyisoprene, polyethers such as polyethylene glycol, polypropyleneglycol and polytetramethylene, silicones, such as polycarbonates and polydimethylsiloxane, polymers of (meth)acrylic acid and/or its derivatives, and mixtures and copolymers of them with the polymerized unsaturated group in the molecule. The content of the liquid resin is preferably 30% or more of total resin (a). In respect of the atmospheric stability particularly preferred unsaturated polyurethanes, polycarbonate having a fragment.

The term "liquid resin"mentioned herein refers to a polymer having properties easy fluidity and deformability, while maintaining the ability to cure in deformed during cooling and under ELAST is ru, having the property immediately to deform in response to applied external force and return to its original state within a short time, when the external force is removed.

When the resin (a) is a liquid resin at 20°C, composition based photosensitive resin is liquid at 20°C. When the original form for the formation of three-dimensional images obtained from this composition is molded into a sheet or cylindrical shape, can be obtained a satisfactory accuracy in thickness and accuracy in dimensions. The viscosity of the composition is based on the photosensitive resin in this invention at 20°C is from 10 PA*s to 10 kPa*s, more preferably from 50 PA*s to 5 kPa ° C. If the viscosity of the composition is based on the photosensitive resin is 10 PA*s or more, produced by printing the matrix has sufficient mechanical strength, easily retains its shape, even when molded into a cylindrical printing matrix, and is easily recycled. If the viscosity is 10 kPa*s or less, a printing matrix is easily deformed even at normal temperature, is easily formed into a sheet or cylinder of the printing matrix, easily processed, and the way is easy. In particular, to obtain a cylindrical printing matrix having high precision in the thickness of the form, the viscosity to the notizie-based photosensitive resin, preferably, should be 100 PA*s or more, preferably 200 PA*s or more, more preferably 500 PA*s or more, in which there is the phenomenon of scapania composition based photosensitive resin under the action of gravity during formation on cylindrical base.

The organic compound (b) of the present invention is a compound having the polymerized unsaturated group with an average molecular weight less than 1000. The average molecular weight should preferably be less than 1000 for ease of dilution of the resin (a). The polymerized unsaturated group is defined as the polymerized unsaturated group involved in radical or polyprionidae polymerization, as described in the sections devoted to the organosilicon compound (C) and the resin (a).

Specific examples of the organic compounds (b) are olefins such as ethylene, propylene, styrene, divinylbenzene, acetylene, (meth)acrylic acid and its derivatives, halogenlampen, unsaturated NITRILES such as Acrylonitrile, aromatic compounds such as phenols and arylisocyanate, unsaturated dicarboxylic acids such as maleic anhydride, maleic acid, fumaric acid and derivatives, vinylacetate, N-vinylpyrrolidone and N-vinyl - carbazole. (Meth)acrylic acid and its derivatives I which are preferred examples in the sense of the relative content in the sample, rates and decomposing under the action of laser light and the like. Derivatives are alicyclic compounds having cycloalkyl group, bicycloalkyl group, cycloalkenyl group and the like, aromatic compounds having a benzyl group, phenyl group, fenoxaprop, fluorenyl group and the like, and compounds having alkyl group, halogenated alkyl group, alkoxyalkyl group, hydroxyalkyl group, aminoalkyl group, glycidyloxy group and the like, and esters with polyvalent alcohols, such as alkylene glycol, polyoxyethyleneglycol and trimethylolpropane.

Compounds having apachegroup and entering polyprionidae polymerization, an organic compound (b)may include compounds obtained by the reaction of epichlorohydrin with various kinds of alcohols, such as diols or trioli, or epoxysilane, obtained by the action of percolat on the ethylene linkage in the molecule. Specific examples of these compounds are epoxysilane, such as diglycidyl ether of ethylene glycol, diglycidyl ether of diethylene glycol, deglazed ether of triethylene glycol, deglazed broadcast tetraethyleneglycol, deglazed ether of polyethylene glycol, deglazed ether of propylene glycol, deglazed broadcast tripropyleneglycol, deglazed the FYR of polypropylenglycol, deglazed ether of neopentyl glycol, deglazed ether of 1,6-hexandiol, deglazed ether of glycerol, triglyce ether of glycerol, triglyce ether of trimethylolpropane, deglazed ether of bisphenol a, deglazed ether of hydrogenated bisphenol a, diglycidyl esters of adducts of ethylene oxide or propylene oxide to bisphenol a, diglycidyl ether polytetramethylene, diglycidyl ether poly(dipteropeltis), diglycidyl ether poly(adaptatively), diglycidyl ether poly(caprolactone)diol.

In this invention one or more of the organic compounds (b)having these polymerized unsaturated group may be selected according to the aforementioned purposes. For example, if the connection is applied to the printing form, at least one denosine aliphatic, alicyclic or aromatic derivative must be enabled to suppress swelling under the action of an organic solvent, such as alcohol or ester, which is the solvent in the ink for printing.

To improve the mechanical strength of the printing plate obtained from compositions based on resins in this invention, at least one alicyclic or aromatic compound, preferably, should be included as an organic compound (b). In this case, the content of the derived composition is yet preferably 20% or more, more preferably 50% or more by weight of the total amount of organic compounds (b). The above-described aromatic derivative may be an aromatic compound having elements such as nitrogen and sulphur.

To improve the deformation elasticity printed form methacrylyl monomer can be used, as described in JP-A-7-239548, or the selection may be carried out using the technical information on the well-known photosensitive resins for printing etc.

In the application, which requires the stability to solvents, resin (a) and/or the organic compound (b) in this invention are preferably compounds having in the molecular chain of the at least one bond selected from the following: carbonate bond, a tie simple ether linkage of ester, and/or having at least one molecular fragment consisting of aliphatic saturated hydrocarbon chains or unsaturated aliphatic hydrocarbon chains having a urethane bond. Among them, compounds having a carbonate communication, or compounds having aliphatic hydrocarbon chains, show a particularly high resistance to ether solvents, which are often used as an ink solvent.

Composition based photosensitive resin in this invented and polymerizability the action of light or electron beam to achieve the product's properties as a printing plate or the like, and at this time can be added polymerization initiators. The polymerization initiator may be selected from those that are commonly used, for example, radical polymerization, cationic polymerization or anionic polymerization, as described in "Polymer Data Handbook - Basic Part", edited by The Society of Polymer Science, Japan (published by Baifukan Co., Ltd., 1986). The binding compositions based on resins by photopolymerization using a photopolymerization initiator of the is a useful method that allows to produce the original printing plates with good performance, while maintaining the properties of the stability during storage of the composition-based resin in the present invention, and well-known initiators can be used in this capacity. As an initiator of photopolymerization initiating the radical polymerization reaction, especially widely used, the initiator of photopolymerization, exciting the hydrogen atom (d), degradable initiator of photopolymerization (e) as a particularly effective initiators for the photopolymerization.

Aromatic ketones are preferably used as the photopolymerization initiators, exciting the hydrogen atom (d), although this is not a special restriction. Aromatic ketone is easily transformed into an excited triplet state by optical excitation, and for this excited state is the mechanism of chemical reactions, in which hydrogen is extracted from the environment with simultaneous generation of radicals. It is possible to assume that the generated radicals are involved in the reaction of the photopolymerization. The initiator of photopolymerization, exciting the hydrogen atom (d) in this invention can be any compound that is capable of removing the hydrogen atom with the formation of radicals through an excited triplet state. Aromatic ketones can be benzophenone, michler ketone, xanthene, tioksantena and anthrachinone, and preferably using at least one of these compounds. Specific examples of benzophenone and derivatives thereof include benzophenone-3,3', 4,4'-tetracarbonyl acid and 3,3', 4,4'-tetramethoxybenzene. The designation "michler ketone is applied to the michler ketone and its derivatives. The designation "xanthene" applies to the Xanten and its derivatives, substituted alkyl group, phenyl group and halogen-substituted group. The designation "thioxanthone" applies to thioxanthone and its derivatives, substituted alkyl group, phenyl group and halogen-substituted group, which may include ethylthioxanthone, methylthionine, chlorothioxanthone. The designation "xanthene" applies to the Xanten and its derivatives, substituted alkyl group, fenil the Oh group and halogen-substituted group and the like. Added the number of the initiator of photopolymerization, exciting the hydrogen atom (d), is preferably in the range of 0.1-10 wt.%, more preferably in the range of 0.5-5 wt.% from the total amount of the composition based on the photosensitive resin. If the added amount is in this range, the ability to restore the surface of the cured material can be ensured sufficiently, and also can be guaranteed weather resistance when the composition is based on the photosensitive resin fotofacials in the air.

Degradable initiator of photopolymerization (e) refers to compounds in which after absorption of light occurs splitting reaction in the molecule and generates free radicals, and has no special restrictions. Specific examples of the initiator are alkyl ethers of benzoin, 2,2-dialkoxy-2-phenylacetophenone, acetophenone, acylated esters Asimov, azo compounds, organic sulfur compounds and diketones, and preferably using at least one of these compounds. Alkyl ether of benzoin may be isopropyl benzoin ether, isobutylene ether of benzoin, compounds described in "Photosensitive Polymers" (Kodansha Co., Ltd., 1977, p.228). 2,2-Dialkoxy-2-phenylacetophenone can be 2,2-dimethoxy-2-phenylacetophenone,2,2-diethoxy-2-phenylacetophenone. Acetophenone can be acetophenone, trichloroethene, 1-hydroxycyclohexanone, 2,2-diethoxyacetophenone. Acylated ester Asimov may be 1-phenyl-1,2-propandiol-2-(o-benzoyl)oxime. Organic sulfur compounds can be aromatic thiols, mono - and disulfides, thiuram sulfide, dithiocarbamate, S-acyl, dithiocarbamate, thiosulfonate, sulfoxidov, sulfinate and dithiocarbamate. The diketones can be methyl and benzyl-benzoylformate. Added the amount of degradable initiator of photopolymerization (e) is preferably in the range of 0.1-10 wt.%, more preferably 0.3-3 wt.% from the total amount of the composition based on the photosensitive resin. If the added amount is in this range, the ability to restore the surface of the cured material can be ensured sufficiently, and also can be guaranteed weather resistance when the composition is based on the photosensitive resin fotofacials in the air.

The compound having in the same molecule as an initiator of photopolymerization, exciting the hydrogen atom as a functional substituent, and degradable initiator of photopolymerization as a functional substituent, can also be used as initiator fotop is liberizatsii. An example of such a connection can be α-aminoacetophenone. Such compounds can be, for example, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-he and compounds expressed by the General formula (6):

[Formula 5]

(In the formula, R2each, independently can be a hydrogen atom or alkyl group having from 1 to 10 carbon atoms, and X is alkalinous group having from 1 to 10 carbon atoms.)

The added amount of the compounds having in the same molecule as an initiator of photopolymerization, exciting the hydrogen atom as a functional substituent, and degradable initiator of photopolymerization as a functional substituent, is preferably in the range of 0.1-10 wt.%, more preferably 0.3-3 wt.% from the total amount of the composition based on the photosensitive resin. If the added amount is in this range, the mechanical properties of the cured material can be ensured sufficiently, and also can be guaranteed, even if the composition is based on the photosensitive resin fotofacials in the air.

