Near-infrared radiation-absorbing reactive polymer particles, production method and use thereof

FIELD: chemistry.

SUBSTANCE: invention discloses polymer particles with size between 60 nm and 1000 nm and containing a polymer which contains a hydrophobic backbone chain formed by at least one segment which absorbs near-infrared radiation, bonded with chloroform which absorbs near-infrared radiation, having an absorption peak between 700 and 1100 nm; and at least one segment which is transparent for near-infrared radiation. The invention also discloses a method of producing said particles, a coating composition containing said polymer particles and a reactive iodonium oligomer, as well as a negative lithographic offset printing plate which contains a substrate, a hydrophilic bottom layer and a laser-developed top layer, where the laser-developed top layer contains said polymer particles.

EFFECT: disclosed particles enable to obtain coatings which ensure sufficient runability and machine developability of negative lithographic offset printing plates.

32 cl, 35 dwg, 4 tbl, 23 ex

 

References to related applications

This application has a priority based on provisional application U.S. no. 60/823415, filed August 24, 2006. All of the above documents are entered as a reference.

The technical field to which the invention relates

This invention relates to polymeric particles suitable for coatings, printing plates, and the plates and coatings containing these particles. More specifically, these new polymer particles and coatings are suitable for lithographic offset printing plates for direct digital imaging using laser radiation in the near infrared region.

The level of technology

Machine-show negative lithographic offset printing plates is known from the prior art. For example, U.S. patent No. 5569573 relates to lithographic printing plates containing the solidity of the laser layer containing microencapsulation oleophilic substance in a hydrophilic polymer binder.

European patent No. 0770495 relates to lithographic printing plates containing substances that absorb infrared radiation in the near field, a polymeric binder and thermoplastic particles can stick together when heated.

U.S. patent No. 6983694 relates to a machine-show negative is Vietnam printing plates, covered sensitive to infrared radiation in the near field covering compositions containing thermoplastic polymer particles such as polystyrene or a copolymer of poly(Acrylonitrile) particles, erectionspeedo hydrophilic polymer binder and absorbing in the NIR dyes.

U.S. patent No. 6262740 refers to negative offset printing plates, covered sensitive to infrared radiation in the near field covering compositions containing methoxyethylamine copolymers, phenolic resins, itaniemi salt and absorbing in the NIR dyes.

U.S. patent No. 6124425 and 6177182 relate to machine-show negative offset printing plates, coated with a thermally reactive copolymers, absorbing in the near infrared region, which undergo reactions with the formation of crosslinks in cationic polymerization upon irradiation with light of near infrared region. The chromophore group absorbing infrared radiation in the near field attached to the polymer main chain through ether and ammonium communication. These polymers that absorb in the near infrared region, is prepared in the form homogeneous solutions.

U.S. patent No. 6960422 relates to the preparation of a negative Hep is the shaft of the printing plates, which contain sensitive to infrared radiation of the composition for the first layer containing molecular dyes that absorb in the near infrared region, the generators of the radical polymerizable under the action of the radicals, urethane compounds, reactive polymeric binder and other excipients.

European patent No. 1234662 relates to the preparation of the negative offset printing plates that cover compositions which contain a compound that absorbs infrared radiation in the near field, onevia initiators and urethane polymers containing poly(ethylene oxide)side chains. These urethane polymers do not absorb radiation in the near infrared region.

U.S. patent No. 6969575 and 7001704 relate to machine-show negative offset printing plates having a layer forming the image, which contains microcapsules that absorb infrared radiation in the near field, and a compound generating acid. Similarly, U.S. patent No. 7001673 and 7078145 relate to the preparation of machine-show negative offset printing plates. Covering songs contain microcapsules that absorb infrared radiation in the near field, which is prepared by emulsification with a high speed mixer fatty phase containing a hydrophobic polymer clay is s, substances that absorb radiation in the near infrared region and initiators in the hydrophilic polymer aqueous solutions. The preparation of these microcapsules is complex, and coverage data show low resistance to scratching and require an external coating layer.

U.S. patent No. 6037102 and European patent application No. 1117005 relate to the preparation of the negative photosensitive coating compositions containing copolymers, grafted poly(ethylene oxide)-side chains. These copolymers do not absorb radiation in the near infrared region.

U.S. patent No. 6582882 relates to the preparation of grafted polymers and copolymers for use in offset printing plates containing poly(ethylene oxide)side chains which are grafted to a hydrophobic polymer main chain containing no crosslinking. These polymers do not absorb radiation in the near infrared region.

U.S. patent No. 6899994 and discussed with him the patent application U.S. No. 2003/0157433; 2003/0664318 and 2005/0123853 relate to machine-show negative offset printing plates, which cover thermally manifested compositions containing a polymeric binder, initiation systems and components that can be polimerizuet. Described polymeric binders are copolymers without crosslinks containing polietilenoksidnoy and polypropylene PP is Lenovo blocks or grafted copolymers, copolymerizable with hydrophobic monomers such as styrene, substituted styrene, alpha-methylsterol, ester of acrylic acid, methacrylic acid, Acrylonitrile, acrylamide, methacrylamide, venilale, vinyl ether, a simple vinyl ester and alpha-olefin. Components that can be polimerizuet are viscous liquid oligomers containing a large number of acrylic and methacrylic functional groups. Initiating the system contains dyes that absorb in the near infrared region, and connections, producing radicals, such as triazine and itaniemi salt.

All of these coating compositions and printing plates have some drawbacks, such as: they have a sticky surface, which causes difficulties in processing and storage, show phase separation and/or crystallization surfaces require a high power laser to get the image, have a weak adhesion with the substrate and, therefore, unable to provide sufficient reduce resistance during continuous operation, are not machine-show because of the staining dye, causing darkening of the background, have low resistance to scratching, require a layer of top coating and/or special surface treatment of the substrate and are expensive or slozhnotsvetovye is passed.

Thus, there remains a need for new materials and new coatings for lithographic plates, which would allow to overcome some or all of these disadvantages of the prior art.

The present description refers to a number of documents, the content of which is introduced in this description fully by reference.

The invention

First, this invention relates to polymeric particles having a particle size of between about 60 nm and about 1000 nm and containing polymer. This polymer contains (a) a hydrophobic main chain, (b) the segment that absorbs infrared radiation in the near field, which is connected for this purpose with a chromophore that absorbs infrared radiation in the near field region having a peak absorption between about 700 nm and about 1100 nm; and (c) transparent to infrared radiation in the near field of the segment.

In the variants of implementation, the polymer particle may have a particle size of between about 200 nm and 600 nm. Also, in the variants of implementation, the polymer may have a molecular weight of about 3000 daltons or more.

In specific embodiments, the implementation, the polymer may have the following structure:

in which

• G1 is absorbing segment;

• G2 depict is to place a transparent segment;

• G1 and G2 form a hydrophobic main chain;

• a and b independently represent molar relationship between 0.01 and 0.99; and

• the chromophore covalently or electrostatically attached to a hydrophobic main chain as side groups.

In the variants of implementation, absorbing segment may contain:

where NIR is the chromophore; R1 represents hydrogen or C1-C18alkyl; X represents an anionic counterion bromide, chloride, iodide, tosilata, triflate, cryptomaterial, dodecylbenzensulfonate, tetraphenylborate, alkyldiphenylamine, tetrafluoroborate or hexafluoroantimonate;

• M is oxygen, sulfur or dialkylamino;

• a is the molar ratio between 0.01 and 0.99; and

• m represents the number of repeating units between 1 and 5.

In other embodiments, implementation, absorbing segment may contain polyether linker covalently linking the chromophore and the polymer main chain. More specifically, absorbent segment may contain:

in which

• a is the molar ratio between 0.01 and 0.99;

• R represents hydrogen or methyl;

• R1 is C1-C8alkyl or C1-C8alkyloxy; w represents the number of repeating units between 10 and 50;

• m, not only is that the number of repeating units between 1 and 10;

• Y represents a linear or branched C2-C4alkyl;

• Q represents a spacer elements group;

• NIR represents the chromophore; and L represents

in which Q-NIR and (YO)Wgroups are shown for clarity and j represents the number of repeating units between 0 and 10.

In more specific embodiments, the implementation, the spacer elements may be to:

in which L and NIR groups are shown for clarity, R2 represents C1-C8alkyl or C1-C8alkoxy; R3 is the same as R2 or a phenyl ring substituted by H or R2; and A represents an anion. In the variants of implementation, this anion can be bromide, chloride, iodide, tosylate, tetraphenylborate, alkyldiphenylamine, tetrafluoroborate or hexafluoroantimonate.

In specific embodiments, implementation, two polymer main chain of the polymer particles sew through two absorbing segment and one chromophore. In other embodiments, the implementation, the chromophore can be:

in which each of D1 and D2 independently represents-O-, -S-, -Se-, -CH = CH - or-C(CH3)2; each of Z1 and Z2 independently represents one or more fused substituted or unsubstituted aromatic ring; h represents an integer between 2 and 8; n represents 0 or 1; M represents the waters of the genus or Na, K or cationic counterion tetraalkylammonium salt.

A1 is bromide, chloride, iodide, tosylate, triflate, cryptomaterial, dodecylbenzensulfonate, tetrafluoroborate, tetraphenylborate or triphenyl-n-butylboron, as an anionic counterion; R3 represents hydrogen or alkyl; and each R4 and R5 independently represents alkyl, arylalkyl, hydroxyalkyl, aminoalkyl, carboxyethyl, sulfoalkyl, acetoxyethyl, polyester or Deputy, which can be polymerizate, of the formula:

in which m represents the number of repeating units between 0 and 50 and R is hydrogen or methyl.

