JP2006152273A - Radiation-curable composition and cured product thereof, and laminated form of the cured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-curable composition giving a cured product having high surface hardness and interlaminar adhesion and causing no metal corrosion at high temperatures and humidity, to provide the cured product, and to provide a laminated form having the cured product's layer and suitably usable for optical recording media, etc. <P>SOLUTION: The radiation-curable composition comprises silica particles, a monomer having a urethane linkage or hydroxyalkylene group and/or its oligomer, and a (meth)acrylate other than the above monomer and/or oligomer, wherein the content of the acid groups in the above monomer and/or oligomer is less than 0.1×10<SP>-4</SP>eq/g and the above (meth)acrylate has acid group(s). The cured product obtained by curing the composition by radiation irradiation is provided. The laminated form having the cured product's layer is also provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a radiation curable composition, a cured product thereof, and a laminate thereof. Specifically, a radiation curable composition that has excellent surface hardness and interlayer adhesion, and can give a cured product that does not cause metal corrosion under high temperature and high humidity, and the cured product, and the cured product. It is related with the laminated body suitably used for optical recording media etc ..

  Radiation curable compositions are widely used as various coating materials and adhesive materials, or for optical applications. For example, as a specific example of the optical application of the radiation curable composition, a protective film for an information recording layer in an information recording medium, particularly an optical recording medium, in particular, a study on a next generation high density optical disk using a blue laser has been made in recent years. (See Patent Document 1). In Patent Document 1, urethane (meth) acrylate is used for the protective layer. However, since the protective layer is made thicker than the conventional one, the protective layer alone is insufficient in hardness, and further colloidal silica. Laminating fine particles and a cured product of an ethylenically unsaturated compound as a hard coat layer provides a balance between strength and cure shrinkage. However, such a laminated type protective film is still insufficient practically in terms of cost and operability.

  On the other hand, the applicant of the present invention has silica particles composed of a hydrolyzate of an alkoxysilane oligomer, a monomer having a urethane bond such as urethane (meth) acrylate or / and an oligomer thereof, or a hydroxyalkylene group such as epoxy acrylate. When a radiation curable composition containing a monomer or / and oligomer thereof and having an acidic group in the monomer or / and oligomer thereof is used for optical applications, a cured film having a thickness of several tens of μm or more on the substrate It was found that a layer of the cured product having a surface hardness and transparency and excellent adhesion to the substrate can be provided even in the laminate in which the above layer is formed (see Patent Document 2).

However, the present inventor has further studied this curable composition, and as a result, in a laminate in which a layer of a cured product having a thickness of several tens of μm or more is formed on a substrate, the laminate is silver or a silver alloy. In the case of including an easily corrosive metal layer such as the above, it has been found that there is a defect that the metal layer is easily corroded in a high temperature and high humidity environment, and there is room for improvement in this respect.
JP 2002-245672 A International Publication No. 04/041888 Pamphlet

  As described above, in a cured product of a radiation curable composition that requires surface hardness and interlayer adhesion as conventionally used for a protective film of an information recording layer, a high temperature, high Therefore, the present invention has excellent surface hardness and interlayer adhesion, and causes metal corrosion under high temperature and high humidity. It is an object of the present invention to provide a radiation curable composition capable of giving a cured product free of heat, a cured product thereof, and a laminate having a layer of the cured product and suitably used for an optical recording medium or the like. .

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the silica particles and the monomers having urethane bonds or hydroxyalkylene groups or / and oligomers thereof, and (meth) acrylates other than the monomers or / and oligomers. And a cured product of a radiation curable composition in which the monomer or / and oligomer does not substantially contain an acidic group and the (meth) acrylate contains an acidic group achieves the object. The present invention has been completed and the present invention has been completed. That is, the gist of the present invention is that the monomer or / and oligomer thereof having silica particles, urethane bond or hydroxyalkylene group, and the monomer or / and oligomer. A radiation curable composition containing a (meth) acrylate other than the urethane The content of the acidic group in the monomer and / or oligomer thereof having a slip or hydroxyalkylene group is less than 0.1 × 10 ^-4 eq / g, and a radiation curable which the (meth) acrylate contains an acidic group The composition and the cured product obtained by curing the radiation curable composition by irradiation with radiation, and a laminate having a layer of the cured product.

  According to the present invention, a radiation curable composition having excellent surface hardness and interlayer adhesion, and capable of giving a cured product that does not cause metal corrosion under high temperature and high humidity, and the cured product thereof, and It is possible to provide a laminate that has a layer of the cured product and is suitably used for an optical recording medium or the like.