Can also be applied to the initiator of photopolymerization, generating acid and initiating the reaction polyprionidae polymerization n is on the action of light. Examples of such polyprionidae initiator can be the initiators fotonation polymerization, such as aromatic diazonium salts, aromatic itaniemi salts, aromatic sulfonate salt, as well as the photopolymerization initiators, absorbing light and generating base. Added the number of the initiator of photopolymerization is preferably in the range of 0.1-10 wt.% from the total amount of the composition based on the photosensitive resin.

The compositions based photosensitive resin in this invention, it is preferable to add inorganic porous material (f). Inorganic porous material (f) is the inorganic particles having very small pores or very small air bubbles in the particles, is added to remove the sticky debris generated in large quantities during laser engraving and also prevents the stickiness of the plate surface. Inorganic porous material (f) in this invention is added mainly for the removal of liquid sticky debris, and its efficiency is strongly dependent on the average particle size, specific areas on the surface, the average pore size, pore volume and value loss on ignition.

Inorganic porous material (f) in this invention preferably have the t average particle size of from 0.1 to 100 μm. If you use inorganic porous material having a smaller particle size, powder dust flies and pollutes the apparatus for engraving, when the original form is obtained from compositions based on resins of the present invention, laser engraved and in addition may have problems, such as increased viscosity, the delay of bubbles and the formation of powdery dust in the process of mixing the inorganic porous material with the resin (a) and organic compound (b).

If you use inorganic porous material having a larger average particle size, there is a tendency to defects in the relief image during the laser engraving and clarity of printed materials falls. The preferred range for the average particle size is in the range from 0.5 to 20 μm, most preferred range from 3 to 10 μm. The average particle size of the inorganic porous material in the present invention is a value measured with a laser device to measure the dispersion of particle diameters.

The size of the specific surface area of the inorganic porous material (f) in this invention is in the range from 10 to 1500 m2/g, more preferably in the range from 100 to 800 m2/, If the size of the specific surface area is 10 m2/g or more, the disposal of liquid oblo the Cove during laser engraving proceeds satisfactorily, if the size of the specific surface area is 1500 m2/g or less, the increase in viscosity and thixotropy of the composition based on the photosensitive resin can be prevented. The size of the surface area in this invention was determined based on the equation BETH for the adsorption isotherms of nitrogen at -196°C.

The average diameter of pores of the inorganic porous material (f) in this invention is highly dependent on the adsorption of liquid debris generated at the stage of laser engraving. The average diameter of pores is in the range from 1 to 1000 nm, more preferably in the range from 2 to 200 nm, even more preferably in the range from 2 to 50 nm. If the average pore diameter is 1 nm or more, can be guaranteed adsorption of liquid debris generated at the stage of laser engraving, and if the average pore diameter of 1000 nm or less, the size of the surface area of the particles is so large that the adsorption of liquid debris may also be insufcient. The reason why the adsorption of liquid debris is low when the average pore diameter of less than 1 nm, it is not quite clear, but it can be assumed that the liquid debris sticky and are not included in the micropores, so adsorption is low.

In this invention, the average pore diameter is a value measured by adsorption of nitrogen. On the s, having an average pore diameter of from 2 to 50 nm are called mesopores, and porous particles having mesopores have an extremely high ability to adsorbirovanny liquid debris. The distribution of the pore diameter of the present invention measured from the adsorption isotherms of nitrogen at -196°C.

The pore volume of the inorganic porous material (f) in this invention is in the range from 0.1 to 10 ml/g, more preferably in the range from 0.2 to 5 ml/year If the pore volume of more than 0.1 ml/g, the adsorption of liquid debris is sufficient, and if the pore volume of 10 ml/g or less, the mechanical strength of the particles can be guaranteed. In this invention, the method of adsorption isotherms of nitrogen was used to measure pore volume. Pore volume in this invention was determined from the adsorption isotherms of nitrogen at -196°C.

In this invention, the adsorption of the oil was used as an index to study the adsorption of liquid debris. Adsorption of the oil was determined by the amount of oil adsorbed on 100 g of the inorganic porous material. The preferred range for the adsorption of oils for use in this invention is from 10 to 2000 ml/100 g, more preferably in the range from 50 to 1000 ml/100 g If the adsorption of oil is 10 ml/100 g or more, the disposal of liquid debris generated at the stage of La the agreement engraving, is sufficient, and if the adsorption of the oil is 2000 ml/100 g or less, can be guaranteed mechanical strength of the inorganic porous material. Measurement of the adsorption of oil was carried out in accordance with JIS-K5101.

Inorganic porous material (f) in this invention is generally retains porosity without deforming or melting when applying laser light near infrared range. Weight loss, when the inorganic porous material (f) is kept at 950°C for 2 hours, is 15% or less, more preferably 10% or less.

The particle shape of the inorganic porous material in the present invention is not specifically limited, and can be used spherical particles, of flat particles, acicular particles, amorphous particles, particles having protrusions on the surface, or the like. Spherical particles are particularly desirable in the sense abrasive resistance. Hollow particles, spherical granules having a uniform pore size, such a silicon sponge, and the like, can also be used. Examples of the inorganic porous material may be a porous silica gel, mesohorny silica gel, porous Zirconia, silica gel, porous alumina and porous glass. For materials having air gaps from a few nm to 100 nm, t is such as layered clay, the diameter of pores cannot be determined and, consequently, the distance between the air gaps between the layers is defined as the diameter of pores.

Further, the colored organic material such as a pigment and a light absorbing dye having a wavelength of laser light may be captured in such pores or gaps of air.

The sphericity is defined as the index for characterizing spherical particles. In this invention, the sphericity is defined as the ratio (D1/D2) of dimension D1range comprising a maximum projection of the particle size D2range comprising a minimum projection of the particle. The sphericity equal to 1.0 for the sphere. The sphericity of the spherical particles used in this invention is in the range from 0.5 to 1.0, more preferably in the range of 0.7 to 1.0. If the sphericity of the particles is 0.5 or more, the abrasion resistance of the particles is satisfactory. The sphericity of 1.0 is the upper limit of sphericity. For use as spherical particles, it is desirable that more than 70% of particles or better 90% of the particles had a sphericity of 0.5 or more. As a method for measuring the sphericity can be used a method in which the sphericity is measured on the photographs obtained by scanning electron microscope. At the present time the photo is taken from this led is rising, when a monitor is visible at least 100 particles. The above D1and D2can be measured directly on the pictures, but more preferably be treated with a device type of scanner for digitizing pictures and then process the data using software for image analysis.

The surface of the inorganic porous material may be coated with organic silicon sizing, technologicheski the sizing or other organic compound to provide surface treatment, resulting in a more hydrophilic or more hydrophobic particles.

In this invention one or more inorganic porous material (f) can be selected, and by adding inorganic porous material (f) is effectively achieved improvements such as prevention of liquid debris during laser engraving and prevent buildup of three-dimensional printed form.

In the composition based on the photosensitive resin of the present invention, the organic compound (b) is in the range from 5 to 200 parts by weight, more preferably in the range from 20 to 100 parts by weight, counting from 100 parts by weight of the resin (a). The content of the inorganic porous material is in the range from 1 to 100 parts by weight, more preferably in the range from 2 to 50 frequent the nd by weight, even more preferably from 2 to 20 parts by weight.

If the organic compound (b) is below the above range, there are difficulties in balancing hardness, elongation and pulling forces obtained printing plates or the like, and if the content of organic compounds (b) of the above-mentioned range, the shrinkage during polymerization and curing so great that disturbed the accuracy in thickness.

If the content of inorganic porous material (f) the below mentioned range, there may be cases where, depending on the type of resin (a) and organic compounds (b), when the laser engraving formation of liquid debris is not prevented sufficiently, and if the content of inorganic porous material (f) of the above-mentioned range, the printing form has a tendency to become brittle. In addition, transparency can be broken, and the stiffness will be too high, especially when the printing form is used as a flexographic printing form. When the composition is based on the photosensitive resin is cured by light, especially ultra-violet light for the manufacture of the engraving laser printing matrix, the transmittance of light affect the curing reaction. Thus, it is preferable to use a porous material, there is a corresponding index of refraction, close to the refractive index of the composition based on the photosensitive resin.

The method for mixing the inorganic porous material and a composition based on the photosensitive resin may be either a method in which a thermoplastic resin is heated to melting and inorganic porous material (f) is added directly to the resin, or a method in which thermoplastic resin and the polymerized organic compound (b) are mixed first, and then to the mixture is added an inorganic porous material (f).

In addition to compositions based on resins in this invention may be added as the polymerization inhibitor, an ultraviolet light absorber, a dye, pigment, lubricant, surfactant, plasticizer, perfume and similar substances according to the purpose and application.

The engraving laser printing matrix in this invention is prepared by photopolymerization and curing the composition on the basis of a photosensitive resin containing organosilicon compound (C). Thus, terhmernosti patterns obtained by the reaction between the polymerized unsaturated groups of organic compounds (b) or by the reaction of the polymerized unsaturated group of the resin (a) and organic compounds (b), and composition based photosensitive resin becomes nerastvorim the Oh in the ether, ketannah, aromatic, alcohol, and halogenated solvents that are typically used. In the reaction between the organic compounds (b), between the resins (a) or between the resin (a) and organic compound (b) polymerized unsaturated group disappears. When the photosensitive material crosslinks and cures with the use of an initiator of photopolymerization, a photopolymerization initiator of the decomposed under the action of light and, thus, unreacted initiator of photopolymerization and the decomposition product can be identified through solvent extraction, crosslinked and polymerized material and further analysis GC-MS method (method gas chromatography with subsequent mass spectrometric analysis), LC-MS-method (method of liquid chromatography and subsequent mass spectrometric analysis), GPC-MS method (method gel-distribution chromatography with subsequent mass spectrometric analysis) or LC-NMR method (method of liquid chromatography with subsequent analysis by spectroscopy nuclear magnetic resonance). Further, by using GPC-MS method, LC-MS-method, GPC-NMR method unreacted polymer, unreacted organic compound (b) and a relatively low molecular weight product obtained from the reaction of the polymerized unsaturated group in EXT Egorovna solvent material, can be identified in this solvent extracted material. For insoluble in the solvent component with high molecular weight, forming triggernometry structure, if there is a fragment formed by the reaction of the polymerized unsaturated groups as component substances with high molecular weight, can be installed by pyrolysis GC-MS-method.

For example, the presence of the fragment formed from the polymerized unsaturated group such as a methacrylate group, an acrylate group or vinyl group, can be established from the analysis of the peaks of the mass spectrum. Pyrolysis-GC-MS method is a method in which the sample is decomposed by heating, the components of the product gas is separated by gas chromatography and then removed the mass spectrum. If the product obtained from the reaction of the photopolymerization or unreacted initiator of photopolymerization to be detected simultaneously with unreacted curable unsaturated group or a fragment derived from a polymerized unsaturated groups in the crosslinked and cured material, it can be concluded that this material was obtained by fotoschule and curing the composition on the basis of a photosensitive resin.

Identification of the organosilicon compound (C)present in the composition is based photosensitive resin or potassium and cured material, can be made using different analytical methods described above.