In the variants of implementation, the transparent segment may contain styrene, substituted styrene, alfamethylstyrene, 4-vinylphenol, 3-vinylbenzene, ester of acrylic acid, methacrylic acid, Acrylonitrile, acrylamide, methacrylamide, venilale, complex, vinyl ether, vinyl ester, 9-vinylcarbazole or vinylphosphonic acid, as a transparent Monomeric units, and mixtures thereof.

In other embodiments, implementation, transparent segment may contain transparent Monomeric units obtained by the polymerization of polyester monomers of the formula:

H2C=C(R)-COO-(YO)W-Y-T

H2C=C(R)-COO-CH2CH2-NHCO-O(CH2CH2O)W-CH[CH2-(OCH2CH2)W-Y-T 2

or mixtures thereof, in which

• R represents hydrogen or methyl;

• Y represents C2-C4alkyl;

• w represents the number of repeating units between 5 and 50; and

• T is hydroxy, alkoxy, aryloxy, carboxylic acid, acid or phosphoric acid as end groups and their salts.

In the variants of implementation, the transparent segment may contain:

• poly(ethylene glycol)(meth)acrylate,

• poly(propylene glycol)(meth)acrylate,

• poly(ethylene glycol-block-propylene glycol)(meth)acrylate,

• poly(ethylene glycol-block-caprolacton)(meth)acrylate,

• alkilany ether poly(ethylene glycol)(meth)acrylate,

• alkilany ether of poly(propylene glycol)(meth)acrylate,

• alkilany ether poly(ethylene glycol-block-propylene glycol)(meth)acrylate,

• transparent Monomeric units of Olkiluoto ether poly(ethylene glycol-block-caprolacton)(meth)acrylate or mixtures thereof.

In the variants of implementation, the transparent segment may contain one or more transparent Monomeric units obtained by polymerization of a monomer having two functional groups, which can be polimerizuet whereby are merging two polymer main chain through a single transparent Monomeric unit.

In more specific embodiments, the implementation, the monomer having two functional the global group, you can polymerizate may be:

• divinylbenzene,

• poly(ethylene glycol)di(meth)acrylate,

• poly(propylene glycol)di(meth)acrylate,

• statistical copolymer - poly(ethyleneglycol)di(meth)acrylate,

• poly(propylene glycol)-block-polycaprolactone(meth)acrylate,

• poly(ethylene glycol)-block-polytetrahydrofuran(meth)acrylate,

• literalinclude(meth)acrylate,

• literalinclude(meth)acrylate or mixtures thereof.

The present invention also relates to a method of manufacturing polymer particles. The method includes (a) providing a chromophore that absorbs infrared radiation in the near field, the first and second monomers, which can be polimerizuet; where the second monomer and the chromophore contains suitable functional groups for their connection; the polymerization of the monomers in the hydrophilic environment in the presence of initiator, whereby obtain polymer particles; and attaching a chromophore to the second monomer on the surface of the polymer particles.

In embodiments, the implementation of this method, the chromophore can be attached to the second monomer via a covalent bond. Alternatively, the chromophore can be attached to the second monomer via electrostatic interaction.

In specific embodiments, the implementation, the initiator may be 2,2'-asabiriza utionary, the ammonium persulfate, benzoyl peroxide or copper bromide.

In the variants of implementation, hydrophilic medium may be water, alcohol, acetonitrile, dimethyl ketone or a mixture.

The present invention also relates to a cover composition containing polymer particles of the present invention and reactive itaniemi oligomer.

In the variants of implementation, covering the composition may contain between about 10 and about 90% of the dry weight of the polymer particles. Also, covering the composition may contain between about 10 and about 80% of the dry weight of the reactive yedoniah oligomer. In specific embodiments, implementation, reactive iodonium the oligomer can be Tuxedo® 06C051A photopolymer.

Also, in the variants of implementation, covering the composition may further contain a polymeric binder. More specifically, the cover composition may contain between about 2 and about 40% of the dry weight of the polymeric binder. In specific embodiments, implementation, polymeric binder can be Tuxedo® XCP10 or Tuxedo® XAP02.

In the variants of implementation, covering the composition may further contain a coloring agent, a stabilizer, a light-sensitive substance, or a mixture thereof. Covering the composition may contain between when listello, 0.5 and about 10% of the dry weight colorants, stabilizers, light-sensitive substances or mixtures thereof.

The present invention also relates to a negative lithographic offset printing plate, containing (a) a substrate; (b) a hydrophilic bottom layer; and (c) the upper layer, forming an image upon irradiation of a laser, in which the upper layer, forming an image upon irradiation of the laser contains polymer particles of the present invention. More specifically, the upper layer forming an image upon irradiation of the laser may include covering the composition of the present invention, as described above.

Detailed description of the present invention

Polymer particles that absorb infrared radiation in the near-field

Now consider the present invention in more detail, it relates to polymeric particles, absorbing infrared radiation in the near field containing polymer having at least one peak absorption between 700 and 1100 nm (i.e. in the range of infrared radiation in the near field), and methods for their manufacture and use.

More specifically, the polymer contained in the polymer particles that absorb infrared radiation in the near field, the present invention has a hydrophobic polymer main chain and contains at least one Sigma is t, absorbing infrared radiation in the near field, and at least one segment that is transparent to infrared radiation in the near field.

As used in this description, the segment that absorbs infrared radiation in the near field, is a segment of a polymer containing one or more Monomeric units, which absorb infrared radiation in the near field. Similarly, the segment is transparent to infrared radiation in the near field, is a segment of a polymer containing one or more thermally directionspublic Monomeric units, are transparent to infrared radiation in the near field.

As used in this description, "the main chain of the polymer is the number of covalently linked atoms, which together form a continuous chain of the polymer.

In this polymer, the segments that absorb infrared radiation in the near field, that is, at least, some of the absorbing monomer units contained therein, is connected for this purpose with at least one chromophore that absorbs infrared radiation in the near field, i.e. the chromophore having at least one peak absorption between 700 and 1100 nm. As explained below, the transparent segments contain one or more thermally directionspublic Monomeric units, are transparent to infrared radiation the Oia in the near field.

Polymer particles that absorb infrared radiation in the near field, have a particle size between 60 and 1000 nm. In specific embodiments, implementation, polymer particles that absorb infrared radiation in the near field of the present invention may have a particle size of between 200 and 600 nm.

Segments that absorb infrared radiation in the near field, absorb the incident infrared radiation in the near field and generate heat, which causes coagulation of the polymer particles. As used in this description, "coagulation" refers to the process by which neighboring polymer particles are in contact and fused.

When the polymer particles used in the cover compositions of the present invention, the data segments also become sensitive to reactive iodonium the oligomers present in the coating to generate free radicals. Without being bound by theory, believe that this is probably the result of hemolytic cleavage reaction. Then, the formed free radicals cause the formation of crosslinks between the reactive functional groups (for example, acrylates and methacrylates) reactive iodonium oligomers and polymeric binder, if any.

Coagulation of the polymer parts and the formation of cross-reactive iodonium oligomers and, if they are, a polymeric binder make outer space covering more strongly related; causing that they are better attached to the substrate. Coatings containing polymer particles that absorb infrared radiation in the near field of the present invention, therefore, are especially preferred for machine manifestations, but are not limited to a single application.

In contrast, the segments are transparent to infrared radiation in the near field, are transparent to infrared radiation in the near field, which means that they, in particular, doesn't react chemically or physically with this exposure. In other words, the data segments are thermally directionspanel. They are subjected to coagulation of the polymer particles, but they are not the driving force or the cause of this coagulation or any other physical or chemical changes in the infrared radiation in the near field.

In the variants of implementation, the molecular weight of the polymer can be greater than, or equal to about 3000 daltons.

In the variants of implementation, the chromophores that absorb infrared radiation in the near field, can be covalently attached to the main polymer chain or attached via electrostatic interaction. Camisoles in this description, "covalently attached" means associated covalent bond. Covalent bond is a well-known form of chemical bonding that is characterized by the distribution of pairs of electrons between atoms. As used herein, "attached through electrostatic interaction" refers to the associated ionic bond. The ionic bond is a well-known type of chemical bond due to the electrostatic forces between two oppositely charged ions.

General chemical structure of the polymer contained in the polymer particles that absorb infrared radiation in the near field of this invention may be:

in which

• G1 represents a segment of absorbing infrared radiation in the near field;

• G2 is thermally directionspanel, i.e. transparent to infrared radiation in the near field, the segment; and

• G1 and G2 form a hydrophobic main chain;

• a and b independently represent molar relationship, which may vary between 0.01 and 0.99; and

• the chromophore covalently attached or electrostatically bind with hydrophobic main chain as side groups.

As used herein, "side group"is a group of atoms attached to the bases of the second long chain molecules, such as a polymer.

Segments that absorb infrared radiation in the near-field

Segments that absorb infrared radiation in the near field of the present invention, can be obtained as described for segment E, which absorbs infrared radiation in the near field" in the U.S. patents 6124425 and 6177182 that are entered into this description by reference.

In specific embodiments, implementation, chromophores that absorb infrared radiation in the near field, can be attached to the polymer main chain by covalent bonds, such as segments that absorb infrared radiation in the near field, the following:

in which

• NIR represents a chromophore that absorbs infrared radiation in the near field;

• R1 is hydrogen or alkyl with 1-18 carbon atoms;

• X represents an anionic counterion bromide, chloride, iodide, tosilata, triflate, triptorelin carbonate, dodecyl of benzosulfimide, tetraphenylborate, alkyl-triphenylborane, tetrafluoroborate or hexafluoroantimonate;

• M is oxygen, sulfur or dialkylamino;

• a is the molar ratio, which may vary between 0.01 and 0.99; and

• m represents the number of repeating units, which may vary between 1 and 5.

