Method of producing scratch-resistant coating for optical information carriers
SUBSTANCE: composition for coating of optical transparent information carriers is described, the composition being curable by UV radiation and including (A) from 1 to 60% by mass of at least one colloid oxide of metal, (B) from 0.1 to 50% by mass of at least one silyl acrylate hydrolysis product having a general formula (I): , (I) where a means an integer from 0 to 2, b means an integer from 1 to 3, and the sum a+b is from 1 to 3, R independently means non-branched or branched alkyl residue with 1 to 8 carbon atoms, cycloalkyl residue with 3 to 8 carbon atoms, unsubstituted or substituted aryl residue with 6 to 10 carbon atoms in the aryl portion, R1 independently means hydrogen, non-branched or branched alkyl residue with 1 to 8 carbon atoms, cycloalkyl residue with 3 to 8 carbon atoms, unsubstituted or substituted aryl residue with 6 to 10 carbon atoms in the aryl portion, R2 independently means hydrogen, non-branched or branched alkyl residue with 1 to 8 carbon atoms, unsubstituted or substituted aryl residue with 6 to 10 carbon atoms, R3 means single bond, or non-branched or branched, if necessary, substituted alkylene residue (alkane dienyl residue) with 1 to 8 carbon atoms in alkylene residue, or, if necessary, substituted arylene residue (aryl dienyl residue) with 6 to 10 carbon atoms in arylene residue, (C) from 25 to 90% by mass of at least one acrylate monomer of general formula (II) where n means a number from 1 to 6, R4 means hydrogen, non-branched or branched alkyl residue with 1 to 8 carbon atoms, unsubstituted or substituted aryl residue with 6 to 10 carbon atoms in the aryl portion and where substituents R4 may be the same or different; R5 means unsubstituted or substituted organic residue having a valency from 1 to 6 such as, if necessary, substituted, non-branched or branched aliphatic or aromatic hydrocarbon residue with 1 to 20 carbon atoms, and (D) from 0.01 to 15% by mass of at least one UV photoinitiator, respectively, with respect to the total mass of the composition, the composition being intended for coating transparent, polycarbonate-based, optical information carriers.
EFFECT: proposed composition is scratch-resistant and highly adhesive to the substrate surface.
3 cl, 2 tbl, 4 ex
The object of the invention is a method of obtaining a transparent, scratch resistant coating materials, optical media, and materials for optical recording of information.
Background of the invention
Recently, materials for optical recording of information is increasingly used as a modified means of recording and/or archiving large amounts of data. Materials for recording information in these tools, accounts subjected to limited local changes such optical properties as the maximum absorption, reflection or extinction coefficient, if they were subjected to irradiation, for example, by a laser beam. The local change in optical properties can be used for recording information.
However, because of the scratches on the read side of the optical recording medium for reading laser also mean the local change in optical properties, they lead to false information and thus violations of the reading process. Through the use of programs designed to compensate for the defects, to a certain extent, you can compensate for such caused by surface defects read errors, but to compensate more significant surface defects on these programs, as you know, aprigo the us.
For optical media using a typical transparent thermoplastic polymers, such as polycarbonate, polymethyl methacrylate and the corresponding chemical modification. These thermoplastic polymers have excellent mechanical stability from the point of view of changes in linear dimensions, as well as high transparency and toughness, but they possess a certain sensitivity to scratching effects. Consequently, polycarbonate substrates sensitive to the damaging effects caused by scratches, abrasion and mechanical erosion. Due to the known sensitivity used for recording substrates to scratch seemed advisable to find technical ways to reduce the sensitivity of the substrates to scratching, especially their reading side.
The preferred protection of the substrate from physical abrasion is applied to the material of the substrate coating consisting of a scratch resistant material. However, transparent, scratch resistant coating have a number of requirements concerning the ability to use speed curing, its technical characteristics and, last but not least, optical and electrical properties. For this purpose have already been proposed ways nanese the Oia certain compositions, providing a known protecting substrates from scratching.
For example, in U.S. patents US 4,455,205, US 4,491,508 and US 4,198,465 as scratch resistant protective coating polymers are encouraged to use fototerapia acrylates. As suitable for coating substrates mentioned various polymers, metals and metallic thermoplastics. About the coating on the transparent substrates has not been reported. Specialists it is unclear how described in these patents compositions can be used to cover the transparent optical media, since these compositions contain colloidal silicon dioxide. The fact that optical media must have especially high transparency (transmittance greater than 80%) in the wavelength range of the read and write lasers, especially when reading or writing light beam passes through the substrate twice. Thus the range of wavelengths of the laser should cover not only visible light (750 nm), and ultraviolet region (300 nm). In addition, various protective coatings optical storage media are described in the literature (see Zech, Spie "Review of Optical Storage Media, Optical Information Storage, Vol.177, 1979, pp.56 ff or, for example, U.S. patent US 5,176,943 and Japanese patent application JP 02-260145).
The described composition is La coatings consist of an ultraviolet-curable (UV) rays or electron beam acrylate binder, which, if necessary, can be mixed with sleepingon (external lubrication) and/or additional additives and which, if necessary, is applied to the substrate with a layer thickness of from 0.004 to 10 microns, using the method of centrifugal casting.
Measures to protect CDS and DVDs from scratching impacts are described, for example, in U.S. patent US 5,939,163, according to which is applied acrylic coating thickness of from 0.01 to 30 μm, preferably from 0.05 to 10 microns.
Although described in the mentioned patent composition for coating and provide a known protection from scratching, due to too low a protective effect to implement these systems have not succeeded. In addition, the described system after atmospheric exposure, i.e. storage in certain climatic conditions, prone to blushing, or reduction, or complete loss of adhesion to the substrate.
The present invention is the creation on the read side of the optical media coverage received economical way, resistant to scratching and high adhesion to the surface of the substrate, which is due to the high hardness of the corresponding utverzhdenii film protects the surface of the substrate from mechanical scraping impact, resistant against environmental influences ("Atmos the nuclear effects in accordance with the climatic tests) and does not cause the occurrence of such technical deficiencies, as, for example, the increase in double refraction, attenuation of signals, the deformation disks, color or turbidity of the surface, change the readability or zapisyvaete information focused laser beam.