The amount of finely dispersed inclusions inorganic porous material present in the crosslinked and cured material can be determined by tigania on the air, all organic components and weighting the residue. The presence of finely dispersed inclusions inorganic porous material in the above balance can be inferred from observations of the morphology of the electron emission scanning high-resolution microscope, the distribution of particle diameter can be measured with a laser device for scanning the distribution of particle diameter and pore volume, pore diameter and specific surface area installed by adsorption of nitrogen.

The engraving laser printing matrix in this invention contains the organosilicon compound in the printed matrix and/or in the surface of the printed matrix. Contained organosilicon compound can be identified by the method of solid-state nuclear magnetic resonance (solid-state29Si-NMR), in which there is a core of silicon, having an atomic weight 29. In this method, the organosilicon compound and the inorganic compound of silicon can be separated on the observed chemical shifts of the nuclei to Omnia. Next, what is the functional group attached to the silicon atom, can also be set from the chemical shift. The organosilicon compound in this invention is a compound having a peak at -90 ppm or higher (low field region) in solid state29Si-NMR spectrum. Inorganic silicon compound of the present invention has a signal located in the high field region from -90 ppm in the solid-state29Si-NMR spectrum. In the case of the system in which the organosilicon compound and an inorganic silicon compound contains at the same time, the relative ratio of silicon originating from organosilicon compounds, and silicon originating from the inorganic silicon compound, can be determined from the integral value of peaks observed.

The relative content of silicon atoms derived from organosilicon compounds in the engraving laser printing matrix in this invention is preferably from 0.01 to 10%. If the relative content is within these limits, the removal of sticky debris generated when a surface treatment such as cutting, grinding and polishing is easy and effectively achieved preventing ink stains, improved abrasion resistance and prevent buildup of nepobedimosti printed matrix.

The relative content of silicon atoms derived from organosilicon compounds can be quantitatively determined using plasma-ionization spectrometry silicon atoms or the above-described29Si-NMR method. In the case of the system in which the organosilicon compound and an inorganic silicon compound contains at the same time, the silicon content can be installed plasma-ionization spectrometry. However, in this method, silicon, originating from organosilicon compounds, and silicon originating from the inorganic silicon compound, can not be separated, and the use of the above-described29Si-NMR method, the silicon originating from organosilicon compounds can be separated and quantified. Thus, the relative content of silicon atoms derived from organosilicon compounds in this invention is defined as Wsix(Iorg/(Iorg+Iino)), where the ratio of the weights of the silicon atoms to the total weight of the sample is determined from the plasma ionization spectrometry as Wsiobtained from the solid-state method29Si-NMR value of the integral of the peak originating from organosilicon compounds, designated as the Iorgand the value of the integral of the peak originating from neorganicheskoi the silicon compound, designated as the Iino. Here the unit of measurement for Wsiare weight %. Plasma ionization spectrometry of the present invention is a method useful for the quantitative determination of extremely low concentrations. A model for the definition can be either a thin layer having a cross-section obtained by cutting deep into utverzhdenii photosensitive resin, or a sample obtained by cutting a region near the surface layer.

Another method that can determine the organosilicon compound in the engraving laser printed matrix may be pyrolytic GC-MS method. In particular, if contained silicon compound is a silicon compound, a cyclic silicon compound is formed when the cured photosensitive resin contained in the engraving laser printed matrix decomposes when heated, then a cyclic silicon compound can be separated and identified using GC-MS-method.

As the method for molding compositions based on resins in sheet or cylinder in this invention can be used in existing methods of molding resins. Examples of the method may be a method of casting, the method in which the resin is forced through the nozzle, or pumped with such a machine as a pump or Trouser in which dalimania, or plumits roller and then with a knife to achieve consistency in thickness. In this case, it is also possible to perform molding by heating the resin without breaking links that violate the characteristics of the resin. The resin also may be subjected to milling, grinding, and similar operations as needed. Typically, the composition-based resin is formed on the base, called pripravenem sheet, but there may be cases when the resin is molded directly on the printing cylinder. Can be used cylindrical base made of a fiber (FRP), plastic or metal. Having a fixed thickness of the cylindrical base may be hollow to reduce weight. The role of the black film on the cylindrical basis is to ensure stability of the printed matrix in size. As the material for this could be elected as the material having high stability in size. When a study was conducted using the coefficient of linear expansion, it was found that the upper limit is 100 ppm/°C, more preferably 70 ppm/°C. Specific examples of the material may be polyester resin, polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, polybismaleimide resin, polysulfone resin, polycarbonate resin, polyphenylenether resin, polyphenyl tiefere resin, polyethersulfone resin, liquid crystal resin, composed entirely of aromatic polyester resins, and epoxy resins. Further, these resins may be used in multiple layers. For example, can be used canvas in which layers of polyethylene terephthalate having a thickness of 50 μm, connected across one with a fully aromatic polyamide film having a thickness of 4.5 μm, or the like. As pripravenou sheet may be used porous cloth, for example, cross stitched woven fiber and a nonwoven or film with pores.

If the porous cloth is used as pripraveny sheet, cured photosensitive resin and pripraveny sheet together with the formation of a strong adhesion by impregnation of the pores of the composition based photosensitive resin and the subsequent vodootvedenie. Fiber, forming a tangle or non-woven material can be an inorganic fiber such as glass fiber, alumina, carbon fiber, alumina fiber, boron fiber, silica fiber high quality potassium-titanate fibers, sapphire fibers, natural fibers such as cotton, hemp, synthetic fibers, such as viscose fiber, acetate fiber, and synthetic fibers such as nylon, polyester, acrylic, vinylon, p is liviniere, polyolefin, polyurethane, polyimide and aramid. Cellulose produced by bacteria, is highly crystalline nanowalker, this material allows you to fine non-woven material with high stability in size.

Methods for reducing the coefficient of linear expansion pripravenou sheet may be methods in which the added metal circle, or a method in which resin is impregnated or covered with mesh fabric, such as wholly aromatic polyamide or the like, fiberglass or similar. For the method of the metal circle can be applied to commonly used organic particulate matter, inorganic particulate matter, such as metal oxides and metals, organic-inorganic composite particulate matter and the like. Porous particulate matter, hollow particulate matter, microcapsule particles and layered complex particles incorporating a low-molecular compound can also be used. Particularly useful particulate matter oxides of metals such as aluminum, silicon, and titanium oxide and zeolite, rubber particulate matter from polystyrene-polybutadiene copolymer, organic particulate matter natural products, such as vyskocil licenca cellulose and the like.

Adhesion with a layer of the composition on the basis of a photosensitive resin or adhesive layer can be improved in this invention the physical or chemical surface treatment pripravenou sheet or cylindrical base. Methods of physical treatment can include methods of sandy streams, the method of vapor blast with injection fluid containing particulate matter, a method of corona treatment, a method of plasma processing, the method of irradiation with ultraviolet or vacuum ultraviolet rays. Methods of chemical treatment can include a method of processing a strong acid/strong alkali, a method of processing an oxidant, the method of processing a crosslinking agent.

Layer molded composition based photosensitive resin crosslinks under the action of light, forming a printed matrix. A layer of a composition based on the photosensitive resin may also be crosslinked by light during molding. Light sources used for curing may be a mercury lamp, high pressure mercury lamp, ultrahigh pressure, ultraviolet fluorescent lamp, a germicidal lamp, carbon arc, a xenon lamp and metal halogen lamp. Light is applied to a layer of a composition based on the photosensitive resin should preferably have wavelengths from 200 to 300 nm. In which W is STI, the initiator of photopolymerization, exciting a hydrogen atom, often has a strong optical absorption in this wavelength range, and thus, if you are using light having a wavelength of from 200 to 300 nm, the surface hardness of the cured layer of the composition on the basis of a photosensitive resin can be ensured sufficiently. One light source can be used for curing, however, because the strength of the resin in some cases improved by the use of two or more types of light sources with different wavelengths, can be used two or more types of light sources.

The thickness of the printed matrix for use in laser engraving can be arbitrarily set in accordance with the purposes of the application, but is preferably from 0.1 to 7 mm, when a printing matrix is used as a printing form. In some cases, many materials having different compositions may form a multilayer material. For example, on the outer surface can be formed in a layer that is suitable for engraving with a laser having the oscillation wavelength in the near-infrared range, such as a YAG laser, a fiber-optic laser or semiconductor laser, and below this layer, suitable for engraving an infrared laser, such as laser based on dioxide gas from the of Lerida or laser visible/UV range. By the formation of such a multilayer structure of relatively large elements of the stereotype can be engraved by laser on the basis of carbon dioxide gas with extremely high and extremely thin elements of the stereotype can be engraved near the surface of the near infrared laser such as a YAG laser, a fiber-optic laser or semiconductor laser. As it is extremely thin elements of the stereotype can be engraved on a relatively small depth, the thickness of the layer that is sensitive to near infrared laser, is preferably in the range from 0.01 to 0.5 mm. Thus, by laminating a layer that is sensitive to near infrared laser, and a layer sensitive to laser infrared range, the depth of the elements of the stereotype of the engraving laser near infrared range, can be precisely controlled. This is possible due to the phenomenon of the difficulty of engraving laser near infrared range of the layer sensitive to infrared lasers. The difference in the accuracy of the elements of the stereotype, suitable for laser engraving, stems from differences in the vibrational wavelength-specific laser devices, namely differences in the diameter of the beam of laser light, which can the be reduced. When laser engraving is carried out by this method, the etching may be performed by various laser apparatus having a laser infrared and near infrared laser, respectively, or engraving can be performed by an apparatus having a laser, infrared, and near infrared laser.

The wetting ability of the surface of the engraving laser printing matrix in this invention is an extremely important factor for receiving and carrying the ink. When the study of surface tension conducted at 25°C, 20 μl of the indicator fluid with a surface energy of 30 mn/m, quantitatively selected by the introduction of a certain type, bury on the surface of the engraving laser printing matrix and within 30 seconds was measured, the maximum size of the area, on which was spread a drop, the drop's diameter ranged from 4 to 20 mm in diameter, more preferably from 5 to 15 mm. Indicator liquid often spreads spherically, but not always spherical, and depending on the shape of the surface of the printed matrix. In the latter case, the diameter of the minimum circle, fully describing the zone of distribution, is defined as the maximum diameter of the sphere, on which was spread a drop. If the maximum diameter of the sphere is, to spread the drop is in the range from 4 to 20 mm, there is no possibility that the ink will be ejected, making the printed material is fuzzy, and prevents the effect of saving ink on the plate surface.

The present invention shock-absorbing layer formed by the elastomer may also be placed under the engraving laser layer. The thickness of the layer subjected to laser engraving, is usually from 0.1 mm to several mm, and thus, under pripravenem layer can be placed materials that comprise different compositions. Cushioning layer is, preferably, an elastomeric layer having a hardness on the Shore A 20 to 70 degrees or have stiffness in ASCER-C from 10 to 60 degrees. If the hardness in Shore A is 20 degrees or more or stiffness in ASCER-C is 10 degrees or more, the print quality can be guaranteed, since the layer formed accordingly. If the hardness in Shore A is 70 degrees or less or stiffness in ASCER-C is 60 degrees or less, the layer can play the role of shock-absorbing layer. The most preferred range of hardness on the Shore A 30 to 60 degrees and ASCER-C is from 20 to 50 degrees. The amount of hardness in Shore A and rigidity ASCER-C in this invention is measured together with the thickness of amortis the dominant layer.