In other embodiments done by the means, the chromophores that absorb infrared radiation in the near field, can be attached to the polymer main chain through a polyether linker. Non-limiting examples of segments that absorb infrared radiation in the near field, which contains a polyether linker, include:

in which

• a is the molar ratio between 0.01 and 0.99;

• R represents hydrogen or methyl;

• R1 is C1-C8alkyl or C1-C8alkyloxy; w represents the number of repeating units between 10 and 50;

• m represents the number of repeating units, which may vary between 1 and 10;

• Y represents a linear or branched alkyl with 2 to 4 carbon atoms;

• L is divalently linker, which can have the following structure,in which Q-NIR and (YO)Wthe group also provided for clarity and j represents the number of repeating units, which may vary from 0 to 10:

• Q represents a spacer elements group, incorporating a chromophore that absorbs infrared radiation in the near field, to devalentino the linker; and

• NIR represents a chromophore that absorbs infrared radiation in the near field.

In more specific embodiments, implementation, Q spacer elements, the group may have to follow what their patterns, in which L and NIR groups are also shown for clarity:

in which R2 represents a C1-C8alkyl chain or C1-C8alkoxy chain; R3 is the same as R2 or a phenyl ring substituted by H or R2; and A represents an anion. In even more specific embodiments, the implementation, the anion A may be bromide, chloride, iodide, tosylate, tetraphenylborate, alkyldiphenylamine, tetrafluoroborate or hexafluoroantimonate.

The chromophore that absorbs infrared radiation in the near field region (NIR), attached to the absorbing segments, can have the following structure:

in which

each D1 and D2 is independently-O-, -S-, -Se-, -CH=CH - and-C(CH3)2; each of Z1 and Z2 independently represents one or more condensed substituted or unsubstituted aromatic ring; h can vary from 2 to 8; n represents 0 or 1; M represents hydrogen or a cationic counterion selected from Na, K and tetraalkylammonium salts.

A1 represents an anionic counterion bromide, chloride, iodide, tosilata, triflate, cryptomaterial, dodecylbenzensulfonate and tetrafluoroborate, tetraphenylborate or triphenyl-n-butylborane. Each R3 and R7 independently represent hydrogen or alkyl; and each R4 and R5 independently represents alkyl, aryl alkyl, guide oxyalkyl, aminoalkyl, carboxyethyl, sulfoalkyl, acetoxyethyl, polyester or Deputy, which can be polymerizate, of the formula:

in which m represents the number of repeating units, which may vary between 0 and 50; and R represents hydrogen or methyl.

Options exercise of the polymer particles of the present invention, the stitching between the two polymer main chains can occur through two segments that absorb infrared radiation in the near field, and one chromophore that absorbs infrared radiation in the near field as in example 10 (figure 34). In this case, the NIR chromophore can be part of two segments that absorb infrared radiation in the near field and, therefore, must allow two covalent bonds. An example of such NIR chromophore is:

in which A1 represents a counterion. In specific embodiments, implementation, this counterion may be bromide, chloride, iodide, tosylate, triflate, cryptomaterial, dodecylbenzensulfonate and tetrafluoroborate, tetraphenylborate or triphenyl-n-butylboron.

As used herein, "cross-connection" is a covalent bond linking one polymer main chain with the other.

In specific embodiments, implementation, segments, absorbing infrakrasnoe radiation in the near field, may be, as shown in figures 1-10, in which R represents hydrogen or methyl, a represents a molar ratio ranging between 0.1 and 0.9, and w represents the number of monomer units which can vary between 5 and 70, R4 and R5 are as described above for NIR chromophore, and A1 represents a counterion. In specific embodiments, the implementation, the counterion may be bromide, chloride, iodide, tosylate, triflate, triptorelin carbonate, dodecylbenzensulfonate and tetrafluoroborate, tetraphenylborate or triphenyl-n-butylboron.

The segment is transparent to infrared radiation in the near-field

The segments are transparent to infrared radiation in the near field, can be obtained by polymerization of one or more of the following comonomers include styrene, substituted styrene, alfamethylstyrene, 4-vinylphenol, 3-vinylbenzene, ester of acrylic acid, methacrylic acid, Acrylonitrile, acrylamide, methacrylamide, venilale, vinyl ether, vinyl ester, 9-vinylcarbazole and vinylphosphonic acid.

Also, the segments are transparent to infrared radiation in the near field, can be obtained by polymerization of a linear or branched polyester monomers having the following General structure:

H2C=C(R)-COO-(YO)W-Y-T

H2C=C(R)-COO-CH2CH2-NHCO-O(CH2CH2O)W-CH[H 2-(OCH2CH2)W-Y-T]2and mixtures thereof, in which

• R represents a hydrogen atom or methyl group;

• Y is an alkyl chain with 2 to 4 carbon atoms;

• w represents the number of repeating units, which may vary between 5 and 50; and

• T is hydroxy, alkoxy, aryloxy, carboxylic acid, acid or phosphoric acid as the terminal group, and their salts.

More specifically, the segment that absorbs infrared radiation in the near field can contain one or more of:

• poly(ethylene glycol)(meth)acrylate,

• poly(propylene glycol)(meth)acrylate,

• poly(ethylene glycol-block-propylene glycol)(meth)acrylate,

• poly(ethylene glycol-block-caprolacton)(meth)acrylate,

• Olkiluoto ether poly(ethylene glycol)(meth)acrylate,

• Olkiluoto ether of poly(propylene glycol)(meth)acrylate,

• Olkiluoto ether poly(ethylene glycol-block-propylene glycol) (meth)acrylate or

• Olkiluoto ether poly(ethylene glycol-block-caprolacton)(meth)acrylate.

The segments are transparent to infrared radiation in the near field can be obtained by polymerization of one or more monomers having two functional groups which can be polimerizuet, which may form a network of cross-links within the chain. Non-limiting examples of the quiet monomers include:

• divinylbenzene,

• poly(ethylene glycol)di(meth)acrylate,

• poly(propylene glycol)di(meth)acrylate,

• statistical copolymer - poly(ethylene glycol-propylene glycol)di(meth)acrylate,

• poly(propylene glycol)-block-polycaprolactone(meth)acrylate,

• poly(ethylene glycol)-block-polytetrahydrofuran(meth)acrylate,

• literalinclude(meth)acrylate, and

• literalinclude(meth)acrylate.

Examples of polymers made through their segments, are transparent to infrared radiation in the near field can be found in figures 11-13, in which a and b are molar relationship, which may vary between 0.01 and 0.99; k, h and I are the molar relationship, which can vary between 0.02 and 0,098; and m and w are the number of repeating units, which may vary between 5 and 50.

Both types of formation of crosslinks, i.e. the formation of cross-links through two segments that absorb infrared radiation in the near field, and one chromophore that absorbs infrared radiation in the near field and the formation of crosslinks through the segment, transparent to infrared radiation in the near field may be present simultaneously.

Ways to get

The present invention also relates to methods of producing the above polymer particles that absorb infrared radiation in b is igna area.

Polymer particles that absorb infrared radiation in the near field, can be made using dorectory synthesis, in which particles are prepared by polymerization with the transfer of the atoms of free-radical or ionic polymerization of the monomers in the hydrophilic environment, such as water, alcohol, acetonitrile, dimethyl ketone or a mixture thereof, using appropriate initiators. Then, the chromophores that absorb infrared radiation in the near field, grafted on the surface of the polymer particles through covalent binding.

More specifically, the polymer particles can be made: (A) providing a chromophore absorbing infrared radiation in the near field, the first and second monomers, which can be polimerizuet; where mentioned second monomer and the above-mentioned chromophore contains suitable functional groups to form between a communication; (B) polymerize mentioned first and second monomer in the hydrophilic environment in the presence of initiator, whereby obtain polymer particles; and (C) attaching the said chromophore to the mentioned second monomer on the surface of the aforementioned polymer particles.

The initiator are compounds that cause the reaction of polymerization. You can use any initiator known to specialists in this field of technology, which is suitable for the sing in this way. For experts in the field of technology it is useful to select and use these initiators for the present polymerization. Non-limiting examples of initiators are 2,2'-azobisisobutyronitrile, ammonium persulfate, benzoyl peroxide and copper bromide.

Covering songs

The present invention also relates to a covering compositions for use in the production of negative manifested laser lithographic offset printing plates.

More specifically, the present invention relates to covering compositions containing (a) the above-mentioned polymer particles that absorb infrared radiation in the near field, (b) reactive itaniemi oligomers, and optionally, (c) reactive polymer binder, and (d) colorants and stabilizers.

The composition of this invention may contain between about 10 and about 80% of the dry weight of the polymer particles and between approximately 10 and approximately 80% of the dry weight iodonium oligomers. If they are present, the polymer binder can be between approximately 2 and approximately 40% of the dry weight of the composition. Each of the coloring agents and stabilizers can be between approximately 0.5 and approximately 10% of the dry weight of the composition.

Reaktsionnosposobnykh the e itaniemi oligomers:

Reactive itaniemi oligomers are iodonium salts containing one or more functional groups which can undergo radical and/or cationic polymerization. More specifically, itaniemi salt can contain groups that can radically polimerizuet, such as acrylate, (meth)acrylate and vinyl ether. These groups, which can be subjected to radical polymerization, it is possible to replace the aryl rings of itaniemi salt through urethane and/or urea linkages. The structure of these polymerizable iodonium oligomers described in provisional patent application U.S. No. 60/747474, which is introduced in this description by reference.

More specifically, reactive itaniemi oligomers can be an oligomer, commercially available from American Dye Source, Canada under the trade name Tuxedo® 06C051A photopolymer.