The coatings produced from the known systems based on organic fototerapia acrylate, have a thickness of from 7 to 12 microns, in the curing process they strongly seated, and the resulting shrinkage causes deformation of plates made of polycarbonate, which leads to the loss of the ability of the media to the reproducibility or repeatability/readability.
Through the implementation of appropriate measures coating thickness can be reduced, however, this leads to a significant decrease in resistance to scratching.
It has been unexpectedly discovered that the use of special UV-curable inorganic lacquer systems are provided as high adhesion of the coating to the substrate materials and sufficient transparency and excellent resistance to scratching at the low values of thickness, that the geometrical parameters of the optical media do not change or change within acceptable limits.
Used according to the invention compositions based on acrylate resins containing modified alkoxysilylated metal oxides, to the which are formed by the interaction of the products of hydrolysis of alkoxysilylated with metal oxides.
Thus, the present invention provides an optical information carriers, provided with a coating, which is obtained by radiation curing a radiation-curable composition for coating containing at least one colloidal metal oxide, at least one hydrolysis product of at least one alkoxysilylated at least one acrylate monomer and at least one photoinitiator.
Radiation curable compositions for coating, it is advisable contain:
(A) from 1 to 60 wt.%, at least one colloidal metal oxide,
(B) from 0.1 to 50 wt.%, at least one material formed as a result of hydrolysis of at least one alkoxysilane, preferably having the formula (I),
(C) from 25 to 90 wt.%, at least one acrylate monomer, preferably having the formula (II)
(D) from 0.01 to 15 wt.%, at least one photoinitiator
in relation to the total weight of the composition.
Suitable colloidal metal oxides are silicon dioxide, zirconium dioxide, titanium dioxide, aluminum oxide and zinc oxide.
Preferred is colloidal silicon dioxide. It is advisable to use colloidal metal oxides in the form of a dispersion of particles of oxides of metals in water is the ed and/or in the environment of an organic solvent. Such a colloidal dispersion of particles of metal oxides can be obtained either by hydrolysis of the corresponding metal oxide, based on the aqueous solutions of the respective Metallistov alkali metals by removing alkali metal ions by means of ion exchangers. Depending on the conditions of receiving the formed colloidal water or spirtovanie dispersion of metal oxides with the distribution of particle sizes, which corresponds to the interval from 1 to 1000 nm. The particle size of the oxides of metals, intended for use in compositions for coating according to the invention preferably should not exceed 100 nm. A typical distribution of the particles of silicon dioxide in size corresponds to the interval from 5 to 40 nm.
Granulometric composition of metal oxides can be determined either by using a scanning electron microscope by optical measurements, the calculated number of particles, or by electronic counting devices (e.g., classifier Coulter-Multisizer 3, Beckman Coultert Inc. or Laser Diffraction Sizer CDA 500, Malvern Instruments, Ltd. UK). If you use very small particles (less than 100 nm), the highest precision sizing provides a method Zeta-Civern.
Metal oxides, in particular particles of silicon dioxide, contain tetrafunctional (Q) atoms of the metal or silicon, and provide the underlying hardness of compositions for coating. On the surface of these colloidal metal oxide in a state of Zola, there are functional hydroxyl group.
These functional groups can react condensation, for example, with trifunctionally greatselection formula (I) ("modified silicone acrylates", formed by hydrolysis of the acrylate-modified tralkoxydim) with particle formation patterns "core-shell" ("core-shell").
Dispersion of colloidal silica can be purchased from different manufacturers, such as DuPont, Nalco Chemical Company or Bayer AG. Purchased colloidal dispersion of silicon dioxide can be acidic or alkaline form. To obtain compositions for coatings, it is preferable to use an acidic form of dispersions, which compared with alkaline forms provides the best properties of the coatings.
Example with satisfactory properties of colloidal silicon dioxide is Nalcoag 1034A.RTM. This product contains about 34 wt.% silicon dioxide. The examples are also given specified values of moisture content. Thus, for example, 520 grams of product Nalcoag 1034A.RTM contain about 177 grams of silicon dioxide.
Composition for coating according to the invention preferably contain from 1 to 60 wt.%, especially prefer is Ino from 5 to 40 wt.% colloidal metal oxides, accordingly, in relation to the total number of songs.
According to the invention is preferably used in component (C) is a hydrolysis product of similarility having General formula (I):
a represents an integer from 0 to 2, preferably 0,
b denotes an integer from 1 to 3, preferably 1, and
the sum a+b is from 1 to 3, preferably 1.
R in the formula (I) denotes unbranched or branched alkyl residue with 1 to 8 carbon atoms, cycloalkyl residue with 3 to 8 carbon atoms or optionally substituted aryl residue with 6-10 carbon atoms in the aryl part. If there are multiple residues R (equal to 2), they may be the same or different. Unbranched or branched alkyl residues with 1 to 8 carbon atoms are, for example, methyl, ethyl, propyl, butyl, and so forth.
Preferred residues R are methyl, ethyl, propyl, cyclohexyl, hexyl, octyl, isopropyl and isobutyl. Preferred are alkyl residues. Particularly preferably R is methyl and ethyl.
Optionally substituted aryl residues R with 6-10 carbon atoms are, for example, phenyl or raftiline residues, which can be substituted by one or more, preferably one to three of the Deputy is mi, selected from the group comprising alkali with 1-6 carbon atoms and halogen atoms such as fluorine, chlorine, bromine or iodine; an aryl residues R can be, for example, phenyl, toluyl, xylyl, naphthyl, chlorophenyl, and so on.
Preferred aryl residue R is phenyl.
R1in the General formula (I) means hydrogen, an unbranched or branched alkyl residue with 1 to 8 carbon atoms, cycloalkyl residue with 3 to 8 carbon atoms or optionally substituted aryl residue with 6-10 carbon atoms in the aryl part; if there are several groups of R1(a+b is greater than 1), they may be the same or different.