Hereinafter, a typical example is shown and explained in detail about an embodiment of the invention.
The radiation curable composition of the present invention comprises silica particles, a monomer having a urethane bond or a hydroxyalkylene group or / and an oligomer thereof, and a (meth) acrylate other than the monomer or / and the oligomer [in the present invention, “ “(Meth) acryl” means “acryl” or / and “methacryl”, and so on. The content of acidic groups in the monomer having a urethane bond or hydroxyalkylene group or / and oligomer thereof is less than 0.1 × 10 ⁻⁴ eq / g, and the (meth) acrylate is acidic It is characterized by containing a group.
Hereinafter, each component which comprises the radiation-curable composition is explained in full detail.

[Components of radiation curable composition]
(1) Silica particles and other inorganic components In the radiation curable composition of the present invention, silica refers to silicon oxide in general, regardless of the ratio of silicon to oxygen and whether it is crystalline or amorphous. Examples of the silica particles include industrially sold silica particles dispersed in a solvent, silica particles in powder form, and silica particles derived and synthesized from raw materials such as alkoxysilanes. However, because of the ease of mixing and dispersion as a radiation curable composition, silica particles dispersed in a solvent, or silica particles derived and synthesized from a raw material such as alkoxysilane are more preferable.

  In the present invention, the silica particles are preferably ultrafine particles, and the number average particle diameter is preferably 0.5 nm or more, more preferably 1 nm or more. When the number average particle size is too small, the cohesiveness of the ultrafine particles is extremely increased, and the transparency and mechanical strength of the cured product tend to be extremely decreased, and the characteristics due to the quantum effect tend not to be remarkable. is there. Further, it is preferably 50 nm or less, more preferably 40 nm or less, further preferably 30 nm or less, particularly preferably 15 nm or less, and most preferably 12 nm or less.

  The silica particles are preferably silica particles having a particle size of more than 30 nm, more preferably silica particles having a particle size of more than 15 nm, preferably 1% by weight or less, more preferably 0%, based on the radiation curable composition. .5% by weight or less. Or it is 1 volume% or less preferably with respect to hardened | cured material, More preferably, it is 0.5 volume% or less. If it is contained in a large amount, light scattering increases, which is not preferable because the transmittance decreases.

  For the determination of the number average particle diameter, a numerical value measured from a transmission electron microscope (TEM) observation image is used. That is, the diameter of a circle having the same area as the observed ultrafine particle image is defined as the particle size of the particle image. The number average particle diameter is calculated using, for example, a known image data statistical processing method using the particle diameter determined in this way, and the number of ultrafine particle images (number of statistical processing data) used for such statistical processing should be as large as possible. Is desirable. For example, in terms of reproducibility, the number of randomly selected particle images is 50 or more, preferably 80 or more, and more preferably 100 or more. Calculation of the volume% in hardened | cured material is converted with the volume of the bulb | ball which makes the particle size determined by the above a diameter.

  As the silica particles dispersed in the solvent, for example, those having a solid content of 10 to 40% by weight can be used. Specific examples of the dispersion medium include alcohols such as methyl alcohol, isopropyl alcohol, n-butyl alcohol and isobutyl alcohol; glycols such as ethylene glycol; esters such as ethyl cellosolve; amides such as dimethylacetamide; xylene and the like Hydrocarbons; ketones; ethers; and mixtures thereof, among which isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, ethyl cellosolve, and mixtures thereof are compatible with organic components. It is preferable from the viewpoint of transparency of the cured product obtained. Here, as the silica particles, those subjected to surface treatment with a surface treatment agent such as a surfactant or a silane coupling agent can be used. By using the surface treatment agent, aggregation and particle coarsening can be prevented, and a highly dispersed and transparent radiation curable composition can be obtained.

  Examples of silica particles derived and synthesized from a raw material such as alkoxysilane include silica particles made of a hydrolyzate of an alkoxysilane oligomer. Conventional ordinary silica particles generally have a broad particle size distribution, for example, particles containing particles having a particle size larger than 50 nm. For this reason, the transparency is often poor and the particles tend to settle. There is also. Although what isolate | separated the particle | grains of a big particle size (what is called a cut product) is also known, there exists a tendency which is easy to carry out secondary aggregation, and most things which transparency is impaired. In that respect, according to a specific synthesis method of hydrolysis of an oligomer of alkoxysilane, silica particles having a very small particle diameter can be stably obtained, and the silica particles have a property of being difficult to aggregate. There is an advantage that high transparency can be obtained.