The above shock-absorbing layer may be made of any material having rubber elasticity, such as a thermoplastic elastomer, phototherapy elastomer, thermoset elastomer, although not limited specially.

Cushioning layer may be porous elastomeric layer having micropores of nanometer size. Conveniently, and in this invention it is preferable to use a material that becomes elastomer after curing, in particular material on the basis of liquid compositions on the basis of a photosensitive resin, which is cured by the action of light in a planar or cylindrical printing form.

Specific examples of thermoplastic elastomers, which are used for the cushioning layer may be styrene thermoplastic elastomers, such as SBS (polystyrene-polybutadiene-polystyrene), SIS(polystyrene-polyisoprene-polystyrene), SEBS(polystyrene-polyethylene/polybutylene-polystyrene), olefinic thermoplastic elastomers, urethane thermoplastic elastomers, essential thermoplastic elastomers, amide thermoplastic elastomers, silicon thermoplastic elastomers and fluorine thermoplastic elastomers.

Fototerapia elastomers can be a material obtained by mixing photopolymerizing MES is a measure plasticizer, the initiator of photopolymerization and similar compounds with the above-described thermoplastic elastomer and the liquid composition was obtained by blending photopolymerizable monomer, initiator of photopolymerization and the like with blastomeres resin. In this invention the number of degrees of freedom in the choice of material is extremely high, therefore, in contrast to the concept of composition-based photosensitive resin, for which the function of education clear of stereotypes is an important factor, there is no need to form a clear stereotypes under the action of light, but you must guarantee a certain degree of mechanical strength during curing of the composition by exposure of the treated surface on the light.

Further, there may be used cernosice rubber, besserdechie rubber, such as organic peroxides initiators condensation of phenolic resins, dioxin of quinone, oxides of metals.

Further, there may be used materials obtained three-dimensional stitching trecarichi liquid rubber using reactive vulcanizing agent for receiving an elastomeric rubber.

In this invention, when multiple layers to form a multilayer coating, the above pripraveny sheet can be placed below the shock-absorbing layer, for example, Naib the more advanced parts of the original printing plates or between the layer of photosensitive resin, suitable for laser engraving, and shock-absorbing layer, i.e. in the middle of the original PCB.

In this invention, the reduction of buildup on the surface and improving the wettability of the ink can be achieved through education of the modifying layer on the surface of the engraving laser printed matrix. Modifying layers may be covering films, processed compound that reacts with surface hydroxyl groups, such as a silane sizing, or titanium sizing, or covering films, processed liquid celanova compound, or a polymer film containing a porous inorganic material.

Widely used the silane coupling agents are compounds having in the molecule a functional group easily reacts with surface hydroxyl groups of the material. For example, such functional groups can be trimethoxysilyl group, triethoxysilyl group, trichlorosilyl group, diethoxyaniline group, dimethoxysilane group and demonopolisierung group, monoatomically group, monoatomically group, monochloramine group. Of these functional groups at least one is present in the molecule and reacts with the surface hydroxyl groups of the material, zafiksirovan the mi on the surface of the material. Further, in this invention as compounds containing silenly the sizing may be applied to compounds having at least one group of the following: calolina group, methacryloyl group, amino group with active hydrogen, epoxypropan, vinyl group, performanceline group and mercaptopropyl as reactive functional groups in the molecule, or compounds having long-chain alkyl group.

Titanium coupling agents can be compounds such as triisopropyl triisostearate the titanate, isopropyl-Tris(diastereotopic) titanate, isopropyl-three(N-amino-ethyl-amino-ethyl) titanate, tetraoctyl bis(decreasingother) titanate, Tetra(2,2-deallocker-1-butyl)bis(ditridecyl)fosfato the titanate, bis(artillerist)oxyacetic the titanate, bis(dioctylphthalate)ethylene titanate, isopropyl dioctanoyl the titanate, isopropyl timetabel isostearoyl the titanate, isopropyl trilateralization the titanate, isopropyl isostearoyl diacel the titanate, isopropyl three(dioctyladipate) titanate, isopropyl trikomiti the titanate, tetraisopropyl bis(dioctylphthalate) titanate.

If the molecule sizing or, in particular, silicon compounds, fixed on the surface has a curable reactive group of the covering film can become stronger by merging this soy is inania the action of light, heat or electron beam after it is fixed on the surface.

In this invention the above-mentioned sizing is diluted with a water-alcohol or water-spirit-acetic acid mixture to achieve the desired concentration of the sizing. The concentration of the sizing in the processing liquid is preferably from 0.05 to 10.0 wt.%.

How the sizing will be further described in this invention. The processing liquid containing the above-described sizing, distributed over the surface of the printing matrix or printed form after laser engraving. The method for coating the sizing is not specifically limited, can be applied a method immersion method, spraying method, coating roller, the method of application brush and the like. The temperature of the covering and the time covering not specifically limited, but the temperature of the covering is preferably from 5 to 60°, and the covering is preferably from 0.1 to 60 seconds. Next, the applied liquid layer on the surface of the resin forms preferably dried by heating, and the heating temperature is preferably from 50 to 150°C.

Before the surface of the printing plate treated with sizing, a hydroxyl group, linking the sizing can be densely formed on the surface of the printing form by a method, which applies the I am the light of a xenon excimer lamp, or similar, which operates in the vacuum ultraviolet range with a wavelength less than 200 nm, or a method of subjecting the surface to the action of high-energy atmospheric plasma, or the like.

If the layer containing the inorganic porous material, opens on the surface of the printing form, very small irregularities can be formed on the surface of the printing form during the processing of the layer of high-energy atmospheric plasma or the like, and maybe slight etching on the surface of the organic layer. Under this treatment buildup on the surface of the printing form are reduced, and the inorganic porous material is a better adsorbent for ink, thus, it is possible to expect the effect of improving the wettability of ink.

When laser engraving formed image is converted into a digital form and the laser forming apparatus, using the computer, the relief image on the original form. The laser for use in laser engraving is any laser that has a wavelength at which the original form has an absorption, but for engraving with high speed high precision laser desirable, and preferred examples are laser-based gaseous carbon dioxide, YAG laser, infrared laser or solid is positive emission laser infrared range, semiconductor laser. The second higher harmonic of the YAG laser, copper vapor laser, an ultraviolet laser having a wavelength of the oscillator in the ultraviolet range, for example, excimer laser, YAG laser, translated into the third and fourth higher harmonic capable of producing a disconnection in the organic molecule and are suitable for micromachining. The laser can be either permanent laser radiation, or by a pulsed laser. In General, the resin has an optical absorption at a wavelength of about 10 μm, which corresponds to the wavelength of the laser oscillator on the basis of carbon dioxide gas, and therefore there is no need to add a component that helps the absorption of laser light, but YAG laser has a wavelength of about 1.06 µm, and there is a large number of resins having absorption at this wavelength. Preferably should be added to the dye or pigment, which helps absorption. Examples of such coatings are poly(substituted)phthalocyanine compounds and metal-containing phthalocyanine compounds, cyanine compounds, squareone dyes, halogenopyrimidines dyes, chlorinefree dyes, metal-thiolate dyes, bis(chalcogenides)polymethine dyes, oceandrive dyes, biomineralize polymethine dyes, melocia the new dyes and quinoid dyes. Examples of pigments are Chernozemye inorganic pigments such as carbon black, graphite, copper chromite, chromium oxide, grammability aluminate, copper oxide, iron oxide, metal powder such as iron, aluminum, copper, zinc and the like, and these metals, doped silicon, magnesium, phosphorus, cobalt, Nickel, yttrium and the like.

These dyes and pigments can be used individually or in combination of two or more types, or can be combined in any form, such as a multilayered structure.

However, in the case of systems in which the composition is based on the photosensitive resin cures under the action of light, the added amount of organic/inorganic compounds, such as a dye or pigment having a strong optical absorption at the length of the light used for curing, preferably is in the range that does not violate photoallergenicity, and the ratio of the additive to the total number of compositions on the basis of a photosensitive resin, preferably, should be 5% or less, more preferably 2% or less.

Laser engraving is usually performed in the presence of oxygen-containing gas, in General, in the presence of air or gas flow, but can be performed in the atmosphere of carbon dioxide or nitrogen atmosphere. Powdered or liquid is materials, appearing in small quantities on the surface of bulk printing plate after completion of the etching can be removed by an appropriate method such as a method in which the materials are washed with a solvent, water Pavam or the like, or a method in which water purifier pulverisette of spray high pressure, or a method in which pulverisette a jet of high pressure.

In this invention the surface of the engraving laser printed matrix can be heated, which helps engraving laser, when the laser light for laser engraving of the printing matrix forms the separated elements of the stereotype. Methods for heating the engraving laser printing matrix is a method in which a flat or cylindrical crucible apparatus engraving laser heated by the heater, or a method in which the surface of the engraving laser printed matrix directly heated by an infrared heater. Through this stage of heating can be improved characteristics of laser engraving. The heating temperature is preferably from 50 to 200°S, more preferably in the range of from 80 to 200°S, even more preferably in the range of from 100 to 200°C.

In this invention the additional exposure in which light with a wavelength of from 200 to 450 nm deistvie is on the surface of the printing form, on which the formed elements of the stereotype can be performed after removal of the powdery and sticky liquid debris remaining on the surface of the mold after engraving using laser light, forming the separated elements of the stereotype. Additional exposure is a method that is effective at removing buildup on the surface. Additional exposure may be conducted at any ambient atmosphere, the atmosphere of inert gas or in water. Additional exposure is particularly effective when the initiator of photopolymerization, exciting the hydrogen atom contained in the applied composition on the basis of a photosensitive resin. Next, to receive additional exposure surface of the printing form can be treated with a solution of the initiator of photopolymerization, exciting a hydrogen atom, and only then exposed. Printing plate can be exposed by light in the solution of the initiator of photopolymerization, exciting a hydrogen atom.

Printing matrix in this invention can be applied for various kinds of products such as printing rollers for embossing, relief images for stereotyping pastes dielectric, resistor, conductor in the production of electronic devices, the formation of stereotypes of functional materials, such as antireflection film of color filter or filters, near-infrared optical devices, education stereotype for orienting layer, ground layer, luminescent layer, electron transport layer, or layer of sealing material in the production of display elements or liquid crystal display, an organic electroluminescent display or the like, a relief image for sabonervnih materials for ceramic products, relief images for advertising forms, templates or matrices for different types sabonervnih products, screen printing forms, rotary screen printing forms, paintings for printing or roller for normalization of the amount of ink that is in contact with the fabric, transferring the ink, or with anilox roller, not forming a stereotype.

The invention will be further described based on examples, but the invention is not restricted by these examples.