As for unbranched or branched alkyl residue R1with 1-8 carbon atoms or optionally substituted aryl residue R1with 6-10 carbon atoms and their preferred values, then they are similar to the above for the substituents R.
R1preferably means methyl or ethyl.
R2in the General formula (I) means hydrogen, an unbranched or branched alkyl residue with 1 to 8 carbon atoms or optionally substituted aryl residue with 6-10 carbon atoms, and the group R2may be the same or different.
As for unbranched or branched alkyl residue R2with 1-8 atom is mi carbon or optionally substituted aryl residue R2with 6-10 carbon atoms and their preferred values, then they are similar to the above for the substituents R.
R2preferably means hydrogen and/or methyl, and methyl group as R2may be, in particular, substituted and the carbon atom adjacent to the carbonyl carbon atom (methacrylates). Preferably all the substituents R2mean hydrogen, and the substituent R2attached to the carbon atom adjacent to the carbonyl carbon atom, may also be the stands.
R3in the General formula (I) means a single bond or unbranched or branched, optionally substituted alkalinity balance (ascandilwy balance) with 1-8 carbon atoms in Allenova residue, or optionally substituted Allenby balance (alldaily balance) with 6-10 carbon atoms in Allenova residue. Alkalinity residue, if necessary, preferably substituted by one to three substituents, more preferably one Deputy, selected from the group comprising halogen and hydroxy. Allenby residue, if necessary, preferably substituted by one to three substituents, more preferably one Deputy, selected from the group comprising alkyl group with 1-6 carbon atoms is, atoms by halogen, in particular fluorine, chlorine, bromine or iodine, and hydroxy.
Examples R3are the following balances:
linear alkylene residues, for example methylene, ethylene, trimethylene, tetramethylene and so forth, preferably unbranched residues, optionally branched halogenated alkylene residues with 2 to 8 carbon atoms, optionally branched gidroksilirovanii alkylene residues with 2 to 8 carbon atoms, allenbyi radicals with 6-10 carbon atoms, such as phenylene (1,2-phenylene, 1,3-phenylene and 1,4-phenylene), tollen, naftilan and so on, halogenated allenbyi radicals with 6-10 carbon atoms in Allenova parts and so on.
R3preferably means a single bond, methylene or ethylene.
Used according to the invention similarility General formula (I) are known and described in particular in U.S. patent US 4,491,508 that are appropriate references.
Similarility formula (I) are preferably acrylate and methacrylate compounds, in particular:
CH2=CHCO2-CH2CH2CH2CH2-Si(och3)3and so on.
The products of hydrolysis (In) alkoxysilylated, preferably having the formula (I), which are the part used according to the invention a composition for coating, obtained by interaction of alkoxysilylated with water.
When it comes to partially or completely hydrolysed alkoxysilylated. As a result of hydrolysis are formed corresponding hydroxycitrate the ATA, which can interact with each other and with the hydroxyl groups of the colloidal metal oxide by condensation.
Believe that the products of hydrolysis interact with colloidal metal oxides with the formation of the relations Si-O-metal.
As described in more detail below when considering obtaining compositions for coating according to the invention, the formation of the products of hydrolysis of similariton can occur before or in the process of getting used according to the invention compositions for coating.
Appropriate content is used according to the invention product (C) used according to the invention a composition for coating is from 0.1 to 50 wt.%, preferably from 1 to 15 wt.%, accordingly, with respect to the total amount of the composition.
Used according to the invention the acrylate monomer (S) preferably have the General formula (II):
in which n denotes a number from 1 to 6, R4means hydrogen, an unbranched or branched alkyl residue with 1 to 8 carbon atoms or optionally substituted aryl residue with 6-10 carbon atoms in the aryl part, where the substituents R4may be the same or different; R5means, optionally substituted organic residue, the valence of which extending t is from 1 to 6.
n preferably is an integer from 1 to 4, particularly preferably from 2 to 4.
As for unbranched or branched alkyl residue with 1 to 8 carbon atoms or optionally substituted aryl residue with 6-10 carbon atoms as R4and preferred values for these residues, they are similar to the above for the substituents R in the formula (I).
R4preferably means hydrogen and/or methyl, and methyl group as R4may be substituted, including the carbon atom adjacent to the carbonyl carbon atom (methacrylates). Preferably all the substituents R4mean hydrogen (acrylates), and the substituent R4attached to the carbon atom adjacent to the carbonyl carbon atom, can also be stands (methacrylates).
R5means organic residues having a valence from 1 to 6, preferably from 2 to 4, which optionally can be substituted. Valence refers to the number of acrylate groups n. R5preferably means, if necessary, substituted unbranched or branched aliphatic or aromatic hydrocarbon residue with 1-20, preferably 1-10 carbon atoms. As for the divalent residues, they are similar balances listed above for R3.
5if necessary, preferably contains from one to three substituents, such as halogen or hydroxy.
Acrylate monomers of formula (II) are mono - and polyfunctional monomers.
Monoacrylate are alkylacrylate and alkyl methacrylates, optionally substituted with hydroxyl groups, such as hydroxyethylacrylate and so on. Acrylate monomers of formula (II) introduced into the compositions according to the invention in amounts of at least from 5 to 25 wt.%, preferably from 5 to 10 wt.% to improve the adhesion of the coatings to the substrates.
In the composition used according to the invention a composition for coating preferably includes at least one acrylate containing at least two ethylene-unsaturated groups, optionally in combination with mono - or polyfunctional acrylate.
Examples of polyfunctional acrylates of formula (II) are the following compounds:
and so forth,
and so forth,
and so on.
The acrylates of this type is known, in connection with which it is possible to refer to the compounds described in U.S. patents US 4,491,508 and US 4,198,465.
Used according to the invention, the composition for coating preferably contains a mixture of two or more polyfunctional acrylate monomers of formula (II), more preferably a mixture of one diacrylate with one polyfunctional acrylate. Suitable mass ratio diacrylate and polyfunctional acrylate in compositions for coating containing a mixture of diacrylate and polyfunctional acrylates, ranges from 0.5:99 to 99:0.5, and particularly preferably from 1:99 to 99:1. For example, you can use a mixture of diacrylate with triacrylate General formula (II).