This product is obtained by heating 137 grams of a solution of 1,3-dioxolane containing 245 grams of Desmodur™ N100 (supplied by Bayer Canada), 310 grams of poly(ethylene glycol)acrylate (Mn ~375 supplied by the company Sigma-Aldrich, Canada), 244 grams of pentaerythritoltetranitrate (SR-444, supplied by Sartomer company, USA), 1 gram of hydroquinone (supplied by the company Sigma-Aldrich, Canada), 10 grams of Irganox 1035 (supplied by the company Ciba Specialty Chemicals, Switzerland) and 1 gram of dilaurate dibutyrate (supplied Sigma-Aldrich, Canada) at 60°C in oxygen atmosphere and continuous stirring for 10 hours. Was collected from the reaction vessel a sample of the reaction mixture, and its FTIR spectrum recorded on KBr tablets, showed a-N=C=O peak at 2274 cm-1. Then, slowly added to the reaction mixture of 75 grams [4-(2-hydroxy-1-tetradecenoic)phenyl]vinylidenechloride (supplied by American Dye Source Inc., Canada), which was stirred at 60°C for an additional 6 hours. Was collected from the reaction vessel a sample of the reaction mixture, and its FTIR spectrum recorded on KBr tablets, showed a-N=C=O peak at 2274 cm-1. Then, were added to the reaction mixture of 100 grams of dipentaerythritol (SR-399 delivered by the company Sartomer, USA), which was stirred at 60°C for an additional 3 hours. Was collected from the reaction vessel a sample of the reaction mixture, and its FTIR spectrum recorded on KBr tablets did not show-N=C=O peak at 2274 cm-1that reflected the fact that the reaction was completed. Received net viscous product was diluted 1,3-dioxolane to get 85% on dry residue solution. Possible theoretical chemical structure of this reactive yedoniah oligomer shown in figures 14-19.

Polymeric binder

The polymer binder used in the compositions of this invention provide properties, sposob is appropriate to form a good film, and solubility in aqueous solutions having a pH between 2 and 14.

More specifically, the polymeric binder can be cellulose polymers, non-ionic side groups, such as hydroxy, polyethylene oxide, polypropyleneoxide or polietilenoksid. Cellulosic polymers may contain anionic side groups, such as carboxylic acid, sulfonic acid, phosphoric acid, and their corresponding salts of lithium, sodium and potassium. Cellulosic polymers may contain cationic side groups, such as tetraalkylammonium salt. Cellulose polymer may contain reactive functional groups such as acrylate, methacrylate and vinylether that may be the formation of crosslinks in free radical polymerization.

Cellulose polymeric binder may be a binder, commercially available from American Dye Source, Inc. (Canada) under the trade name Tuxedo® XCP10, which has a theoretical chemical structure, shown in figure 20.

Methacrylate-containing cellulosic polymer Tuxedo® XCP10 photopolymer prepared by heating to 90 grams of 1,3-dioxolane containing 9.0 grams of hydroxypropylcellulose (Klucel E, supplied by the company Aqualon, USA) and 0.1 gram of dilaurate dibutyrate (supplied by the company Sigma-Aldrich, Canada) at 60°C under stirring and in an atmosphere of oxygen. Was slowly added to actionnow a mixture of one gram of 2-isocyanatoacetate (supplied by the company Sigma-Aldrich, Canada) and continued to stir at 60°C for 3 hours. Was collected from the reaction vessel a sample of the reaction mixture, and its FTIR spectrum recorded on KBr tablets did not show-N=C=O peak at 2274 cm-1that reflected the fact that the reaction was completed. Got a transparent viscous product with 10% solid residue.

The polymeric binder may also be soluble in water acetylene copolymers with 4-hydroxyproline, 3-hydroxyproline, 2-hydroxyproline, alkyl and hydroxyl functional groups. In the variants of implementation, the alkyl can be linear or branched alkyl having from 1 to 12 carbon atoms. Acetylene copolymers may also contain reactive towards free radicals functional groups such as acrylate and methacrylate.

Soluble in water acetaline binder copolymer may be a binder, commercially available from American Dye Source, Inc. (Canada) under the trade name Tuxedo® XAP02, which has a theoretical chemical structure, shown in figure 21, in which a = 0.02 and b = 0,18, c = 0,78 and d = 0,02.

Soluble in water acutally copolymer Tuxedo® XAP02 photopolymer synthesized by heating to 220 grams dimethylsulfoxide solution containing of 44.0 grams of polyvinyl alcohol (Celvol 103 supplied by the company Celanese, USA)at 60°C with continuous stirring and the nitrogen atmosphere. As a catalyst to the solution was added concentrated sulfuric acid (1.0 grams). Thirty minutes was slowly added to the reaction mixture of 12.2 grams of 4-hydroxybenzaldehyde. The reaction was continued at 60°C for 20 hours. Acutally copolymer was obtained by planting in acetone and then dried in air to constant weight. Was slowly added to 150 grams of dimethyl sulfoxide, which is dissolved 48.5 grams of the above obtained acatalog copolymer, of one and half a gram of 2-isocyanatoacetate (supplied by the company Sigma-Aldrich, Canada) and 5 drops of dilaurate disutility. The reaction mixture was stirred at 60°C in oxygen atmosphere for 3 hours. Was collected from the reaction vessel a sample of the reaction mixture, and its FTIR spectrum recorded on KBr tablets did not show-N=C=O peak at 2274 cm-1that reflected the fact that the reaction was completed. Tuxedo® XAP02 photopolymer was obtained by planting in acetone, then filtered and air-dried to constant weight.

Dye and stabilizers

Not necessarily, the coating of this invention may also contain dyes, to ensure a good printing image after image acquisition using a laser. You can use any dye known to experts in the art and suitable for the use of the Finance in the present compositions. These dyes may be, for example, Victoria blue BO, crystal violet, malachite green, and their derivatives. Also, these dyes can be components svetooborudovaniya that can be derived triarylamine, Xanten and isobenzofuranone. These give the color of the connection can be colorless and, then, to become painted or change its color from one to another in the presence of free radicals or acids. More specifically, these compounds can be:

3',6'-bis[N-[2-chlorophenyl]-N-methylamino]Spiro[2-butyl-1,1-dioxo[1,2-benzisothiazol-3(3H),9'-(9H)xanthene]] (prepared by the method of U.S. patent No. 4345017);

3',6'-bis[N-[2-[methanesulfonyl]phenyl]-N-methylamino]Spiro[2-butyl-1,1-dioxo[1,2-benzisothiazol-3(3H),9'-(9H)xanthene]] (prepared by the method of U.S. patent No. 4345017);

9 diethylamino[Spiro[12H-benzo(a)xanthene-12,1'(3'H)-isobenzofuran)-3'-one] (supplied by BF Goodrich company, Canada);

2'-di(phenylmethyl)amino-6'-[diethylamino]Spiro[isobenzofuran-1(3H),9'-(9H)xanthene]-3-one (supplied by BF Goodrich company, Canada);

3-[butyl-2-methylindol-3-yl]-3-[1-octyl-2-methylindol-3-yl]-1-(3H)-isobenzofuranone (supplied by BF Goodrich company, Canada);

6-[dimethylamino]-3,3-bis[4-dimethylamino]phenyl-(3H)-isobenzofuranone (supplied by BF Goodrich company, Canada);

2-[2-octyloxyphenyl]4-[4-dimethylaminophenyl]-6-phenylpyridine (the village is supplied by BF Goodrich company, Canada);

3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-asafetida (Blue-63, supplied by the firm Yamamoto Chemicals, Inc., Japan);

3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)Teledom (Blue-502, the company supplied Yamamoto Chemicals, Inc., Japan);

3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)Teledom (Blue-503, the company supplied Yamamoto Chemicals, Inc., Japan);

3-[2,2-bis(1-ethyl-2-methylindol-3-yl)vinyl]-3-(4-diethylaminophenyl)Teledom (GN169 supplied by the company Yamamoto Chemicals, Inc., Japan).

3,3-bis(1-n-butyl-2-methylindol-3-yl)Teledom (Red-40, supplied by the firm Yamamoto Chemicals, Inc., Japan); or

leucocrystaland purple and leucomalachite green, which are delivered by the company Sigma-Aldrich, Canada.

The above components cutabrasives can be used in combination with light-sensitive substances, such as derivatives of triazine and Rivisondoli. Photosensitive substances of this invention can be triazine B, triazine E and orthochlorobenzalmalononitrile. The combination of the components of svetooborudovaniya and light-sensitive substances can be used in the coatings of the present invention in amounts in the range from 0.5 to 5% of the dry weight.

Covering compositions of this invention may also, optionally, contain photo - and thermal stabilizers to prolong the shelf life of the printing plates in the process of storing the value and use. These stabilizers can be methoxyphenol, hydroxyphenol, phenothiazines, 3-mercaptotriazoles, monomethylamine ether of hydroquinone, 2,4-dihydroxybenzophenone and other phenolic compounds, which are commercially available, thanks Ciba Specialty Chemicals, such as Irganox 1035, Irganox 1010 and Irganox 565. These stabilizers can be used in the coatings of the present invention in amounts in the range from 0.5 to 5% of the dry weight.

Negative lithographic offset printing plates

This invention also relates to a negative lithographic offset printing plates, which contain a substrate, a hydrophilic bottom layer and show laser top layer containing the above-mentioned polymer particles.

More specifically, show laser top layer may contain the above-mentioned covering composition.

The substrate can be fibrillated or electrolytic powdered aluminum, which, then, antiserum phosphoric acid or a mixture of phosphoric and sulfuric acid. Also, the substrate may be a polyester, which cover a hydrophilic layer containing silicon dioxide, aluminum oxide or titanium oxide, made from polymers, such as polyvinyl alcohol and polyvinylacetals copolymer.

In the variants of implementation, hydrophilic bottom layer contains soluble entering the polymers and/or copolymers of acrylic acid, methacrylic acid, vinylphosphonic acid, poly(ethylene glycol)acrylate end-phosphoric acid residue, a poly(ethylene glycol)methacrylate end-phosphoric acid residue, a poly(ethylene glycol)acrylate end balance carboxylic acid, poly(ethylene glycol)methacrylate end-carboxylic acid residue, a poly(ethylene glycol)acrylate end balance sulfonic acids or poly(ethylene glycol)methacrylate with limit balance sulfonic acids.