1. Laser engraving

Laser engraving was performed using the dioxide carbon engraving machine (trademark "ZED-mini-1000"produced by ZED Co., Ltd. (England)) with laser-based gaseous carbon dioxide with an output of 250 produced by Coherent Co., Ltd (USA). The engraving was carried out by the education elements of the stereotype, including points (frequency 10%, 80 lines per inch), screening by convex lines having a width of 500 μm, and the spacing Lin is th, having a width of 500 μm. Since the area of the upper part of the small pixels cannot be guaranteed, and the elements of the stereotype beyond models and become fuzzy, if the engraving depth is set too high, the depth of the engraving was established by 0.55 mm

2. The number of times of deletion fragments and residual ratio of fragments

The wreckage of the three-dimensional printed form after engraving laser were cleaned with a non-woven fabric (Trade mark "BEMCOT M-3"manufactured by Asahi Kasei Co. (Japan)), soaked in ethanol or acetone. The number of operations required to remove the sticky liquid debris generated after engraving, was equal to the number of times of deletion fragments. If the number of times is large, this means that the amount of liquid debris is large. The number of times of deletion fragments for excellent printing form is 5 or less times, preferably 3 or less times.

Further, the weight of the printed matrix after laser engraving, printing plates immediately after laser engraving and relief printing form after clearing away all the debris was measured, and the residual ratio of debris during the engraving was determined by the following formula:

(Weight forms immediately after engraving - weight stereotype after clearing away all fragments) / (Weight of the original form to the engraving - weight stereotype immediately after vicisti the shards) x 100.

The residual ratio of debris for superior printing form is 15 wt.% or less, preferably 10 wt.% or less.

After removal of debris remaining on the relief image was produced additional exposure by ultraviolet range with respect to the surface of the printing form. The light used for additional exposure, was the light of the ultraviolet fluorescent lamp, chemical lamp with a maximum at 370 nm) and a bactericidal lamp (germicidal lamp with a maximum at 253 nm).

3. View pixels

View pixels 80 lpi (lines per inch) with the engraving area points of 10% was observed through an electron microscope at magnification of 200x500x. If the points are conical type or pseudokoningii view (divergent view obtained by cutting a cone near their tops, parallel in the projection of the bottom of the cone), the printing form is satisfactory in appearance of the pixels.

4. Pore volume, average pore diameter and specific surface area of porous material and non-porous material

2 g of porous or non-porous material, was placed in a test tube and dried under reduced pressure preoperational apparatus at 150°and 1.3 PA for 12 hours.

Pore volume, average pore diameter and specific surface area vysushennogo is porous or non-porous material were measured by adsorption of nitrogen at atmospheric pressure and the temperature of liquid nitrogen using Autosorp 3MP (trade mark), produced by Quantachrome Co. (USA). Separately, the specific surface area was calculated using BET equation. Pore volume and average pore diameter were calculated based on the method of analysis of pore distribution, called bjh's (Brrett-Joyner-Halenda), assuming a cylindrical model for the adsorption isotherms during desorption of nitrogen.

5. Loss on ignition of porous and non-porous material

The weight of the porous or non-porous material that was recorded before the measurement. The sample for measurement was then placed in a high temperature electric muffle furnace (brand: model "FG31"manufactured by Yamato Scientific Co., Ltd. (Japan)) and calcined at 950°C for 2 hours in an atmosphere of air. Weight change after treatment was determined as loss on ignition.

6. The standard deviation in the distribution of the diameters of the particles of the porous material and porous material

Measurement in the distribution of the diameters of the particles of the porous material and porous material was carried out using a laser apparatus for measuring the distribution of particle diameter (brand model SALD-2000 J"produced by Shimadzu Co. (Japan)). Patent description of the apparatus in the catalogue was written that it is possible the measurement of particle diameters in the range of 0.03 to 500 μm. When using methanol as the environment dis is ergonovine ultrasound was applied for 2 minutes to disperse the particles and obtain fluid for measurement.

7. Viscosity

The viscosity of the composition is based on the photosensitive resin was measured at 20°on the viscometer Brucellosis type (Trade mark model B8H"manufactured by Tokyo Keiki Co., Ltd. (Japan)).

8. Test abrasion resistance

Printing matrix having a thickness of 2.8 mm was made separately, and the test for abrasion resistance was carried out in accordance with JIS-K6264. The load applied to the test sample, was of 4.9 N, the rotation speed of the disk was 60 ± 2 revolutions per minute, the number of tests usually was 1000, then the loss in the abrasion was measured. The area in which they were performed testing was 31,45 cm2. For excellent printing form loss during abrasion is 80 mg or less. If the loss in the abrasion is low, a printing matrix can be used for a long time and high-quality printed material can be obtained.

9. Measurement of resistance to surface abrasion

Printing matrix having a thickness of 2.8 mm was made separately, and the amount of resistance to surface abrasion μ was measured by the apparatus for measuring friction (brand model "TR", produced by Tokyo Seiki Seisaku-Sho, Ltd. (Japan)). Ballast placed on the sample surface, has an area of 63.5 mm2and the weight W 200 g, and the speed of ejection sostav the La 150 mm per minute. Lined paper (paper not containing return securities received from the net weight and having a thickness of 220 μm, which is used for cardboard, brand: White Liner", produced by Oji Paper Co., Ltd.) was attached to the surface of the ballast so that its flat surface facing to the surface, and the ballast is horizontally moved, so that the lined paper was between the printed matrix and ballast, surface printed matrix and a flat surface lined paper were in contact with each other for the measurement of resistance to surface abrasion μ. The amount of resistance to surface abrasion μ represents the ratio of the measured load Fd to the weight of the ballast, namely the coefficient of dynamic friction, expressed as μ = Fd/W, and is a dimensionless quantity. The average value of the measured loads in the range where the measured values were stable after the start of motion of ballast, namely from 5 to 30 mm, was defined as Fd. For the printing plate, it is preferable to have a low value of resistance to surface abrasion μ. For excellent printing form, the value of resistance to surface abrasion μ is 2.5 or less, and, if the magnitude of resistance to surface abrasion μ low deposition paper powder on the surface of the printing form at the time of printing as little and, thus, can be obtained a high-quality printed materials. If the magnitude of resistance to surface abrasion μ exceeds 4, the phenomenon of sediments paper powder occurs during printing on paper, such as cardboard, and, in this case, often blocked carrying the ink on the printed material in the area where was deposited a paper powder, which leads to defects.

10. The measurement of average molecular weight

The average molecular weight of the resin (a) and the organosilicon compound (C) were determined using gel-distribution chromatography (GPC method) and showed conversion to polystyrene, typical of known molecular weight resins. High-speed GPC apparatus (trademark "HLC-8020"manufactured by Tosoh Corporation (Japan)) and polystyrene closed column (trademark "TSKgel GMHXL", produced by Tosoh Corporation (Japan)) were used for measurements when using tetrahydrofuran as eluent. The column temperature was set at 40°C. there was obtained a resin solution in THF with a concentration of 1%, and 10 μl of this solution was injection in the GPC chromatograph. As a detector for the resin (a) was used detector UV light, operating at a frequency of 254 nm. For organosilicon compounds (C) detection was carried out parallactic re what ractometer. For resin (a) and the organosilicon compound (C)used in examples and comparative examples of the present invention, the polydispersity (Mw/Mn)determined by GPC method, was greater than 1.1 and, therefore, used an average molecular weight (Mn)determined by GPC method. For organosilicon the polydispersity (Mw/Mn)determined by GPC method, was greater than 1.1, and therefore the molecular weight was calculated from the molecular structure, identified by spectroscopy nuclear magnetic resonance (NMR method).

11. The measurement of the amount of the polymerized unsaturated groups

The average number of the polymerized unsaturated groups in the molecule synthesized resin was determined by removal of unreacted low molecular weight components by liquid chromatography and then analysis of the molecular structure by spectroscopy nuclear magnetic resonance (NMR method).

12. Research printing

Printed circuit Board produced by laser engraving, was applied to the study of printing. For printing was used proofing machine (trademark "Flexiploofer 100", produced by KR Co., Ltd. (England)), the above-described printing plate was attached to a printing cylinder with two-sided tape and the printing was performed on pokrytiyami pogatchnik method when using the blue-green water of the ink. When applying excessive pressure between the anilox roller and printing cylinder (state of application of pressure greater than 0.8 mm in comparison with the conventional transfer of ink to the form), only after printing 10 sheets with pressure between the printing cylinder and the printing cylinder is set at 0.15 mm, the level of ink remaining on the plate surface was visually observed.

13. Test the wetting ability of the printed matrix

To determine the wetting ability of the engraving laser printed matrix 20 ál of the indicator fluid with a surface energy of 30 mn/m (trademark "Wetting Tension Test Mixture No.30,0", produced by Wako Pure Chemical Industries, Ltd.), quantitatively selected by the introduction of a certain type, bury on the surface and within 30 seconds was measured, the maximum size of the area, on which was spread a drop; this value was used as an indicator for wetting ability. Than this value higher, the more easily the surface wetted by the indicator. For satisfactory engraving laser printing matrix, this value is from 4 to 20 mm

14. Method of measuring solid29Si-NMR

Measurement of solid-state29Si-NMR was made in "DSX400" (trademark)manufactured by Bruker Co., Ltd. The measurements were performed at the conditions of observation:kernel29 Si, the observed frequency: 79,4887 MHz, the number of playthroughs: 540, width: 6 MC/s, the relaxation time: 480 seconds, the frequency of rotation at the magic angle: 3500 Hz, the frequency of magic angle: 5000 Hz, the pulse method: hpdec, the diameter of the ampoule 7 mm. As an external standard chemical shifts was used dimethylsilicone rubber, and one peak at -22 ppm was recorded.

15. Plasma ionization spectrometry

Accurately weighed sample of the engraving laser printed matrix was subjected to dry ashing with charring of the sample under the action of the heater and the ashing of the charred sample in an electric muffle furnace at 500°and then fused with alkali mixed with two reagents for alkaline fusion (powders), for example potassium carbonate-sodium tetraborate and sodium, rafted the resulting mixture at 1200°C, cooled thus obtained sample was then dissolved in hydrochloric acid and was measured on plasma ionization spectrometer (trade mark "IRIS/AP"manufactured by Thermo Element Co., Ltd.). The measured wavelength was 251,612 nm. The radiation intensity of the sample was compared with the calibration curve obtained in the preliminary study, where it was determined the concentration of silicon present in the system, and of the calibrated concentration and weight of the engraving laser is m printed matrix, measured during the calibration study, it was determined the relative content of silicon in the engraving laser printed matrix.

16. Pyrolytic chromas(GC/MS)-dimension

Chromas(GC/MS)measurement was performed on "HP5973"manufactured by Agilent technologies Co., Ltd. The sample is decomposed by heating in a muffle furnace at 550°using pyrolytic apparatus (trademark "Py-2020D"manufactured by Frontier Laboratories Ltd.), introduced in GROMACS(GC/MS) to separate and identify. Mass analysis was performed by ionization of the sample using mass spectroscopy electron impact. A sample of about 0.3 mg, placed in a muffle furnace, precision weighed.

17. Measurement of hardness on the Shore A

Measurement of hardness on the Shore A was produced in an automatic determinant of the stiffness produced by Zwick Co., Ltd. (Germany). As the amount of hardness in Shore A used the value obtained for 15 seconds after the measurement.

18. Measurement of stiffness along ASCER-C

When the shock-absorbing layer has air bubbles, preferably the measurement of stiffness along ASCER-C.

Measurement of stiffness along ASCER-C was carried out using the determinant of the stiffness of the rubber (trademark "model ASCER-C"manufactured by Koubunshi Keiki Co., Ltd.). As the amount of rigidity in ASCER-C used the value obtained for 15 seconds after the measurement.