Examples of mixtures of diacrylate and polyfunctional acrylate is a mixture of hexaniacinate with trimethylolpropane (TMPTA), hexaniacinate with pentaerythritoltetranitrate, dietilenglikoluretan with pentaerythritol and dietilenglikoluretan with trimethylolpropantriacrylated. Especially preferred are compositions for coatings containing two polyfunctional acrylate monomial is the RA of formula (II).
A suitable content of the acrylate monomer (C) used according to the invention a composition for coating ranges from 25 to 90 wt.%, preferably from 40 to 85 wt.%, accordingly, with respect to the total amount of the composition.
In accordance with a particular embodiment of the invention, the content of monofunctional acrylates (n=1) as component (C) in relation to the total amount of component (C) is from 5 to 50 wt.%, preferably from 5 to 25 wt.%, still preferably from 5 to 10 wt.%.
Used according to the invention photostructurable compositions for coatings contain necessary for the photosensitization number of at least one photoinitiator (D), there is such a quantity, which is able to initiate the flow of fototerapia under the action of UV radiation. The required number of photoinitiator in General ranges from 0.01 to 15 wt.%, preferably from 0.1 to 10 wt.%, from 1 to 8 wt.%, even more preferably from 1.5 to 7 wt.% in relation to the sum of all composite parts for coating. When increasing the number of photoinitiator get a composition for coating, which cures faster.
As photoinitiators (D) connections can be used, for example, described in U.S. patent US 4,491,508 and US 4,455,20. Suitable for use according to the invention photoinitiator, in particular methylbenzofuran, are sold under various trade names.
Used according to the invention, the UV-curable composition for coating preferably consist mainly of components (A)-(D). However, experts know that to be used according to the invention the compositions for coating, if necessary, may be added known additives in amounts not detrimental to the solution according to the invention, for example soluble salts, Soaps, amines, non-ionic and anionic surfactants, acids, bases, and prevent gelatinization of the substance. Additionally, there may be added a variety of tools that contribute to a spill, as well as wetting agents, light stabilizers and dyes.
Such additives are described, for example, in U.S. patents US 4,491,508 and US 4,455,205.
Various surfactants that can be included in the compositions to cover known and do not require special explanations. They are described, for example, in the following literature: Kirk-Othmer "Encyclopedia of Chemical Technology, Vol.19, Interscience Publishers, New York, 1969, s.507-593; "Encyclopedia of Polymer Science and Technology, Vol.13, Interscience Publishers, New York, 1970, s.477-486.
Other monomers neurilemoma type, in particular N-organic is whether sterols, like some monoacrylates, such as isobutylacetate, phenoxyethylacrylate or hydroxyethylmethacrylate serve both to improve properties of the formed utverzhdennym product film, which is manifested in increasing its flexibility, and to increase the adhesion of the coating to the substrate materials. In addition, they provide a lower viscosity when cooked mixture.
Used according to the invention, the UV-curable composition for coating can be obtained by mixing components (a)to(D) and, if necessary, other components.
In the mixing process in the presence of aqueous colloidal metal oxide and able to be mixed with water, alcohol silicrylic can be hydrolyzed. When implementing different technological operations of aqueous colloidal metal oxide may be added to similarity, which was hydrolyzed in aqueous alcoholic solution at room temperature or the temperature of reflux distilled solvent used.
Suitable solvents are, for example, any miscible with water, alcohols, and the azeotropic mixture of alcoholic solvents. Examples of such solvents are isopropyl alcohol, 4-methoxypropanol, n-butanol, 2-butanol, ethanol and similar alcohols.
To obtain solvent free product, azeotropic mixture in the water and alcohol are removed from the composition by distillation. In those cases, if the alcohol is initially hydrolyzed mixture is not used for complete removal contained in a mixture of water need to add necessary for azeotropic distillation of the alcohol.
In addition, the present invention relates to a method of coating on the read side of the optical storage media such as CD, superaudio-CD, CD-R, CD-RW, DVD, DVD-R, DVD-RW and DVR. The following table presents a systematic review of currently known optical and magneto-optical media. The preferred media are CD-R, CD-RW, DVD, DVD-R, DVD-RW and DVR.
|CD-ROM||Information||Indelible||Design and storage|
|DVD-R||recorded||information||(polycarbonate) with a layer|
|user||Not re -||memory:|
|DVD-RW||recorded||information||(polycarbonate) with a layer|
|record with the phase transformation (PC-R)|
CD-DA=Compact Disk - Digital Audio (CD - digital audio),
CD-ROM=Compakt Disk - Read Only Memory (CD-ROM - permanent memory),
DVD-ROM=Digital Versatile Disk - Read Only Memory digital versatile disc - permanent memory),
CD-R=Compakt Disk - Recordable (CD - recordable),
DVD-R=igital Versatile Disk - Recordable (digital versatile disk - recordable),
CD-RW=Compact Disk - ReWritable (CD - rewritable),
DVD-RW=Digital Versatile Disk - ReWritable (digital versatile disc - rewritable),
DVR=High Density Disk - Recordable (CD with high density DVD recordable)
to achieve durable to scratch coatings on these optical media using the above-described UV-curable compositions for coating.
Optical media with a coating according to the invention in General consists of a transparent thermoplastic polymers, in particular of polycarbonate based on bisphenol-A polycarbonate-based trimethylcyclohexylidene, fluorenylacetamide, methyl methacrylate), cyclic polyolefin copolymer SOS 513 (manufacturer: Ticona GmbH, Nippon Zeon and Japan Synthetic Rubber, Japan), hydrogenated polystyrene (manufactured by Dow Chemical), and amorphous polyolefins and polyesters (manufacturer Kodak Corp., USA).
If we are talking about applying UV-curable compositions for optical information carriers in the form of discs, such as CD, DVD and DV-R, it is advisable to apply the composition on separate disks by centrifugal casting, and then to carry out the curing under the action of UV radiation.