If not differently stated, as used herein, "alkyl" denotes a linear or branched alkyl group having 1-12 carbon atoms, and "aryl" denotes an aryl group having 5-12 carbon atoms.

Other objectives, advantages and features of the present invention will become more apparent after reading the following non-limiting description of specific embodiments given by way of example only with reference to the accompanying drawings.

Brief description of drawings

In the accompanying drawings:

Figure 1-10 represent segments that absorb infrared radiation in the near field, according to the variants illustrated implementation of the present invention;

Figures 11-13 present polymer with a crosslinking according to the illustrated implementation options this is subramania;

Figure 14-19 represent reactive itaniemi oligomers that can be used with polymer particles according to the variants illustrated implementation of the present invention;

Figure 20 represents theoretical chemical structure of cellulose polymeric binder sold under the trade name Tuxedo® XCP10;

Figure 21 represents theoretical chemical structure of water-soluble acatalog copolymer binder sold under the trade name Tuxedo® XAP02;

Figure 22 represents the chromophores that absorb infrared radiation in the near field, which can be used for the manufacture of polymer particles according to the illustrated variant implementation of the invention;

Figure 23 represents the monomers based on poly(ethylene glycol), which can be used for the manufacture of polymer particles according to the illustrated variant implementation of the invention;

Figure 24 represents the technological structure and thermal stabilizer sold under the trade name Irganox 1035; and

Figures represent 25-35 NIRP01, NIRP02, NIRP03, NIRP04, NIRP05, NIRP06, NIRP07, NIRP08, NIRP09, NIRP10 and NIRP11 polymers according to the variants illustrated implementation of the present invention, respectively.

Description of specific options is sushestvennee

The present invention is illustrated more in detail in the following non-limiting examples.

GLOSSARY

Glossary of various chemicals used in the synthesis of polymer particles that absorb infrared radiation in the near field, and covering the formulations of examples.

Al substrate

An aluminum substrate prepared by fibrillarin or electrolytic grinding, anodization in phosphoric acid. Then it is washed with diluted solutions of water-soluble polymer and dried at 110°C. water-Soluble polymers can be acrylic, methacrylic polymers and polymers vinylphosphonic acid and their copolymers. With regard to included in the description of the examples, you can use the following water-soluble polymers: polyacrylic acid (Colloid 140 supplied by the company Kemira, Pesssyvania, USA), copolymer - poly(acrylic acid-vinylphosphonic acid) (CP30 supplied by the company Rhodia, USA) and the copolymer - poly(acrylic acid-methacrylamide) (PAMA10 supplied by American Dye Source, Canada).

The chromophores that absorb infrared radiation in the near-field

ADS796WS: Dye that absorbs infrared radiation in the near field region (λmax=796 nm in a solution of methanol), supplied by American Dye Source, Canada, which is represented by the structure of figure 22,A.

ADS82WS: Dye, absorbing infrared radiation in the near field region (λmax=828 nm in a solution of methanol), supplied by American Dye Source, Canada, which is represented by the structure of figure 22,B.

ADS825TC: Dye that absorbs infrared radiation in the near field region (λmax=825 nm in a solution of methanol), supplied by American Dye Source, Canada, which is represented by the structure of figure 22,C.

ADS838WS: Dye that absorbs infrared radiation in the near field region (λmax=838 nm in a solution of methanol), supplied by American Dye Source, Canada, which is represented by the structure of figure 22,D.

ADS856WS: Dye that absorbs infrared radiation in the near field region (λmax=856 nm in a solution of methanol), supplied by American Dye Source, Canada, which is represented by the structure of figure 22,E.

ADS825NA: Dye that absorbs infrared radiation in the near field region (λmax=825 nm in a solution of methanol), supplied by American Dye Source, Canada, which is represented by the structure of figure 22,F.

The monomers

AN: Acrylonitrile supplied by the company Sigma-Aldrich Canada.

PEGDA700DA: Poly(ethylene glycol)diacrylate, average Mn~700 supplied by the company Sigma-AIdrich, Canada.

PEGMA2080ME: Methyl ether of poly(ethylene glycol)(meth)acrylate, in the form of a 50% solution in water, average Mn~2080 supplied by the company Sigma-AIdrich, Canada.

PEGMA620CL: Poly(ethylene glycol)(meth)acrylate end chloride, average Mn~615 supplied by American Dye Source, Inc., Canada, who provided the structure of figure 23,A, in which m is equal to approximately 14.

PEGMA1500CL: Poly(ethylene glycol)(meth)acrylate end chloride having an average Mn~1500, which is supplied by American Dye Source, Inc., Canada, represented by the structure of figure 23,B in which w is approximately 30.

PEGMA1500N: Poly(ethylene glycol)(meth)acrylate end-trimethylammoniumchloride with average Mn~1500, which is supplied by American Dye Source, Inc., Canada, represented by the structure of figure 23,C, where w is equal to about 30.

ST: styrene supplied by the company Sigma-AIdrich Canada.

VBC: 4-Vinylbenzoic supplied by the company Sigma-AIdrich, Canada.

VCBZ: 9-Vinylcarbazole supplied by the company Sigma-AIdrich, Canada.

VPD: 4-Vinylpyridin supplied by the company Sigma-AIdrich, Canada.

Reactive oligomers and polymers

Tuxedo® 06C051A: a Mixture of reactive iodonium oligomers, supplied by American Dye Source, Inc. (Canada) under the trade name Tuxedo® 06C051A photopolymer.

Tuxedo® XCP10: Hydroxypropylcellulose having a (meth)acrylate functional group (1.0 mol per gram), supplied by American Dye Source, Inc. (Canada) under the trade name Tuxedo® XCP10 photopolymer.

Tuxedo® XAP02: Soluble in water acutally copolymer having a methacrylate functional group (1.0 mol per gram), supplied by American Dye Source, Inc. (Canada) under the trade name Tuxedo® XAP02 photopolymer.

Initiators, stabilizat the s and dyes

V64: 2,2'-Azobisisobutyronitrile initiator of free radicals, supplied by DuPont (United States) under the trade name Vazo 64™.

Irganox 1035: Technological and thermal stabilizer supplied by the company Ciba Specialty Chemicals (Switzerland), which is represented by the structure of figure 24.

Mercaptothiazole: Mercapto-3-triazole-1H,2,4 supplied by the company PCAS, France.

Blue-503: 3-(2-Ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phtalic supplied by the company Yamamoto Chemicals, Inc., Japan.

Synthesis and characterization of polymer particles that absorb infrared radiation in the near-field

Data synthesis was performed in a 4-necked glass flask equipped with a water refrigerator, mechanical stirrer, addition funnel and an inlet valve for nitrogen or air. The molecular structure of the obtained compounds was determined by FTIR spectroscopy (Perkin-Elmer, Model Spectrum 100). The average molecular weight of the obtained copolymer was determined by exclusion chromatography (Waters, Model Breeze), using a solution ofN,N-dimethylformamide (DMF), and calibrated with polystyrene standards. UV-visible spectra in the near infrared region of the synthesized polymers was measured in methanol solution or on a solid films using UV-VIS spectrophotometer (Perkin-Elmer, Model Lambda 35). The particle size was measured using Utrafine Particle Analyzer (Microtrac, Model UPA 150).

NOTE THE P 1

Polymer particles NIRP01 that absorb infrared radiation in the near field, was synthesized by heating a reaction mixture containing 200 grams of isopropanol, 50 grams of deionized water and 18.0 grams PEGMA1500CL, 40,0 grams'AN and 14.0 grams ST, 1 l 4-necked flask at 75°C in nitrogen atmosphere with continuous stirring. After heating for 30 minutes, was added to the reaction mixture 0.5 g V64. The solution became turbid within 30 minutes of polymerization, reflecting the formation of polymer particles. After 10 hours, the reaction mixture was added 0.5 grams V64 and the polymerization was continued in the next 14 hours at 75°C. Air was introduced into the reaction mixture, which was stirred at 75°C over the next 2 hours to complete the polymerization. Received in-patient milky-white solution of polymer particles. The particles had an average molecular weight of about 65,000 daltons. Then, of 10.5 grams ADS828WS was added to the reaction mixture, which was stirred at 75°C for 5 hours and got a viscous dark green solution of polymer particles that absorb infrared radiation in the near field. The solids content of the solution was adjusted to 20% (by weight)using isopropanol.

A dilute solution NIRP01 in methanol showed a strong absorption band with a maximum at about 825 nm, which shows that romover, absorbing infrared radiation in the near field was cultivated on the surface of the polymer particles. Determined that the average diameter of the resulting polymer particles NIRP01 that absorb infrared radiation in the near field, is approximately 280 nm, and theoretical chemical structure is shown in figure 25, in which a=0,0133, b=0,987, k=0,849, h=0,151 and w=30.

EXAMPLES 2-11

Polymer particles that absorb infrared radiation in the near field, examples 2-10 were synthesized as described in example 1. Compounds prepared in these examples, shown in figures 26-35 and are listed in table 1, together with their characteristics and connections used for their preparation. For clarity, the compound of example 1 are also shown in this table.

In all examples, the time required for the reaction mixture became turbid, was between about 30 and about 90 minutes.

Examples 1-7 relate to polymeric particles, absorbing infrared radiation in the near field without polymer main chains with crosslinking, whereas examples 8-10 relate to polymeric particles, absorbing infrared radiation in the near field, with the polymer main chains with crosslinking.

The particles of examples 8 and 9, which are shown in figures 32 and 33, the stitching is m is waiting for the two Monomeric units, with the number of repeating units is equal to "I". Other Monomeric units of the second polymer are crosslinked crosslinking with shows Monomeric units, not shown.