19. Measurement is their opacity

The opacity of the composition based on the photosensitive resin was measured using opacity meter (trade mark "NDH-1001DP"manufactured by Nippon Denshoku Co., Ltd.). Composition based photosensitive resin was molded to a thickness of 1 mm. In the case of compositions based photosensitive resin, which is liquid at 20°With, was located on a polyethylene terephthalate film form, limited made from rubber edge roller, having a thickness of 1 mm, then the liquid photosensitive resin was poured into a form and the form was covered with a polyethylene terephthalate film to obtain a sample, which then was used for the measurement.

(An example of retrieving 1)

447,24 g polycarbonatediol (trademark "PCDL L4672" (average molecular weight 1990, the value of IT: of 56.4)produced by Asahi Kasei Co.) and 30,83 g colordistance was placed in a collapsible flask with a capacity of 1 l equipped with a thermometer, stirrer, and circulating pump, and the mixture was heated at 80°C for 3 hours, then added 14,83 g 2-methacryloyloxyethyl and the mixture was further aged for 3 hours to form a resin (a)having methacryloyl group at the end of the molecule (with approximately two-curable unsaturated groups per molecule on the average) and the average molecular weight of about 10,000. This resin, which was in the form of thick solo the new syrup at 20° C, was diluted with application of external force and not returned to its original shape even after the termination of the external force.

(An example of obtaining 2)

447,24 g polycarbonatediol (trademark "PCDL L4672" (average molecular weight 1990, the value of IT: of 56.4)produced by Asahi Kasei Co.) and 30,83 g colordistance was placed in a collapsible flask with a capacity of 1 l equipped with a thermometer, stirrer, and circulating pump, and the mixture was heated at 80°C for 3 hours, then added 7,42 g 2-methacryloyloxyethyl and the mixture is then kept for 3 hours to form a resin (A2)having methacryloyl group at the end of the molecule (with approximately one polymerized unsaturated group per molecule on average) and the average molecular weight of about 10,000. This resin, which was in the form of thick malt syrup at 20°was diluted with application of external force and not returned to its original shape even after the termination of the external force.

(Example for the preparation of 3)

500 g of polytetramethylene (trademark "PCDL L4672" (the average molecular weight of 1830, the value of IT: 61,3)produced by Asahi Kasei Co.) and 52,40 g colordistance was placed in a collapsible flask with a capacity of 1 l equipped with a thermometer, stirrer, and circulating pump, and the mixture was heated at 60°C for 3 hours, then was added 7.9 g of monometallofullerenes (Mn400) and 6.2 hydroxypropylmethacrylate, after keeping the mixture for 2 hours was added 20 g of ethyl alcohol and kept for another 2 hours. Was obtained resin (A3)having methacryloyl group at the end of the molecule (having approximately 0.5 polymerized unsaturated groups per molecule on the average) and the average molecular weight of about 20,000. This resin, which was in the form of thick malt syrup at 20°was diluted with application of external force and not returned to its original shape even after the termination of the external force.

(Example 4)

400 g polyetherdiol (trademark "Kuraray Polyol P3010" (average molecular weight 3160, the value of IT: 35,5), produced by Kuraray Co., Ltd.) and 19,13 g colordistance was placed in a collapsible flask with a capacity of 1 l equipped with a thermometer, stirrer, and circulating pump, and the mixture was heated at 80°C for 3 hours, then added 6,74 g 2-methacryloyloxyethyl, and the mixture is then kept for 3 hours to form a resin (A4)having methacryloyl group at the end of the molecule (with approximately two-curable unsaturated groups per molecule on the average) and the average molecular weight of about 25,000. This resin, which was in the form of thick malt syrup at 20°was diluted with application of external force and not returned to its original shape even after the termination of the external force.

(Examples 1-7 and Comparative examples 1-3)

<> Resin (A1), (A2), (A3)obtained in the examples get 1, 2, 3, were used as resin (a), which represents plastomer at 20°to which were added, to obtain a composition based on resin, curable monomer, the organosilicon compound (C), the inorganic porous material, the initiator of photopolymerization and other additives as indicated in table 1.

As the organosilicon compound (C) were applied methylstyryl-modified silicone oil (trademark "KF-410", refractive index: 1,480; average molecular weight 6510 as the weighted average molecular weight, were recorded as two peaks: one at 7890 and the other at 700 ratio of the peaks of 4.2:1, which is liquid at 20°); carbinol-modified silicone oil (trademark "KF-160AS", refractive index: 1, 420mm; average molecular weight: 750, which is liquid at 20°(C)manufactured by Shin-Etsu Chemical Co., Ltd; methylphenylsiloxane oil (trademark "SH510, refractive index: 1,500; average molecular weight: 2890, which is liquid at 20° (C)manufactured by Toray Dow Corning Silicone Co., Ltd. These compounds were silicone compounds, not having the polymerized unsaturated group in the molecule.

As a result of measurement by the measuring opacity the opacity of the composition obtained is based on the photosensitive resin ranged from 25% to 30% in examples 1, 2, 3, 6, 7, which was applied methylstyryl-modified silicone oil. Opacity was 50% in example 4, which was applied carbinol-modified silicone oil and, further, the opacity was 90% in example 5, in which it was applied were-modified silicone oil.

As the inorganic porous material (f) was applied fine porous silica gel brand "Sylosphere C-1504" (hereinafter referred to as S-1504, average particle size: 4,5 μm; specific surface area: 520 m2/g; average pore size: 12 nm; pore volume: 1.5 ml/g; loss on ignition: 2.5 wt.%; adsorption of oil: 290 ml/100 g), "Sylysia 450" brand "Sylysia 450" (hereinafter referred to as CH-450, average particle size: 8.0 µm; specific surface area: 300 m2/g; average pore size: 17 nm; pore volume: 1.25 ml/g, loss on ignition: 5.0 wt.%; adsorption of oil: 200 ml/100 g), "Sylysia 470" (hereinafter referred to as C-470, average particle size: 14,1 μm; specific surface area: 300 m2/g; average pore size: 17 nm; pore volume: 1.25 ml/g, loss on ignition: 5.0 wt.%; adsorption of oil: 180 ml/100 g)manufactured by Fuji Silysia Chemical Ltd. The degree of porosity of applied fine porous silica gel was 780 for Sylosphere C-1504 and 800 for Sylysia 450 in the calculation of the density of 2 g/cm3. Sferic the awn Sylosphere C-1504, observed through a scanning electron microscope, as added porous spherical silica gel, 0.9 or more for almost all particles. Sylysia 450 and Sylysia 470 were porous, but not spherical silica gels.

The obtained composition based photosensitive resin was molded on a polyethylene terephthalate film in the form of a sheet having a thickness of 2.8 mm, and were used ultraviolet rays from a mercury lamp high pressure from the surface on which the layer of the photosensitive resin was exposed to the air. The amount of applied energy amounted to 4000 MJ/cm2(the value obtained by integration in time of the flow, the measured UV-35-APR Filter (trade mark)manufactured by ORC Manifacturing Co., Ltd.). The light from the lamp illuminated on the surface was measured using UV-M02" (trade mark ORC Manufacturing Co.,Ltd.). The illumination from the lamp, the measured UV-35-APR Filter was 19 mW/cm2and the illumination from the lamp, the measured UV-Filter 25, was 2.9 mW/cm2. For example 6 composition based photosensitive resin was molded on a polyethylene terephthalate film in the form of a cloth with a thickness of 2.8 mm, and then the surface was covered with a polyethylene terephthalate cover film having a thickness of 15 μm; the light of the above-mentioned mercury lamps high pressure was applied in the absence of oxygen for from the eridania compositions on the basis of a photosensitive resin and sheet production printing matrix.

Used by the initiator of photopolymerization was benzophenone (as the initiator of photopolymerization, exciting the hydrogen atom (d)) and 2,2-dimethoxy-2-phenylacetophenone (as degradable initiator of photopolymerization (e)).

Composition based photosensitive resin of examples 1-7 and comparative examples 1-3, everything was liquid at 20°C. the Viscosity, measured on a viscometer Brucellosis type was at 20°5 kPa*s for all systems.

For printing matrices was conducted engraving stereotypes laser engraving machine produced by ZED Co., Ltd. The results of the study printed matrices are presented in table 2.

The measurement results of the resistance to surface friction are presented in table 2. Comparative examples 1, 2, 3 show a high value for the resistance to surface friction and losses in the abrasion compared to examples 1-7. Test results wettability shown in table 2, and the size distribution of the indicator was in the range of from 4 to 20 mm for examples 1-7, while for all the Comparative examples, the size was more than 20 mm

The number of times of wyczesany fragments after engraving in table 2 refers to the number of procedures of clearing away necessary to remove the sticky liquid debris generated after engraving, and if this number is large, this is considered, what amount of liquid debris large.

In the study of printing ink residues was sufficient in examples 1-7, but in Comparative examples 1-3 ink obviously remain with blue color and cannot be deleted, although the surface was vicious cloth dipped in ethanol. Pictures showing the printed forms after researching printing for Example 1 and Comparative example 1 shown in figure 1 and figure 2. Figure 2 saving ink is obvious.

Double-sided adhesive tape was pasted on made of FRP tanks, a roller mounted on a pneumatic cylinder with an inner diameter of 213 mm and thickness of 2 mm, and the above-mentioned sheet-fed printing matrix, obtained separately, was wrapped around the tape and recorded. The adhesive was applied in the field of connection and overiden. The cylinder was brought into rotation of the rotary machine and the cutter of the cemented carbide was performed cut to a thickness of 2.5 mm In the case of Examples 1-7, the procedure was completed, when the debris generated during the procedure of cutting, did not stick to the cutting edge. However, in Comparative examples 1-3 debris stuck to the cutting edge, and in each case the operation was stopped to remove debris. For Comparative examples 1-3 are many deep characters cut remained on the surface. Next, deprimere 1-7 and Comparative examples 1-3, the surface was subjected to polishing procedure using fine polishing cloth. For examples 1-7 had no traces of cutting and a smooth surface was obtained. However, for Comparative examples 1-3 traces of cutting partially remained even after performing the polishing procedure.

Solid29Si-NMR spectrum was recorded for sample utverzhdenii photosensitive resin, suitable for laser engraving, obtained in Example 1. Observed narrow forked peak originating from such a silicon compound, as the organosilicon compound with a chemical shift of about -22 ppm and a broad peak located around -110 ppm originating from the inorganic silicon compound, such as a porous silica gel. The ratio of integrated peak intensities derived from organosilicon compounds, and the peak originating from the porous silica gel, (Iorg:Iino) was 1.0:7,37. It was found that forked peak originating from organosilicon corresponds dimethylsiloxane fragment and siloxane fragment having a methyl group and methylstyryl group, with the ratio of integrals 2:1. It is the ratio of integrals coincides with the result of a single measurement1H-NMR used for silicon compounds (trademark "KF-410", produced by Shin-Etsu Chemical Co., Ltd.).