It is preferable application of the drive required for the process quantity of the composition is the form of liquid ring or spiral in the chamber for centrifugal casting, moreover, the composition is applied to the disk in obespylivanii the camera, which is part of the corresponding production line, or if the disk was made to separate involving the aging process stage, the composition is applied after processing disk deionized air; subsequent uniform distribution of the composition on the surface of the substrate by implemented within 1.0 to 10 seconds, increasing the frequency of rotation of the substrate to 1000-10000 per minute and remove excess composition by centrifugation. Using the appropriate program changes the rotation speed of the substrate, the excess composition can be removed so that the full extent to provide a uniform radial distribution of the layer thickness.
Thanks to the implementation of this process on the surface of the substrate is formed of a homogeneous liquid film thickness of from 0.001 to 100 microns. The resulting film thickness depends on the rheological characteristics of the composition for coating, in particular its viscosity, and speed of the centrifugal plate and duration of exposure to high speeds in the process of removing excess composition.
Located on the surface of the uncured substrate film directly after removal of excess composition to be cured with IP is the use of appropriate exposure for example, UV-rays or electron beam, preferably UV radiation, which is suitable to carry out at temperatures from room temperature up to 45°C. For UV irradiation is suitable, for example, the corresponding operating in non-pulsating mode sources. In this case, pulsating sources of UV radiation for practical hardening is used. In principle, for curing radiation-structured compositions for coatings can be used and electron irradiation (electron beam), however, as practice shows, the corresponding devices are too large in size or curing rate is too low.
The radiation power of UV lamps used for curing systems according to the invention is from 1,000 to 20,000 Watts, preferably from 1600 to 2200 Watts (for CD, CD-R, CD-RW, and DVD). Used UV lamp (manufacturer: company Singulus, type: 200 BTZ/DF) is a mercury high-pressure lamps with variable power consumption (from 1000 to 20000 Watt/hour). However, there may be used other standard mercury lamps, if they have the appropriate power required for curing the range of UV-irradiation (250 to 400 nm, preferably from 360 to 380 nm).
In the method according to the invention there is no need to create an atmosphere of inert gas, in particular nitrogen atmosphere, usually polzuemoy to the above described method of curing.
To ensure complete curing, the thickness obtained at the end of the cured coating preferably should not exceed 100 microns. At higher coating thickness resulting from the final curing shrinkage can lead to deformation (spherical curvature) optical media, so that they become naschityvaetsya and non-writeable. The preferred coating thickness corresponds to the interval from 100 to 1 micron. Particularly preferred coating thickness is from 10 to 3 microns.
Used according to the invention the composition is in the General case forms the outer covering of the recorded and read side of the optical storage medium, that is the side provided with the coating of the carrier which permeates the laser beam. However, this composition can be used for coating as a writable and readable side and on the reverse side of the recording media.
Obtained according to the invention coatings have several advantages compared with the prior art.
They are particularly high adhesion to the respective substrates, in particular, to the polycarbonate, in particular measured after aging under conditions of climatic tests (for CD, DVD and DV-R).
In addition, Doc is administered according to the invention the coating in comparison with coatings in accordance with the prior art have a high hardness and resistance to scratching.
In addition, obtained according to the invention the cover CD and DVD ensure the absence of "electronic noise" and additional defects, which could have a negative impact on readability and zapisyvaete information.
The following examples are intended to explain the invention. In the examples used the following test methods.
1. Climatic tests
Equipped with a cover CD or DVD stand in certain artificially created climatic conditions (at a temperature of 70°C, relative humidity of 50%, the exposure time 96 hours); in accordance with another variant of this test CDS or DVDs survive in harsher conditions: at a temperature of 80°C, a relative humidity of 95%, the exposure time 96 hours; in accordance with another variant of this test CDS or DVDs survive in harsher conditions: at a temperature of 70°C, relative humidity of 90%, the exposure time of 500 hours. After an appropriate time in the appropriate above conditions, the CD or DVD within 24 hours incubated in normal climatic conditions, and then measure the deviation from planarity. Then carry out a visual assessment of the condition of the coating. Any areas of peeling from the substrate on which freight could not be found.
Additionally, using the method of cross-hatch test, determine the adhesion of the coating before and after environmental testing. For testing according to the method of lattice incision on the surface of the CD/DVD multiblade knife make parallel cuts. Then the disks rotate 90° and again make parallel cuts. Eventually the coating occurs educated cuts a grid with square cells of 1 mm2. To cover with lattice cut for a short time stick adhesive tape (for example, the tape type SM Scotch 710) and carry her off.
The sample does not stand the test, if the substrate exfoliate at least one of the grid squares. Each of the three samples are subjected to the specified test.
2. Tests resistance to scratching
The resistance of coatings to scratch will determine, using the method of pencil and method for measuring abrasion on the machine Taber.
When using the method of standard pencil pencil rods of 2 mm diameter sharpened on both sides in a thin emery paper so as to form a cutting edge. The pencil is applied to the floor and move forward. If the rod is used pencil has a higher hardness compared with the test coating on the surface of the latter occurs scratch; if the rod pencil me the che test coverage, he leaves no trace (scratches). Evaluation of coating hardness is the hardness of the pencils, which cannot create surface scratches. The specified test three times subjected to each of the samples.
Test the resistance on the machine subjected to Taber provided with a Central hole of the disk. Machine Taber equipped with a slip-disc CS-10F, after every 500 cycles under conditioning (15 cycles using disk S-111). Lots of used goods is 500, the four points of the upcoming abrasion each provided with a coating disks measure turbidity using the device GARDNER. The sample is subjected to a certain number of abrasion cycles, after which the surface is cleaned from the adhering particles. The difference of the turbidity (increase) is determined by the degree of turbidity measured after implementation of the same procedure, minus the initial turbidity. For each dimension, respectively, using five samples.
A mixture consisting of 50 parts of tert-butanol, 16.6 parts of the product Nalcoag 1034A (Nalco Company, Oak Brook, Illinois) and 1 part γ-methacryloxypropyltrimethoxysilane within 5 minutes was heated under reflux. After cooling to room temperature was added to 13.2 parts of a mixture of hexaniacinate and trimethylolpropane the acrylate (1:1). Then under reduced pressure drove the solvent. After distillation, approximately half of the solvent was further added 30 parts of tert-butanol. Drove all solvent and water. Received a clear solution. To 100 parts of the obtained solution was added 1.5 parts α,α-diethoxyacetophenone.