In example 10, the polymer particles that absorb infrared radiation in the near field, have their polymer main chain, which are stitched through a chromophore that absorbs infrared radiation in the near field, as can be seen in figure 34.

Machine-show negative lithographic printing plates

The following examples cover the mixture is applied on the Al substrate using a wire rod, and dried at 80°C hot air. The coating typically weigh approximately 0.9 g/m2.

The coated plate was displayed on the Creo Trendsetter 3244, using energy density specified in the examples. In all cases, the area irradiated by the laser, showed visible brown imprint.

All the developed plate was fixed on the Komori Sheet-Fed Press, Model Sprint S26, using HyPlus-H-Series black ink (supplied by Toyo Ink, Japan) and Mylan-UF200 hydrating solution (supplied by the firm MyLan Chemicals, Vietnam). Usually high-quality printed image on paper after approximately 30 prints and all plates could give more than Cai with high resolution.

EXAMPLE 12

Covering composition for native negative lithographic printing plates prepared by mixing the ingredients listed in table 2.

Obtained covering the mixture usually contains about 7.0 percent by weight of all solids in isopropanol.

The covered plate was shown when the energy density of 150 MJ/cm2.

EXAMPLE 13

Covering solutions prepared analogously to example 12, except that instead of NIRP01 used NIRP08. The covered plate was shown when the energy density of 150 MJ/cm2.

EXAMPLES 14-22

Covering solutions prepared analogously to example 12, except that NIRP01 replaced other polymer particles, absorbing infrared radiation in the near field, as shown in table 3. Coated plates showed at energy densities between 80 and 200 MJ/cm2an increase of 20 MJ/cm2. Energy density listed in table 3 are the densities required to obtain a plate capable of giving 10,000 copies.

EXAMPLE 23

Covering composition for machine-show negative lithographic printing plates prepared by mixing the ingredients listed in table 4.

Received covering compositions typically sod is neigh, approximately 7.0 percent by weight of all solids in isopropanol.

The covered plate was shown when the energy density of 150 MJ/cm2.

Although the present invention is described above by means of its specific embodiments, it can be modified without going beyond the scope and nature of this invention as defined in the attached claims.

1. Polymer particle having a particle size of between about 60 nm and about 1000 nm and containing a polymer which contains a hydrophobic main chain formed of at least: (a) one segment that absorbs infrared radiation in the near field, coupled with a chromophore that absorbs infrared radiation in the near field region having a peak absorption between about 700 nm and about 1100 nm; and
(b) one segment is transparent to infrared radiation in the near field,
where mentioned polymer particle coalesces with neighboring polymer particles under irradiation having a wavelength between about 700 nm and about 1100 nm.

2. Polymer particle according to claim 1, in which the said particle size is between approximately 200 nm and 600 nm.

3. Polymer particle according to claim 1, in which the said polymer has a molecular m is cel approximately 3000 Da or more.

4. Polymer particle according to claim 1, in which the said polymer has the following structure:

in which:
- G1 is mentioned absorbing segment;
- G2 is mentioned transparent segment;
- G1 and G2 form mentioned hydrophobic main chain;
a and b independently represent molar relationship between 0.01 and 0.99; and
mentioned chromophore covalently or electrostatically attached to the above-mentioned hydrophobic main chain as side groups.

5. Polymer particle according to claim 1, in which the aforementioned absorbing segment contains:
,,,or

in which:
- NIR is mentioned chromophore;
- R1 is hydrogen or C1-C18alkyl;
X represents an anionic counterion bromide, chloride, iodide, tosilata, triflate, cryptomaterial, dodecylbenzensulfonate, tetraphenylborate, alkyldiphenylamine, tetrafluoroborate or hexafluoroantimonate;
M represents oxygen, sulfur or dialkylamino;
- a represents the molar ratio between 0.01 and 0.99; and
- m represents the number of repeating units between 1 and 5.

6. Polymer particle according to claim 1, in which the aforementioned absorbing segment contains poliey the hydrated linker, covalently attaching the said chromophore to the mentioned main polymer chain.

7. Polymer particle according to claim 6, in which the aforementioned absorbing segment contains:
,
,
,
or

in which:
- a represents the molar ratio between 0.01 and 0.99;
- R represents hydrogen or methyl;
- R1 is C1-C8alkyl or C1-C8alkyloxy;
- w represents the number of repeating units between 10 and 50;
- m represents the number of repeating units between 1 and 10;
- Y represents a linear or branched C2-C4alkyl;
Q represents a spacer elements group;
- NIR is mentioned chromophore;
- L is:
,or

in which Q-NIR and (YO)wgroups are shown for clarity and j represents the number of repeating units between 0 and 10.

8. Polymer particle according to claim 7, in which the mentioned spacer elements group is:
,,,
,or,
in which L and NIR bands is shown for clarity; R2 represents C1-C8alkyl or C1-C8alkyloxy; R3 is the same as R2 or a phenyl ring, substituted N, or R2; and a represents an anion.

9. The polymer particle of claim 8 in which the said anion is bromide, chloride, iodide, tosylate, tetraphenylborate, alkyldiphenylamine, tetrafluoroborate or hexafluoroantimonate.

10. Polymer particle according to claim 1, in which two main polymer chain stitched through two absorbing segment and one chromophore.

11. Polymer particle according to claim 1, in which the said chromophore is:

or

in which:
each D1 and D2 independently represent-O-, -S-, -Se-, -CH=CH-, or-C(CH3)2-;
each of Z1 and Z2 independently represent one or more fused substituted or unsubstituted aromatic ring;
- h is an integer between 2 and 8;
n represents 0 or 1;
M represents hydrogen or a cationic counterion such as Na, K or tetraalkylammonium salt;
A1 represents an anionic counterion bromide, chloride, iodide, tosilata, triflate, cryptomaterial, dodecylbenzensulfonate, tetrafluoroborate, tetraphenylborate or triphenyl-n-butylborane;
- R3 represents hydrogen or alkyl; and
each R4 and R5 independently depict ablaut alkyl, aryl alkyl, hydroxyalkyl, aminoalkyl, carboxyethyl, sulfoalkyl, acetoxyethyl, polyester or Deputy, which can be polymerizate, of the formula:
,
,
or

in which m represents the number of repeating units between 0 and 50; and R represents hydrogen or methyl.

12. Polymer particle according to claim 1, in which the aforementioned transparent segment contains styrene, substituted styrene, alpha-methylsterol, 4-vinylphenol, 3-vinylbenzene, ester of acrylic acid, methacrylic acid, Acrylonitrile, acrylamide, methacrylamide, venilale, vinyl ester, vinyl ether, 9-vinylcarbazole or vinylphosphonic acid as a transparent Monomeric units.

13. Polymer particle according to claim 1, in which the aforementioned transparent segment contains transparent Monomeric units obtained by the polymerization of polyester monomers of the formula:
H2C=C(R)-COO-(YO)w-Y-T
H2C=C(R)-COO-CH2CH2-NHCO-O(CH2CH2O)w-CH[CH2-(OCH2CH2)w-Y-T]2
or mixtures thereof, in which:
- R represents hydrogen or methyl;
- Y represents C2-C4alkyl;
- w represents the number of repeating units between 5 and 50; and
- T is end groups hydroxy, alkoxy, alloc and, carboxylic acids, sulfonic acids or phosphoric acids and their salts.

14. Polymer particle according to claim 1, in which the aforementioned transparent segment contains monomer units:
- poly(ethylene glycol)(meth)acrylate,
- poly(propylene glycol)(meth)acrylate,
- poly(ethylene glycol-block-propylene glycol)(meth)acrylate,
- poly(ethylene glycol-block-caprolacton)(meth)acrylate,
- Olkiluoto ether poly(ethylene glycol)(meth)acrylate,
- Olkiluoto ether of poly(propylene glycol)(meth)acrylate,
- Olkiluoto ether poly(ethylene glycol-block-propylene glycol)(meth)acrylate,
- Olkiluoto ether poly(ethylene glycol-block-caprolacton)(meth)acrylate or mixtures thereof.

15. Polymer particle according to claim 1, in which the aforementioned transparent segment contains one or more transparent monomer unit obtained by polymerization of a monomer having two functional groups which can be polimerizuet, through which there is a joining of two polymer main chain through a single transparent Monomeric link.

16. Polymer particle according to item 15, in which the above-mentioned monomer having two functional groups which can be polimerizuet is:
- divinylbenzene,
- poly(ethylene glycol)di(meth)acrylate,
- poly(propylene glycol)di(meth)acrylate,
- statistical copolymer poly(ethylene glycol-propylene glycol)di(meth)acrylate,
- poly(n is openinglabel)-block-polycaprolactone(meth)acrylate,
- poly(ethylene glycol)-block-polytetrahydrofuran(meth)acrylate,
- literalistically(meth)acrylate,
- literalistically(meth)acrylate or
- mixtures thereof.

17. The method of obtaining polymer particles according to any one of claims 1 to 16, including:
(a) obtaining a chromophore that absorbs infrared radiation in the near field, the first and second monomers, which can be polimerizuet; where mentioned second monomer and the above-mentioned chromophore contains suitable functional groups for coupling together;
(b) polymerization of the aforementioned first and second monomers in the hydrophilic environment in the presence of an initiator to obtain polymer particles; and
(c) attaching the above chromophore to the mentioned second monomer on the surface of the aforementioned polymer particles.

18. The method according to 17, in which the said chromophore is attached to the second monomer via covalent bonds.

19. The method according to 17, in which the said chromophore is attached to the second monomer via electrostatic interaction.

20. The method according to 17, in which the said initiator is 2,2'-azobisisobutyronitrile, ammonium persulfate, benzoyl peroxide or copper bromide.

21. The method according to 17, in which the aforementioned hydrophilic medium is water, alcohol, acetonitrile, dimethyl ketone or a mixture.

22. Covering composition containing
(a) Polym rye particles according to any one of claims 1 to 16; and
(b) reactive itaniemi oligomer.