Plasma-ionization spectra is roscope was performed for sample utverzhdenii photosensitive resin, suitable for laser engraving, obtained in Example 1. From the comparison of the intensities of radiation from the calibration curve, the relative content of silicon (WSi)contained in the sample, produced 2.22%. Thus, from the result of the plasma-ionization spectroscopy of the solid state29Si-NMR, the relative content of silicon originating from organosilicon compounds, was determined as 0.27% formula 2,22 x(1,0/(1,0 + 7,37)).

Further, as a result of the analysis is capable of laser engraving utverzhdenii photosensitive resin obtained with the use of pyrolytic hromas method, the mass spectrometer was detected connection, presumably cyclic siloxane having, as main parts of the molecule, dimethylsiloxane fragment and siloxane fragment with methyl and methylstyrenes group.

Example 8

Double-sided adhesive tape was pasted on made of FRP tanks, a roller mounted on a pneumatic cylinder with an inner diameter of 213 mm and 2 mm thick polyethylene terephthalate film coated with the adhesive was placed on the tape so that the adhesive layer facing outward, forming a cylindrical base. Composition based photosensitive resin, the same as in Example 1, was heated to 50°and deposited with a thickness of about 2 mm on cilindric the massive basis of the scraper-spatula to evenly apply the toner. Then the light from a mercury high-pressure lamps, the same as used in example 1 was applied at a dose of 4000 MJ/cm2(the value obtained by integration in time of the flow, the measured UV-35-APR Filter on the air for curing a layer of a composition based on the photosensitive resin. Then the roller was mounted on a pneumatic cylinder and placed in a rotary machine, cutting was carried out by the cutter of the cemented carbide during the rotation of the pneumatic cylinder up until the polyethylene terephthalate film is not reached 1.7 mm Cutting was completed, while the cut fragments were not sticking to the knife during cutting. Next, using a polishing film was produced by polishing when spraying a small amount of water, which led to the formation of the smooth surface of the cylindrical printing matrix having a smooth surface, on which there were no traces of cut.

Example 9

100 parts by weight of SBS thermoplastic elastomer (SBS: block copolymer of polystyrene/polybutadiene/polystyrene)having an average molecular weight of about 130000, as resin (a), 5 parts by weight of diacrylate nonan-1,9-diol as an organic compound (b), 30 parts by weight of a liquid polybutadiene having an average molecular weight of about 2000, a plasticizer, 0.6 parts by weight of 2,2-dimethoxy-2-phenylacetophenone the a and 1 part by weight of benzophenone as a photopolymerization initiator of the, 0.3 part by weight of 2,6-di-(tert-butyl)-4-METHYLPHENOL a photopolymerization inhibitor, 1 part by weight methylstyryl-modified silicone oil (trademark "KF-410", produced by Shin-Etsu Chemical Co., Ltd.), mixed at 130°With the mixer until homogeneous compositions on the basis of a photosensitive resin, which was solid at 20°C.

Using the press for extrusion, the resulting composition based photosensitive resin was heated and extruded on a polyethylene terephthalate film having a thickness of 125 μm, formed of sheet composition based on the photosensitive resin having a thickness of 2 mm.

Double-sided adhesive tape was pasted on made of FRP tanks, a roller mounted on a pneumatic cylinder with an inner diameter of 213 mm and thickness of 2 mm, and the above-described sheet composition based photosensitive resin was wrapped around the tape so that the polyethylene terephthalate film is left on the inner side, and thus, the composition based on the photosensitive resin was fixed. The above composition based photosensitive resin was applied into the gaps in the areas of merger and heated to the melting point, whereby was obtained a seamless cylindrical composition based photosensitive resin. Then the light from the mercury lamp high is the second pressure, the same as used in example 1 was applied at a dose of 4000 MJ/cm2(the value obtained by integration in time of the flow, the measured UV-35-APR Filter on the air for curing a layer of a composition based on the photosensitive resin. Then the roller was mounted on a pneumatic cylinder and placed in a rotary machine, cutting was carried out by the cutter of the cemented carbide during the rotation of the pneumatic cylinder up until the polyethylene terephthalate film is not reached 1.7 mm Cutting was completed, while the cut fragments were not sticking to the knife during cutting. Next, using a polishing film was produced by polishing when spraying a small amount of water, which led to the formation of the smooth surface of the cylindrical printing matrix having a smooth surface, on which there were no traces of cut.

Example 10

Composition based photosensitive resin was photoallergen with the formation of the cushioning layer of the printed matrix in the same manner as in example 1 except that the liquid composition based photosensitive resin (trademark "APR F320", produced by Asahi Kasei Co.) was molded into a sheet form having a thickness of 2 mm. On this cushioning layer was deposited with a thickness of 0.8 mm liquid composition based photoacustic Inoi resin, used in example 1, and a printing matrix was produced following irradiation light. The hardness of the cushioning layer on the Shore A was 55 degrees.

The residual ratio of the wreckage after the laser engraving on the basis of carbon dioxide gas was 5.7 per cent, the number of times wyczesany fragments after engraving was 3 or less, and the view points of the raster was tapered and favorable.

The magnitude of resistance to surface abrasion and loss of abrasive test were comparable to those observed in example 1.

Example 11

Printing matrix was produced in the same manner as in example 1, except that used were the organic porous spherical fine inclusion. Organic porous fine inclusions having an average particle size of 8 μm, specific surface area 200 m2/g and an average pore size of 50 nm, were mixed with crosslinked polystyrene. The surface of the printed matrix was overiden.

After engraving laser-based gaseous carbon dioxide sticky liquid fragments were formed in large quantities and the required number of times wyczesany debris exceeded 30. It can be assumed that this is because organic porous fine inclusions were melted and destroyed by the action of light of the laser, t is it that they could not save porosity.

The amount of resistance to surface friction and abrasion loss were comparable to those observed in example 1.

Example 12

Double-sided adhesive tape was pasted on made of FRP tanks, a roller mounted on a pneumatic cylinder with an inner diameter of 213 mm and 2 mm thick polyethylene terephthalate film coated with the adhesive was placed on the tape so that the adhesive layer facing outward, forming a cylindrical base. Composition based photosensitive resin obtained by removing benzophenone, as the initiator of photopolymerization of a composition based on the photosensitive resin of example 1, was heated to 50°and deposited with a thickness of about 2 mm in the cylindrical basis, using scraper-spatula for applying toner. Then the light from mercury lamps high pressure was applied at a dose of 4000 MJ/cm2(the value obtained by integration in time of the flow, the measured UV-35-APR Filter on the air for curing a layer of a composition based on the photosensitive resin.

To 100 parts by weight of the composition based on the photosensitive resin of example 1 was added 1 part by weight of ultra-fine copper oxide (trademark "Nano tek CuO", produced CIKASEI Co., Ltd.), having optical absorption in the near-infrared range, and the mixture was mixed and degassed in the apparatus premesis the deposits and DiaryOne (trademark "Mazerustar DD-300", produced by Kurabo Industries Ltd.) to get the black composition based photosensitive resin. Black composition based photosensitive resin, heated to 50°was a layer having a thickness of 0.1 mm, the above-described layer utverzhdenii composition based photosensitive resin scraper-spatula for applying toner was then applied light of the above mercury lamps high pressure, the same as used in example 1 at a dose of 4000 MJ/cm2(the value obtained by integration in time of the flow, the measured UV-35-APR Filter on the air for curing a layer of a composition based on the photosensitive resin. Then was the above-mentioned cutting tool of cemented carbide, made of silicon nitride, to a thickness of 0.08 mm, and then the surface was subjected to polishing using a polishing tape. Cut off the debris formed during cutting, not sticking to the cutter of the cemented carbide, and on the surface after polishing are no remaining traces of cut.

On the thus obtained cylindrical engraving laser printed matrix of the separated elements of the stereotype, which has a depth of 0.5 mm and a size of 2 cm2were formed with the help of dioxide carbon laser engraving machine (trademark "ZED-mini-1000", manufactured ZEDCo., Ltd. (England), and then the elements of the stereotype by using engraving apparatus on the basis of near infrared laser (trade mark "CDI Classic"manufactured by Esko-Graphics Co., Ltd.(Germany); wavelength: 1.06 µm) were formed by pixels having a depth of 0.01 mm In the observation in the electron microscope, it was found that the shape of the pixels is conical and favorable.

Made separately as described above cylindrical printing matrix was separated by cutting polyethylene terephthalate film from the double adhesive tape, whereby was obtained a sheet printing matrix. Using this sheet printed matrix as the sample, were measured value of resistance to surface friction and abrasion loss in the test for abrasion resistance; the results obtained were comparable with the results in example 1.

Example 13

Liquid composition based photosensitive resin was obtained in the same way as in example 1 except that the resin (a) was applied resin (A4)obtained in example 4, and added 15 parts by weight S-1504 as the inorganic porous material. Liquid composition based photosensitive resin obtained in the same manner as in example 8 was applied onto a cylindrical base and photoallergen with getting otherid is authorized cylindrical photosensitive resin.

Procedures for cutting and polishing were performed by the cutter of the cemented carbide during the rotation utverzhdenii cylindrical photosensitive resin in the same manner as in example 8. The debris generated at the stage of the procedure, cut, were sticky, as compared with example 8, but not stuck on the cutter. Traces of cutting after the polishing process was not observed, and there was obtained a cylindrical printing matrix having a smooth surface.

Concave-convex elements of the stereotype were formed by laser engraving on the surface of the obtained cylindrical photosensitive resin, the wreckage after the engraving were cleaned five times. The shape of the pixels was tapered and favorable.

Comparative example 4 under the conditions of example 12

Double-sided adhesive tape was pasted on made of FRP tanks, a roller mounted on a pneumatic cylinder with an inner diameter of 213 mm and 2 mm thick polyethylene terephthalate film coated with the adhesive was placed on the tape so that the adhesive layer facing outward, forming a cylindrical base. The same as in Comparative example 1, a composition based photosensitive resin was heated to 50°and deposited with a thickness of about 2 mm in the cylindrical basis, using scraper-spatula for applying toner. Then the light from mercury is any high pressure, the same as in example 1 was applied at a dose of 4000 MJ/cm2(the value obtained by integration in time of the flow, the measured UV-35-APR Filter on the air for curing a layer of a composition based on the photosensitive resin.

Then the roller was mounted on a pneumatic cylinder and placed in a rotary machine, cutting was carried out by the cutter of the cemented carbide during the rotation of the pneumatic cylinder as long as the thickness, including polyethylene terephthalate film, not reached 1.7 mm At the stage cut was a phenomenon of the build-up of cut pieces on the cutter, and the cutting rotation was stopped in each case for the surgery, cut off by removing debris from the edge of the cutter. Next, using the film for polishing was conducted polishing spray a small amount of water. The traces were cut slightly visible on the surface. Traces of cutting cannot be completely removed at the stage of polishing.

Comparative example 5

Composition based photosensitive resin having the same composition as in example 1, except that the methacrylate-modified silicone oil (trademark "X-22-164C", produced by Shin-Etsu Chemical Co., Ltd.) was used instead of methylstyryl-modified silicone oil (trademark "KF-410", produced by Shin-Etsu Chemical Co.,Ltd.). The obtained composition based photosensitive resin was dark liquid at 20°opacity was 92%, as shown in the measurement result by the measuring opacity.