Obtained in the manner described above, the UV-curable composition was applied onto a CD-R on an unattended installation for coating type DVD-R2500 company STEAG-Hamatech, using the method of application accepted for production at this facility and was utverjdali within 2 seconds when the consumption power of the UV lamp 2200 Watt/hour.
Properties of the resulting coating are shown in table 1.
A mixture of 52 g of the product Nalcoag 1034A (colloidal silicates) and 10 g γ-methacryloxypropyltrimethoxysilane dissolved in 80 g of Isobutanol, and 80 g of isopropanol for 30 minutes, heated under reflux. After cooling to room temperature, was added one drop of a solution of sodium hydroxide concentration 50%. The solvent was removed by distillation under reduced pressure. A plastic resin was added to 3.2 g of dietilenglikoluretan, 3.2 g of trimethylolpropane and 4 g of N-vinylpyrrolidone. After evaporation of the solvent and water as photoinitiator was added 2.1 g of benzophenone and 2.1 g methyldiethanolamine is per 100 g of the obtained reaction mixture. This composition was applied to a CD-RW automatic installation for coating type DVD-R2500 company STEAG-Hamatech described in example 1 by the method.
Properties of the resulting coating are shown in table 1.
Example 3 (comparative)
Were used for comparison was obtained in the trade, resistant to scratch the varnish is recommended as particularly suitable for coating a transparent thermoplastic polymers. This lacquer comes on the market under the trade name UVT 200 (manufactured by Red Spot and Varnish Co., Evansville, USA).
The varnish was applied onto the substrate in accordance with the terms similar to applying lacquer compositions according to the invention. The centrifugation device for centrifugal casting was performed at a rotational speed of 3000 rpm/min for 2 seconds. To receive the coating thickness of 8.5 microns.
Properties of the resulting coating are shown in table 1.
Example 4 (comparative)
For comparison, CD-R given in example 3, the method was applied specially recommended for CD varnish-type Daicure Clear SD-715 (manufactured by Dainippon Ink &Chemicals, Inc., Japan). Measured after curing the coating thickness was 5 μm.
Mechanical properties of coatings obtained are shown in table 1.
|method lattice||method||turbidity %|
|Example 1||The challenge is sustained||2H||9,1||5,5|
|Polycarbonate uncoated||The test is not passed||The test is not|
Table 2 shows the electrical characteristics of the substrates with the coating and resistance to climatic factors.
|BLER||Radial noise (nm)||Curvature||Atmospheric effects|
|(CD-R)||(the radius deviation in degrees)||(80°C/relative humidity 90%/96 hours)|
|Example 1||12||12||-0,3||The challenge is sustained|
|Example 2||3||5||to-0.05||The challenge is sustained|
|Example 3 (comparative)||25||More than 20||+1,5||Curvature, white color|
|Example 4 (comparative)||15||Over 18||+1,0||Curvature, white color|
|Polycarbonate uncoated||3||4||+1,0||The test is not passed|
BLER=Block Error Rate block error); mean change in comparison with the product without coating; a correction unit/sec., necessary to adjust the reading. BLER point in a velocity error reading per second. Limit value according to the specification 220 errors per second, and for CD-ROM specification should recommend as the maximum average value of 50 errors per second and the maximum peak value 100 errors per second. BLER is crucial for the maximum possible limit the number of errors to ensure security of the information.
Radial noise are measured according to ISO/IEC 10 149 changing tracks within a band of frequencies 500-2500 Hz limiting value corresponds to 30 nanometers. Radial noises occur due to damage to the track. At high peak radial noise tracking system can skip tracks. High average radial noise indicates poorly identified the uneven surface.
The curvature is determined by the angular degrees measured (height) deviations from the metallized top side of the drive from the plane. The curvature is measured for ten different distributed on the upper surface of the disc diameter. It is formed by the angle between the midpoint of the disk and deviation from the plane of the disc surface. According to the specification of the curvature in the outer region as recorded and unrecorded CD-R corresponds to the deviation in height from the plane, constituting ±0.5 mm higher values of curvature cause problems when focusing, and therefore, the loss of high frequency signal.
Despite the fact that the composition for coating the accordance with the comparative experience applied in a thicker layer, the coating has a much lower hardness and a stronger shrinkage of the coating causes a curvature of the optical media.
1. Composition for coating transparent optical media, and it is capable of curing by UV radiation and contains
(A) from 1 to 60 wt.%, at least one colloidal metal oxide,
(B) from 0.1 to 50 wt.%, at least one hydrolysis product similarility having General formula (I)
in which a represents an integer from 0 to 2,
b denotes an integer from 1 to 3, and
the sum a+b is from 1 to 3,
R independently denotes unbranched or branched alkyl residue with 1 to 8 carbon atoms, cycloalkenyl balance with 3-8 carbon atoms, nezameshchenny or substituted aryl residue with 6-10 carbon atoms in the aryl part,
R1independently means hydrogen, an unbranched or branched alkyl residue with 1 to 8 carbon atoms, cycloalkenyl balance with 3-8 carbon atoms, unsubstituted or substituted aryl residue with 6-10 carbon atoms in the aryl part,
R2independently means hydrogen, an unbranched or branched alkyl residue with 1 to 8 carbon atoms, unsubstituted or substituted aryl residue with 6 to 10 atom and carbon
R3means a single bond or unbranched or branched, optionally substituted alkalinity balance (ascandilwy balance) with 1-8 carbon atoms in Allenova residue, or optionally substituted Allenby balance (alldaily balance) with 6-10 carbon atoms in Allenova the rest,
(C) from 25 to 90 wt.%, at least one acrylate monomer of General formula (II)
in which n denotes a number from 1 to 6,
R4means hydrogen, an unbranched or branched alkyl residue with 1 to 8 carbon atoms, unsubstituted or substituted aryl residue with 6-10 carbon atoms in the aryl part, where the substituents R4may be the same or different;
R5means, unsubstituted or substituted organic residue, the valence of which is from 1 to 6, such as, when necessary, zameshannyj unbranched or branched aliphatic or aromatic hydrocarbon residue with 1-20 carbon atoms, and
(D) from 0.01 to 15 wt.%, at least one UV photoinitiator, respectively, relative to the total weight of the composition.