23. Covering the composition according to item 22, containing between about 10 and about 90% by dry weight of the aforementioned polymer particles.

24. Covering the composition according to item 22, containing between about 10 and about 90% by dry weight mentioned reactive yedoniah oligomer.

25. Covering the composition according to item 22, in which the mentioned reactive iodonium the oligomer is Tuxedo® 06C051A photopolymer.

26. Covering the composition according to item 22, which additionally contains a polymeric binder.

27. Covering the composition according to p containing between about 2 and about 40% by dry weight of the aforementioned polymer binder.

28. Covering the composition according to p, in which the mentioned polymeric binder is a Tuxedo® XCP10 or Tuxedo® XAP02.

29. Covering the composition according to item 22, further containing a dye stabilizer, a light-sensitive substance, or a mixture thereof.

30. Covering the composition according to clause 29, which covers the composition comprises between about 0.5 and about 10% by dry weight mentioned coloring substance, stabilizer, light-sensitive substances or mixtures thereof.

31. Negative lithographic offset printing plate, comprising:
(a) a substrate;
(b) a hydrophilic lower the layer, and
(c) show laser top layer, in which the mentioned show laser top layer contains polymer particles according to claim 1.

32. Plate on p, which show laser top layer contains a polymer particle according to claim 1 comprising covering composition according to item 22.



 

Same patents:

Protective coating // 2427601

FIELD: physics.

SUBSTANCE: protective coating has a base consisting of two layers of intertwined rows of threads attached by radiotransparent material, with a film of hydrogenated carbon ingrained with particles of ferromagnetic material is deposited on each layer through vacuum sputtering. On the surface of the film which is deposited on the outer layer of the intertwined rows of threads, there is a lacquer coating obtained from a suspension which contains a fluorinated polymer, zinc sulphide with a hexagonal crystal structure, selenium, sulphur, a catalyst, a wetting agent and a curing agent.

EFFECT: high efficiency of radio absorption and concealment in optical-location infrared band and on laser points of the optical band.

9 cl, 1 dwg, 2 tbl, 14 ex

FIELD: chemistry.

SUBSTANCE: composition contains two liquid components which are combined before applying the composition on the surface of the article. The first component is an epoxy resin hardener and the second is an epoxy resin based composition which contains (in wt %) two dispersed electroconductive filler materials different on the form of particles (graphite 50-70 and carbon fibre 1-5) 0.2-1, thermoplastic polyurethane 0.2-1, epoxy resin - the rest up to 100.

EFFECT: invention enables to lower microwave radiation.

2 cl, 1 dwg, 4 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to formulation and technology of applying electromagnetic wave absorbing coatings on metal or rubber surfaces. The coating for absorbing electromagnetic energy of radar signals in the wavelength range of 1-20 cm is used to lower effective reflecting power of metal and rubber surfaces of ground-based and sea objects (tanks, artillery mounts, ships) for antiradar masking from attack by weapons flying towards a target guided by a radar signal (missiles, artillery projectiles, aeroplanes) based on a composition which contains binder in form of chlorosulphonated polyethylene CSPE-MR which can absorb large amounts of electromagnetic energy and is dissolved in toluene. Also dispersed in the solution is 3-20 mm long carbon fibre on which an insulating coating is deposited, curing agents and a component with large volume of air pockets - micro-glass spheres. The composition contains chlorosulphonated polyethylene CSPE-MR, toluene, magnesium oxide (MgO), zinc oxide (ZnO), polyethylene glycol PEG-35 or monoalkylphenol ether of polyethylene glycol OP-7 or OP-10, diphenylguanidine, micro-glass spheres MSO-A9, carbon fibre UKN-300, used in the composition for a 1st coating layer; carbon fibre Uglen R-9 used in the composition for a 2nd coating layer; steorox-6. The first layer based on the said composition is deposited on metal or rubber surfaces primed with a primer based on glyptal resin in order to increase adhesion by spraying a thickness of up to 2.8-3.2 mm (providing approximately 20-22 passages) and holding after each passage at 15 - 35°C for not less than 15 minutes and drying after applying the 1st layer at 15-35°C for not less than 24 hours or at 65 - 75°C for 3-4 hours. A 2nd layer of the same composition is deposited on top of the 1st layer, where carbon fibre Uglen R-9 is used instead of carbon fibre UKN-300, with total thickness of not less than 5.5 mm (approximately 18-20 passages) with holding and drying similar to those used when depositing the 1st layer.

EFFECT: low effective reflecting power of metal and rubber surfaces of ground-based and sea objects (tanks, artillery mounts, ships) for their antiradar masking from attack by weapons flying towards a target guided by a radar signal (missiles, artillery projectiles, aeroplanes).

1 ex

FIELD: physics.

SUBSTANCE: element is characterised by at least one combination of substrate material selected from polymer, a lacquer coated substrate, fibre material, a substrate with hydraulically bound mass and/or non-woven material, containing components consisting of inorganic and/or organic light filler, hollow spaces formed in the substrate material by gases, dyes, organic pigments, inorganic pigments, inorganic and/or organic nanomaterials. The combination has thermal conductivity of not less than 0.4 [W/m·K], apparent density low of less than 1.4 g/cm3, average reflection in the 400-700 nm wavelength range of visible light less than 50% and average reflection in the 700-1000 nm wavelength range of near-infrared radiation greater than 50%.

EFFECT: low heating in the sun, lower heat output compared to conventional dark surfaces, heat insulating effect.

26 cl, 10 ex, 11 dwg

FIELD: chemistry.

SUBSTANCE: composition contains absorbing filler (80-90 pts. wt); BS-10T adhesive - solution of novalac-type polyvinylformalethylal resin in organic solvents (ethanol and ethylacetate) with addition of ethyl orthosilicate, urotropin and quinoline (26-30 pts. wt); and cyclohexanone (15-20 pts. wt). The absorbing filler used is carbonyl iron, alsifer powder, technical carbon P 803 or a dry colloidal-graphite C-1 preparation.

EFFECT: obtained composition has a wide range of operating temperature, increases attenuation of microwave signals and forms a quality coating.

1 cl, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to radio engineering, particularly to electromagnetic wave absorbers, including in the microwave range and can be used for ensuring electromagnetic compatibility of radio-electronic equipment, biological protection from effects of radio emissions generated by different scientific and household devices, reducing radar visibility of different objects and is aimed at reducing coefficient of reflection of electromagnetic waves and widening the frequency range of the radar absorbent material, as well as simplifying the method of making said material. When making said material, an oxide hexagonal ferrimagnetic material with a W-shape is mechanically treated in a mechanoactivator for 30-300 seconds with power density factor of 20-40 g and mixing it with epoxy resin in the following ratio, wt %: oxide hexagonal ferromagnetic material with W-shape - 70-91, epoxy resin - 9-30.

EFFECT: use of chemical methods and expensive reagents is completely avoided, the material obtained using the said method has lower coefficient of reflection and a wide frequency range and can be used for making efficient radar absorbent coatings.

2 cl, 2 tbl

FIELD: physics.

SUBSTANCE: composite material is proposed for absorbing electromagnetic waves based on magnetodielectric material, which contains polymer dielectric binder, which is a polyorganosilixane oligomer with a catalyst additive, and magnetodielectric finely dispersed filler made from iron-aluminium alloy in ratio of (87.5-88.5):(12.5-11.5) wt % respectively, with the following ratio of initial components in the composite material (wt %): polyorganosiloxane oligomer - 33.5 to 40.0; catalyst - 1.5 to 2.0; magnetodielectric finely dispersed filler - 65 to 58.

EFFECT: material has high absorption coefficient, wide range of operating frequencies and improved operational characteristics.

1 cl, 1 tbl, 1 dwg, 5 ex

FIELD: instrument making.

SUBSTANCE: invention relates to coats absorbing electromagnetic radiation. Proposed coat comprises a warp consisting of aramide high-modulus Kevlar-type fabric with absorbing film applied thereon. Various-type films are applied on every warp. One type represents sawed ferrite with nano-size clusters of Ni and Co ingrained thereto, while the second type is made from evaporated hydrogenated carbon with nano-size clusters of Ni and Co ingrained thereto. The films are evaporated onto aramide fabric on both sides. In designing the fabric structure, layers are taken to alternate so that the concentration of ferromagnetic clusters in films of adjacent layers varies from low (40 to 60% at.) to high (60 to 80% at.).

EFFECT: higher RF absorbing properties in 6 to 40 GHz range and expanded frequency range in lower SHF range band of 2 to 6 GHz.

2 cl, 3 ex, 8 dwg

FIELD: chemistry.

SUBSTANCE: proposed polymer composition contains (in wt pts): synthetic low-molecular dimethylsiloxane rubber CKTH (15-25), cold setting catalyst №68 (0.6-1.0), absorbing filler - P-10 radio carbonyl iron (78-83).

EFFECT: high absorption properties with a small absorption layer.

1 cl, 2 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: proposed coating composition contains 1-15% of the mass is inorganic particles, with the average particle diameter from 5 to 30 nm; 0.05-3% of the mass is inorganic particles, with the average particle size from 0.2 to 5 microns; 1-15% of mass, organic-silane compound of the formula RnSi(OR')4-n, where R represents C1-C8-aminoalkyl group, glycidehydroxyalkyl group or isocyanatealkyl group; R' represents the lowest C1-C6 alkyl group; and n equals a whole number from 0 to 3; 50-85% of the mass is solvent, chosen from water and an organic solvent with an average boiling point of from 60°C to 150°C; 0.1-3% of the mass is photo-catalytic particles and 0.001-2% of the mass is an acid. Also described is the method of preparing the above mentioned coating composition, support such as a film or structural external material, having excellent ability to auto cleaning and resistant to stains, using the above mentioned coating composition, and the method of obtaining it. The coating composition in which inorganic particles containing hydroxyl groups are used can improve the initial hydrophilic nature of the usual coating agents, and also form a hydrophilic coat which has the angle of contact with water 30° or less, due to the use of two types of inorganic particles, having different diameters of particles. The composition can be used in the usual industrial line for constructional external materials without the addition of a separate coating line.