Sheet printing matrix having a polyethylene terephthalate layer as a base, was obtained in the same manner as in example 1. The ratio of residual debris during laser engraving, the number of times wyczesany fragments and pixels were comparable with that obtained in example 1. The magnitude of resistance to surface abrasion amounted to 0.65, the abrasion loss in the test for abrasion resistance was less than 0.5 mg, the size distribution of droplets in the test for wetting ability was 8 mm When a drop of ethanol was applied to the surface, was observed phenomenon of exclusion drops in this test. This phenomenon was not observed in example 1.

KF-410
Table 1
Resin (a)The organic compound (b)Inorganic porous materialThe polymerization initiatorThe organosilicon compound(c)Other additives
Type Containing-tion in the mixTypeContent-the content in the mixTypeThe content in the mixTypeContent-the content in the mixTypeContent

the content in the mix
TypeContaining-tion in the mix
Example 1(A1)100PEMA

BDEGMA
37

12
C-15047,7DMPAP

BP
0,9

1,5
KF-4101,5BHT0,5
Comparative example 1(A1)100the samethe samethe samenothe same
Example 2(A2)100the samethe samethe sameKF-4101,5the same
Comparative example 2(A2)100the samethe samethe same nothe same
Example 3(A3)100the samethe samethe sameKF-4101,5the same
Comparative example 3(A3)100the samethe samethe samenothe same
Example 4(A1)100LMA

PPMA

DEEHEA

TEGDAM

TMPTMA
6

15

25

2

2
C-15047,7the sameKF-160AS1,5the same
Example 5(A1)100BZMA

CHMA

BDEGMA
25

19

6
C-15047,7the sameSH-5101,5the same
Example 6(A1)100the sameCH-4507,7DMPAP1,61,5the same
Example 7(A1)100the sameC-4707,7DMPAP

BP
0,9

1,5
the samethe same

The content in the mixtures are given in the table in parts by weight

Description of abbreviations:

LMA: lauryl methacrylate (Mn254)

PPMA: monomethacrylate of polypropylenglycol (Mn400)

DEEHEA: methacrylate 2-ethylhexylacrylate (Mn286)

TEGDMA: dimethacrylate of tetraethyleneglycol (Mn330)

TMPTMA: trimethacrylate of trimethylolpropane (Mn339)

BZMA: benzyl methacrylate (Mn176)

CHMA: cyclohexyl methacrylate (Mn167)

BDEGMA: methacrylate of butoxydiglycol (Mn230)

PEMA: phenoxyethyl methacrylate (Mn206)

DMPAP: 2,2-dimethoxy-2-phenyl-acetophenone

BP: benzophenone

BHT: 2,6-dibutylamino

Conical and favorable
Table 2
The share of residual fragments after engraving*1(% by weight)The number of times clearing away the debris after engraving (BEMCOT and ethanol)View pixelsThe magnitude of resistance to surface abrasionLoss when grinding (mg)Test for wettability

The size of the RA is the expansion drops (mm)
Example 18,5<3Conical and favorable0,85<0,58
Comparative example 110<3Conical and favorable3,2562,935
Example 27,5<3Conical and favorable0,8<0,510
Comparative example 29<3Conical and favorable3,297,537
Example 39,5<3Conical and favorable0,9<0,59
Comparative example 310<3Conical and favorable3,3of 113.237
Example 413,0<3Conical and favorable1,0<0,59
Example 510,5<3Conical and favorable1,2<0,58
Example 68,0<31,5511
Example 79<3Conical and favorable0,959

*1)"the proportion of the residual fragments after engraving" is calculated by the formula:

(Weight forms immediately after engraving - weight stereotype after clearing away all fragments) /

(The weight of the original form to the engraving - weight stereotype immediately after clearing away the debris) x 100

INDUSTRIAL APPLICATION

This invention is most applicable for making a relief image for flexographic printing plates, high-quality printing plates or screen printing, laser engraving, education stereotype for surface treatment such as embossing, the formation of a relief image for printing tiles or similar, get the stereotype of a conductor, semiconductor or dielectric for electronic device, receiving the stereotype of a functional material such as an antireflection film in the optical device, a color filter or filter near infrared region and, further, the formation of stereotype for orienting layer, ground layer, luminescent layer, electron transport layer, or layer of sealing material in the production of elementobjectreference display, organic electroluminescent display or the like, or a roller for normalization of the amount of ink that is in contact with the fabric, transferring the ink, or with anilox roller, not forming a stereotype.

1. The engraving laser printing matrix obtained by vodootvedenie composition based photosensitive resin, where the composition is based on the photosensitive resin for laser engraving of the printing matrix contains the resin (a)having the polymerized unsaturated group having an average molecular weight in the range of 1000 or more and 200,000 or less, the organic compound (b) with an average molecular weight less than 1000, with the polymerized unsaturated group, and the organosilicon compound (C)having in a molecule at least one Si-O bond and not containing the polymerized unsaturated group, where the content of organosilicon ((C) about 0.1 wt.% or more and 10 wt.% or less by weight of the composition based on the photosensitive resin,

where a printing matrix contains the organosilicon compound in its inner part or on the surface, and the silicon atoms derived from organosilicon have relative content of 0.01% or more and 10% or less, when the organosilicon compound is recorded and quantitatively determined is carried out by a combination of solid-state methods 29Si-NMR (spectroscopy solid-state nuclear resonance, in which the detected engine is an isotope of silicon with an atomic weight of 29) and a flame ionization spectroscopy.

2. The engraving laser printing matrix according to claim 1 in which the organosilicon compound (C) has srednekamennogo molecular weight of 100 or more, and up to 100,000 or less, and 20°is liquid.

3. The engraving laser printing matrix according to claim 1 in which the organosilicon compound (C) comprises the organosilicon compound represented by the average gross formula (1)

where R represents one or more hydrocarbon groups selected from the following: a linear or branched alkyl group which has from 1 to 30 carbon atoms; cycloalkyl group which has from 5 to 20 carbon atoms, unsubstituted or substituted alkyl group having from 1 to 20 carbon atoms, CNS group which has from 1 to 20 carbon atoms; an alkyl group, substituted aryl group having from 1 to 30 carbon atoms (the number of carbon atoms in the alkyl group substitution); halogen-substituted aryl group, which has from 6 to 20 carbon atoms; alkoxycarbonyl group which has from 2 to 30 carbon atoms; monovalent group, is holding a carboxyl group or a salt thereof; monovalent group containing alphagroup or a salt thereof; and polyoxyalkylene group;

each of Q and X is one or more hydrocarbon group selected from the following: a hydrogen atom, a linear or branched alkyl group which has from 1 to 30 carbon atoms; cycloalkyl group which has from 5 to 20 carbon atoms; unsubstituted or substituted alkyl group having from 1 to 20 carbon atoms; CNS group which has from 1 to 20 carbon atoms; aryl-substituted alkyl group which has from 1 to 30 carbon atoms; halogen-substituted aryl group which has from 6 to 20 carbon atoms; alkoxycarbonyl group which has from 2 to 30 carbon atoms; monovalent group containing a carboxyl group or a salt thereof; monovalent group containing alphagroup or a salt thereof; and polyoxyalkylene group,

p, r and s are numbers satisfying the following formulas:

0<R<4,

0≤r<4,

0≤s<4, and

(p+r+s)<4.

4. The engraving laser printing matrix according to claim 3, in which the silicon compound is a compound having at least one organic group selected from the following: aryl group, a linear or branched alkyl group containing as a substituent at least the one aryl group, alkoxycarbonyl group, CNS group and polyoxyalkylene group and a hydrogen atom attached to the carbon atom to which is directly attached organic group.

5. The engraving laser printing matrix according to claim 4, in which the silicon compound has at least one organic group selected from the following: methylstyrene group, sterelny group and carbinol group.

6. The engraving laser printing matrix according to claim 1, where the organosilicon compound (C) is a compound containing at least one organic group selected from the following: aryl group, a linear or branched alkyl group containing as a substituent at least one aryl group, alkoxycarbonyl group, CNS group and polyoxyalkylene group and a hydrogen atom attached to the carbon atom to which is directly attached organic group.

7. The engraving laser printing matrix according to claim 1, additionally containing an initiator of photopolymerization, in which the initiator of photopolymerization contains at least one initiator of photopolymerization (d)exciting the hydrogen atom.

8. The engraving laser printing matrix according to claim 7, in which the initiator of photopolymerization contains at least one initiator of photopolymerization (d), to the Delta hydrogen atom, and at least one degradable initiator of photopolymerization (e).

9. The engraving laser printing matrix of claim 8, in which the initiator of photopolymerization (d)exciting the hydrogen atom contains at least one compound selected from the following: benzophenone, xanthene and anthraquinones; and degradable initiator of photopolymerization (e) contains at least one compound selected from the following: alkyl esters Bessonov, 2,2-dialkoxy-2-phenylacetophenone, acylated esters Asimov, azo-compounds, organic sulfur compounds and diketones.

10. The engraving laser printing matrix according to claim 7 or 8, in which the initiator of photopolymerization is a compound having in the same molecule as an initiator of photopolymerization, exciting a hydrogen atom, and degradable initiator of photopolymerization as a functional substitute.

11. The engraving laser printing matrix according to claim 1, in which the resin (a) is liquid at 20°and the resin (a) and/or the organic compound (b) are compounds bearing element, which has at least one connection selected from the following: carbonate bond, a tie simple ether linkage of ester; and/or which is at least one molecular link selected from the group consisting of aliphatic saturated uglevodorodno the th link and aliphatic unsaturated hydrocarbon chain, and has a urethane bond.

12. The engraving laser printing matrix according to claim 1, in which the covering layer of a composition based on the photosensitive resin has a thickness of 1 mm and has a degree of light absorption 0% or more and 70% or less.

13. The engraving laser printing matrix according to claim 1, where the composition is based on the photosensitive resin which is liquid at 20°C.

14. The engraving laser printing matrix, which is obtained by molding composition based photosensitive resin specified in claim 1, in sheet or cylinder and, further, the crosslinking and curing of a cloth or cylinder under the action of light.

15. The engraving laser printing matrix according to item 13 or 14, having the surface treated with at least one method selected from the following: cutting,. grinding, polishing, blast after crosslinking and curing under the action of light.

16. The engraving laser printing matrix indicated in paragraph 15, in which the elastomer layer is formed by curing the composition on the basis of a photosensitive resin which is liquid at normal temperature.

17. The engraving laser printing matrix indicated in paragraph 15, in which the surface layer of the multilayer material is a layer that can be engraved by laser near infrared radiation.

18. The engraving laser printing matrix according to claim 1, where the Gras is dummy laser printing matrix has a surface with this feature wetting ability, when 20 ml of the indicator fluid with a surface energy of 30 mn (trademark "Wetting Tension Test Mixture No.30,0", produced by Wako Pure Chemical Industries, Ltd.), quantitatively selected by the introduction of a certain type, bury the surface and after 30 seconds was measured, the maximum size of the area, on which was spread a drop, the size of the region in diameter was 4 mm or more and 20 mm or less.

19. The engraving laser printing matrix according to any one of p, 14 and 18, which is the original flexographic printing form or the original form of letterpress printing, or the original form of stencil printing, in which the stereotype is made by way of laser engraving, or roller standard amount of ink that is in contact with the fabric, transferring the ink, or with anilox roller, on which is formed the template.



 

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