2. The composition according to claim 1, intended to cover the transparent optical media-based polycarbonates.
3. The composition according to p., designed to cover a CD, DVD or DVD-R on the basis of polycarbonates.
SUBSTANCE: multilayer record carrier of a writable type has a first recording layer (40) having a first recording stack (50, 51) of a first type and a second recording layer (41) having a second recording stack (54, 55) of a second type. The first and second recording stacks have different writing parameters. Each recording layer has a pre-formed recording control pattern that is readable via a laser beam for indicating the track. At least one recording control pattern comprises recording stack type indicator for indicating the writing parameters of the second recording stack. A recording device has a control unit (20) for adjusting recording parameters in the device in dependence of the recording stack type indicator retrieved from the recording control pattern.
EFFECT: creation of the multilayer optical disc.
8 cl, 7 dwg
FIELD: personal computer hardware, possible use as information storage in computers, audio and video equipment.
SUBSTANCE: effect is achieved by reading and recording information on an immobile disk. Information storage, containing laser emitter, objective, impulse amplifier, buffer memory block and two-sided one-layered disk, additionally features block of sinusoidal oscillations and block for shifting phase for 90°, two amplifiers and two piezo-deflectors with reflectors on end, encoder and decoder, and a layer of photo-receiver is introduced into optical disk between first and second recording layers.
EFFECT: exclusion of disk drive and automatic tracking and regulating systems from composition of information storage.
FIELD: engineering of optical record carriers.
SUBSTANCE: film compact-disk includes registering, reflecting, main and protective layers. Minimization of total thickness of compact-disk film is achieved by discontinuous enclosures of magnetic material, positioned in such a way, that in magnetic field magnetic material not only promotes setting of disk in given position, but also promotes rotation of the disk in its plane, with thickened parts on disk planes, positioned from the center towards the edge of circle in such a way, that air is captured during rotation of disk and forced out by centrifugal forces. The aperture in the middle of the disk is used for influx of air for cooling the disk.
EFFECT: increased efficiency.
FIELD: improved multi-bit magnetic memorizing device with arbitrary selection and methods for functioning and manufacture of such a device.
SUBSTANCE: magnetic memory includes one or more paired cells, each one of which has multilayer magnetic structure. Structure contains magnetic-changeable ferromagnetic layer, ferromagnetic basic layer, having non-changeable magnetization state, and corresponding separating layer which divides ferromagnetic layers. Memory cells are ordered in such a way, that effective remaining magnetization of each cell is not parallel to cell axis which is parallel to its long side. Methods describe functioning process of such a device.
EFFECT: increased data recording density, reduced energy consumption and simplified manufacturing process of memorizing device.
3 cl, 30 dwg
FIELD: optical information recording, possible use for creating holographic optical elements.
SUBSTANCE: in accordance to method for recording information on amorphous chalcogenide film, including effect of laser radiation with energy exceeding width of forbidden zone, film is used based on germanium and gallium chalcogenides, which is produced by means of impulse laser spraying method.
EFFECT: production of high contrast information recording, increased resolution, cheaper information recording process.
3 cl, 4 dwg
FIELD: multi-layered body and method for producing multi-layered image in such a multi-layered body.
SUBSTANCE: multi-layered body contains two layers sensitive to laser radiation with partial overlapping. First and second laser radiation sensitive layers contain colorant, which under effect of laser radiation loses color or under effect of laser radiation changes its color, or laser radiation sensitive layer contains alloyed material, which under effect of laser radiation is subject to blackening. In first layer sensitive to laser radiation a multi-layered laser-induced component part of image may be formed, while in second laser radiation sensitive layer black marking may be formed, preferably a grayscale image, and/or special background layer at sections is located as intermediate layer between laser radiation sensitive layers and acts as locking layer, which is not transparent for laser radiation. In accordance to method of forming of multi-layered image in multi-layered body, multi-layered image is composed of several laser-induced components of image.
EFFECT: creation of multi-layered body, which realizes high degree of protection from forgery and special marking induced by laser.
2 cl, 7 dwg
FIELD: optical recording technologies, namely, engineering of two-layered optical disks with high recording density, and of devices for recording/reproducing from them.
SUBSTANCE: two-layered optical disk with high recording density contains first recording layer and second recording layer, positioned on one side of central plane, dividing the disk in half along thickness, close to surface, onto which light falls. First thickness of substrate from surface, onto which light falls, to first recording layer has minimal value over 68,5 micrometers, second thickness of substrate from surface, onto which light falls, to second recording layer has maximal value less than 110,5 micrometers, while refraction coefficient is within range 1,45-1,70.
EFFECT: minimization of distortion of wave front, provision of possibility of more precise recording of signals onto optical disk or reproduction of signals from optical disk.
8 cl, 10 dwg
FIELD: engineering of data carrier, and of recording and reading devices, compatible with such a data carrier.
SUBSTANCE: each variant of aforementioned data carrier contains recording track, formed by a stream of recesses on the surface of carrier, data of recess represent information recorded on it, which contains main data and sub-code. In accordance to one of variants, information about physical characteristics of current data carrier is recorded in sub-code. In accordance to other variant, data carrier contains multiple individual reading/recording zones, physical characteristics of which are different, and each one of aforementioned zones contains zones for input, zones for program and ones for output, while in sub-code of input zone of each one of aforementioned zones, information about physical characteristics of appropriate individual reading/recording is recorded as well as information about starting position of input zone of next individual reading/recording zone. Each one of variants of recording device contains a certain device for determining physical characteristics of aforementioned data carrier by reading information about these from sub-code, and each variant of reading device contains aforementioned determining device and device for controlling reading.
EFFECT: increased quality of reading and writing of information.
6 cl, 94 dwg
FIELD: engineering of devices for information storage.