EFFECT: improvement in the capability of self-cleaning and resistance to dirtying of the composition and articles with its use.

12 cl, 9 tbl, 1 dwg, 7 ex

FIELD: chemistry.

SUBSTANCE: method involves film processing with gas mix of fluorine and nitrogen at fluorine concentration of 1 to 10 vol. %. Processed film is exposed to ammonia in aqueous solution or in gas mix for 10 seconds or less, with further film fanning with air.

EFFECT: possible application of plyolephine films with marks as package material for food storage due to neutralisation of hydrogen fluoride remaining at the film surface.

3 cl, 5 ex

FIELD: chemistry.

SUBSTANCE: method involves pre-treatment of objects with organic solvent (pentane, hexane, ethanol, carbon treatrachloride or their mixture), drying, treatment with a mixture of inert gas and fluorine with concentration of 2 to 5 vol % for 1 to 10 minutes, and then with the same mixture with concentration of 6 to 30 vol % for 10 to 300 minutes, and simultaneous elastic deformation of the object by bending in two opposite directions.

EFFECT: invention allows for reducing permeability of the material to low-molecular substances, increasing chemical resistance and reducing reagent consumption during modification of objects.

6 cl, 2 tbl, 2 dwg

FIELD: technological processes.

SUBSTANCE: sheet material for production of article from it contains metal wafer and system of polymer coating fixed to it. Internal layer of coating contains PET and modified PET as layer for adhesion of this system with wafer. As barrier layer coating contains layer that includes PET and PBT. External layer contains PET with non-sticking properties, for prevention of this material sticking to blanking tools at normal working temperatures of industrial blanking. Metal wafer is made of steel, or aluminium, or aluminium alloy. System of coating may be produced by extrusion of single layer or joint extrusion of at least two layers. Coating system may be produced by preliminary production of film and its fastening with wafer.

EFFECT: invention makes it possible to improve quality of drink cans production and to increase their shelf life and preservation of taste properties.

18 cl, 2 dwg, 7 tbl

FIELD: chemistry.

SUBSTANCE: method of the polymer surface modification includes processing the polymer surface by a pulsed plasma spraying of graphite target. Spraying is effected with a 0.9-0.9 Hz pulse frequency. In spraying, the surface is subjected to etching by independent ion-beam source in an oxygen-containing mix with inert gas, the oxygen concentration making 10-30 parts by volume.

EFFECT: hydrophilic-hydrophobic nanostructures are obtained on the polymer surfaces, they sizes being comparable to those of biologically-active molecules.

3 tbl, 1 ex

FIELD: polymers.

SUBSTANCE: invention relates to powder-like cross-linked products absorbing different liquid and based on partially neutralized, ethylene-unsaturated and comprising acidic groups of monomers. Invention proposes a powder-like polymeric product subjected for additional cross-linking and absorbing water, aqueous or serosa liquid and blood that is synthesized from: (a) polymerized ethylene-unsaturated and comprising acid groups of monomers neutralized by at least 25 mole%, 55-99.9 wt.-%, and (b) polymerized ethylene-unsaturated copolymerized with monomers of (a) monomers, 0-40 wt.-%; (c) one or some polymerized cross-linking agents, 0.1-5.0 wt.-%, and (d) water-soluble polymer, 0-30 wt.-%. Proposed product possesses the more effective properties being first of all the better capacity for transfer of absorbed liquids in a swollen state. Product can be subjected for surface cross-linking using a combination consisting of an organic cross-linking compound but with exception of polyols and cation as its salt in an aqueous solution. Also, invention proposes a diaper and hygienic article for adults based on the claimed product.

EFFECT: valuable properties of product and articles.

15 cl, 2 tbl, 29 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to a method for impregnating hydroxyl-containing polymers with functional agents by way of swelling in overcritical fluid, which process is intended for use in medicine, biotechnology, agriculture, food and chemical industries as therapeutic agents, adsorbents, depots for biologically active substances, catalysts, etc. Thus, object of invention was to develop efficient method for impregnating densely packed hydroxyl-containing polymers while preserving high hydrophilicity thereof. The problem was solved by pretreating polymer with a hydrogen bond acceptor selected from group consisting of urea, dichloroacetic acid, trifluoroacetic acid, and guanidinium chloride, and performing swelling in overcritical carbon dioxide at 32 to 100°C and pressure 7.5-25.0 MPa, after which treated polymer undergoes desorption to carbon dioxide level 2-10% and subjected to heat treatment at 80-200°C and atmospheric pressure to form cellular plastic, which is impregnated with functional agents in overcritical carbon dioxide medium at 32 to 100°C and pressure 7.5-35.0 MPa with periodicity 1-5 times.

EFFECT: increased efficiency of impregnation of densely packed hydroxyl-containing polymers due to preliminary splitting of hydrogen bonds and increasing porosity of polymers so enabling assortment of impregnated polymers to be enlarged.

3 cl, 1 tbl, 3 ex

FIELD: rubber industry.

SUBSTANCE: invention relates to processes used for surface modification of rubbers based on carbon-backbone rubber precursors. Process consists in treating rubbers with solution of reactive substance in organic solvent followed by treatment for 5-7 h under vulcanization temperature conditions with subsequent drying to remove solvent and heat treatment at vulcanization temperature for 40-60 min. Above-mentioned reactive substance is composed of, wt parts per 100 wt parts solvent: 2-mercaptobenzothiazole 4-5, sulfur 1-2, ultrafine powders of solid lubricants 8-10, phenol-formaldehyde resin 8-10, urotropin 0.5-1.0, and chloroparaffin (more than 70% Cl) 40-50.

EFFECT: increased fireproofness of rubber products at the same wear resistance and resistance to aggressive media.

2 tbl, 2 ex

FIELD: chemistry of polymers.

SUBSTANCE: invention describes a method for applying thin films made of polytetrafluoroethylene on surface of solid bodies. Method involves formation of film from tetrafluoroethylene vapor directly under pressure 0.1-20 torr by effect of electrons beam with energy 1-1000 keV in working chamber separated from electrons source. The process is carried out at density of electrons flow falling on solid body surface in the range from 30 to 6000 μA/cm2 followed by roasting applied films under vacuum or inert atmosphere without intermediate contact with air at temperatures 250-400°C for 0.5-1 h. Roasting films is carried out at 350°C for 1 h, and the process is carried out preferably at electrons flow density falling on surface of solid body in the range 100-3000 μA/cm2, tetrafluoroethylene vapor pressure in the range 1-10 torr and energy pf electrons beam 10-200 keV. The proposed method provides preparing uniform thin films made polytetrafluoroethylene showing high thermal stability and retaining low values of their dielectric penetrability. Invention can be used in electronic engineering, optics and medicinal equipments.

EFFECT: improved applying method.

3 cl, 1 tbl, 9 ex

FIELD: polymer materials.

SUBSTANCE: object of invention is to impart water- and oil-proofing properties to polymers, to reduce adhesion properties, and to modify dielectric properties of treated surface of polymers without changing base properties of polymer matrix. Invention consists in that polymer to be modified is treated with solution of perfluoro-2,4-dimethyl-3-ethyl-3-pentyl radical in perfluorinated solvents having concentrations from 0.5 to 20% at temperature above 80°C.

EFFECT: increased limiting wetting angle.

FIELD: polymer materials.

SUBSTANCE: invention relates to technology of fabrication and modification of man-made fibers and threads, in particular poly(vinylidene sulfide) threads, and can be used in chemical industry for manufacture of filter materials and in medicine as novel surgical threads and implants (endoprostheses) showing biological activity and thrombosis resistance. Thread made from poly(vinylidene sulfide) with carbine coating has diameter 0.10-0.15 mm, linear density from 13.81 to 31.09 tex, knot strength 621-640 MPa, and rupture strength 632-648 MPa. Knitted mesh is made from monofilament poly(vinylidene sulfide) thread and its structure is characterized by density 12-13 courses per 1 cm and contains loops from two thread systems with first system parameters: 6/7, 3/2, 4,5, 1/0, 3/2 and second system parameters: 1/0, 2/3, 1,0, 2/3, 1/0, 2/3. Method of manufacturing knitted mesh comprises making indicated knitted material from indicated thread with density 12-13 course/cm and two indicated thread systems, impregnating the mesh with dimethylsulfoxide or dimethylformamide during 1-4 h, and treating it with 15-17% n-butanol or n-propanol solution of potassium hydroxide. Optimal treatment time is 0.5 to 4 h.

EFFECT: improved physico-mechanical characteristics of articles, to which such properties as chemical stability, thrombosis resistance, biocompatibility, catalytic activity are imparted.

4 cl, 1 tbl, 48 ex

FIELD: chemistry.

SUBSTANCE: disclosed is a copolymer containing silicon groups, obtained via radical copolymerisation of at least one compound with radically polymerisable α,β-ethylene-unsaturated double bond and at least one ionogenic and/or ionic group per molecule; and at least one radically polymerisable cross-linked compound, which contains at least two α,β-ethylene-unsaturated double bonds per molecule in the presence of at least one organosilicon compound containing a polyether group and/or urethane(meth)acrylate, which contains siloxane groups. The copolymer has molar excess of anionogenic/anionic groups relative cationogenic/cationic groups. The invention also discloses a method of obtaining said copolymer and a cosmetic or pharmaceutical agent containing said copolymer.

EFFECT: powder can be easily added to thickening compositions and is suitable for modifying rheological characteristics of cosmetic and pharmaceutical compositions.

18 cl, 2 tbl, 90 ex

Up!