SUBSTANCE: device for information storage contains disks with information carrying layer mounted with possible rotation relatively to common axis, disks rotation drive, reading and/or recording head, positioned on the side of end of one of edge disks and directed towards the latter by its active zone, and also drive for moving aforementioned head in plane, parallel to rotation plane of disks. Information carrying layer at least on one disk, positioned on the side of head, is made with forming of window, transparent for signal, emitted and/or read by head and having shape matching movement trajectory of head, and disks rotation drive is made with possible independent rotation of disks and holding in position, providing for positioning of window in front of active zone of head.
EFFECT: increased efficiency.
8 cl, 4 dwg
FIELD: engineering of information carriers and appropriate reading and recording devices.
SUBSTANCE: variants of information carrier contains information about its configuration recorded thereon as well as information about inertia moment of current information carrier. Recording device contains means for determining physical characteristics of utilized information carrier by reading information about configuration and information about inertia moment from wobbulated groove of information carrier, and recording control means, applying corrections for performing recording process in accordance to physical characteristics of information carrier. Reading device contains means for determining physical characteristics of information carrier by reading information about configuration and information about inertia moment, and recording control means, applying corrections for performing reading operation in accordance to physical characteristics of information carrier.
EFFECT: simple and precise process of determining physical characteristics of information carrier, possible adjustment of reading and recording operations.
4 cl, 93 dwg
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to photoinitiating agents of phenylglyoxylic acid order used in polymerizing compositions to be subjected for hardening. Invention describes a photoinitiating agent of the formula (I): wherein Y means (C3-C12)-alkylene, butenylene, butinylene or (C4-C12)-alkylene that are broken by groups -O- or -NR2- and not following in sequence; R1 means a reactive group of the following order: -OH, -SH, -HR3R4, -(CO)-OH, -(CO)-NH2, -SO3H, -C(R5)=CR6R7, oxiranyl, -O-(CO)-NH-R8-NCO and -O-(CO)-R-(CO)-X; R2 means hydrogen atom, (C1-C4)-alkyl, (C2-C4)-hydroxyalkyl; R3 and R4 mean hydrogen atom, (C1-C4)-alkyl, (C2-C4)-hydroxyalkyl; R, R and R mean hydrogen atom or methyl; R8 means linear or branched (C4-C12)-alkylene or phenylene; R9 means linear or branched (C1-C16)-alkylene, -CH=CH-, -CH=CH-CH2-, C6-cycloalkylene, phenylene or naphthylene; X, X1 and X2 mean -OH, Cl, -OCH3 or -OC2H5. Also, invention describes a method for synthesis of a photoinitiating agent, polymerizing composition and substrate covered by its. Proposed photoinitiating agent possesses the effective introducing capacity and absence of migration in thermal treatments.
EFFECT: improved and valuable properties of agent.
13 cl, 1 tbl, 16 ex
FIELD: rocketry; production of the potting composition for armoring the charge made out of the ballistite propellant.
SUBSTANCE: the invention is pertaining to the field of rocketry and presents the potting composition for armoring the charge made out of the ballistite propellant. The potting composition includes polybutylmethacrylate, butylmethacrylate, methylmethacrylateand in the capacity of the initiator and activator of the hardening - benzoyl peroxide and dimethylaniline. At that polybutylmethacrylate is dissolved in the mixture of butylmethacrylate and methylmetacrylate. The invention ensures manufacture of the qualitative products with the required level of the physical-mechanical and adhesive properties, as well as to reduce smokiness of the gases, and to reduce temperature of the waste gases from 2200°С to 800°С.
EFFECT: the invention ensures manufacture of the qualitative products with the required level of the physical-mechanical and adhesive properties, as well as to reduce smokiness of the gases, and significantly to reduce temperature of the waste gases.
FIELD: polymer materials.
SUBSTANCE: invention relates to polymer composition based on binder, namely unsaturated polyether resin or oligoether acrylates, and may be used in medicine, in production of paint and lacquer materials, etc. Composition comprises, wt parts: unsaturated polyether resin or oligoether acrylates or mixtures thereof, 100; polymerization promoter, in particular complex compound prepared by reaction of vanadium derivatives (vanadium pentoxide, ammonium methavanadate, of methavanadic acid) with orthophosphoric acid/water/butanol mixture, 0.3-0.88; polymerization initiator: cumene hydroperoxide, 0.3-0.44; and modifying additives, 0-20.
EFFECT: optimized makeup involving inexpensive, easily available, and highly efficient promoter.
1 tbl, 6 ex
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention proposes a method for preparing vinylene carbonate mixture. Method involves interaction of monohaloethylene carbonate of the formula (II): wherein X means halogen atom with a dehydrohalogenating agent at temperature in the range 40-80°C but preferably at 60°C in organic solvent medium wherein ethylene carbonate is used as an organic solvent. As a dehydrohalogenating agent method involves using amine, in particular, trialkylamine but preferably triethylamine, and monochloroethylene carbonate is used as monohaloethylene carbonate preferably. Interaction is carried out in inert gas atmosphere preferably. Invention provides preparing vinylene carbonate mixture by a simple and economy method with the high content of vinylene carbonate in the end product. Method provides easily isolation of vinylene carbonate from the prepared mixture by distillation off, for example, under vacuum in the film evaporator. Also, invention relates to a crude vinylene carbonate mixture prepared by above described method that is designated as an additive for lithium-ionic batteries as a component of surface coating material as a monomer for preparing polyvinylene carbonate.
EFFECT: improved preparing method.
7 cl, 3 ex
FIELD: organic chemistry, perfumery.
SUBSTANCE: invention relates to an aromatizing composition containing at least compound of the formula (I): as an active component wherein values w, m, P, X, G, Q and n are given in claim 1 of the invention description, and one or more aromatizing component. Also, invention relates to a method for improving, enhancing or modifying odor, to a method for aromatizing surface, method for enhancing or prolonging the diffusion effect of component on surface and to novel compounds of the formula (I) with exception of compounds enumerated in claim 10 of the invention description and to invention relating to aromatizing article using compounds of the formula (I).
EFFECT: valuable cosmetic properties of compounds.
13 cl, 14 ex