  Here, the hydrolyzate refers to a product obtained by a reaction including at least a hydrolysis reaction, and may be accompanied by dehydration condensation and the like. The hydrolysis reaction also includes a dealcoholization reaction. Alkoxysilane is a compound in which an alkoxy group is bonded to a silicon atom, and these also generate alkoxysilane multimers (oligomers) by hydrolysis reaction and dehydration condensation reaction (or dealcoholization condensation). In order for the alkoxysilane oligomer to be compatible with water and a solvent described later, the alkyl chain of the alkoxysilane used in the present invention is preferably not too long, and usually has about 1 to 5 carbon atoms, preferably the carbon number. It is about 1-3. Specific examples include tetramethoxysilane and tetraethoxysilane.

  The silica particles of the present invention preferably use this alkoxysilane oligomer as a starting material. The reason why the alkoxysilane monomer (monomer) is not used as a starting material is that it is difficult to control the particle size, the particle size distribution tends to be broad, and the particle size is difficult to be uniform. This is because it is difficult to obtain the composition, and there are some kinds of monomers that are toxic, which is undesirable for safety and health. The oligomer can be produced by a known method such as the method described in JP-A-7-48454.

  Hydrolysis of the alkoxysilane oligomer is performed by adding a certain amount of water to the alkoxysilane oligomer in a specific solvent and causing a catalyst to act. Silica ultrafine particles can be obtained by this hydrolysis reaction. As the solvent, one or more of alcohols, glycol derivatives, hydrocarbons, esters, ketones, ethers, etc. can be used in combination. Among them, alcohols, ethers, and ketones can be used. Are particularly preferred.

  Specific examples of alcohols include methanol, ethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, octanol, n-propyl alcohol, acetylacetone alcohol and the like. Specific examples of ethers include tetrahydrofuran, methoxypropanol, methoxybutanol and the like. Specific examples of ketones include acetone, methyl ethyl ketone, and methyl isobutyl ketone. In order to stably present hydrophilic silica particles, it is preferable that the alkyl chains of these alcohols and ketones are short. Particularly preferred are methanol, ethanol, acetone, tetrahydrofuran, methoxypropanol, and methoxybutanol. Among these, methanol and tetrahydrofuran have an advantage of easily removing methanol generated during hydrolysis of the alkoxy oligomer.

  The amount of water necessary for the hydrolysis reaction of the alkoxysilane oligomer is usually 0.05 times or more, more preferably 0.3 times or more the number of moles of alkoxy groups of the alkoxysilane oligomer. If the amount of water is too small, the silica particles do not grow to a sufficient size, and therefore the desired characteristics cannot be exhibited, which is not preferable. However, the amount of water is usually 1.5 times or less, more preferably 1.3 times or less of the number of moles of alkoxy groups of the alkoxysilane oligomer. An excessively large amount of water is not preferable because the alkoxysilane oligomer easily forms a gel. The alkoxysilane oligomer is preferably compatible with the solvent and water used.

  As the catalyst used for the hydrolysis, one or more of metal chelate compounds, organic acids, metal alkoxides, boron compounds and the like can be used, and metal chelate compounds and organic acids are particularly preferable. Specific examples of the metal chelate compound include aluminum tris (acetylacetonate), titanium tetrakis (acetylacetonate), titanium bis (isopropoxy) bis (acetylacetonate), zirconium tetrakis (acetylacetonate), zirconium bis (butoxy). ) Bis (acetylacetonate), zirconium bis (isopropoxy) bis (acetylacetonate), etc., and one or more of these can be used in combination. Narto) is preferably used.

  Specific examples of the organic acid include formic acid, acetic acid, propionic acid, maleic acid and the like. Among these, one or more kinds can be used in combination, and maleic acid is particularly preferably used. When maleic acid is used, there is an advantage that a cured product obtained by radiation curing has a good hue and tends to be less yellowish, which is preferable.

  The amount of these catalyst components to be added is not particularly limited as long as the effect is sufficiently exerted, but is usually preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight based on 100 parts by weight of the alkoxysilane oligomer. It is more than part by weight. However, since the action does not change even if the amount is too large, it is usually preferably 10 parts by weight or less, more preferably 5 parts by weight or less.

By using silica particles composed of hydrolyzed products of alkoxysilane oligomers, radiation-curable compositions can produce ultrafine particles with a much larger particle size than silica particles that are generally used as fillers. There is an advantage that can be added to. In addition, silica particles made of an alkoxysilane oligomer hydrolyzate have the property of not easily agglomerating, so that there is an advantage that the silica particles can be uniformly dispersed in the radiation-curable composition. According to this, even if a large amount of silica particles are added, the radiation transmittance is not impaired, so that a sufficient amount of silica particles can be added to enhance dimensional stability and mechanical strength. Furthermore, by using together the silica particles obtained by such a specific production method and a surface treatment agent for silica particles such as a silane coupling agent described later, a monomer or / and an oligomer thereof described later are added to There is an advantage that a large amount of silica particles can be dispersed without agglomeration. Therefore, the radiation cured product obtained by the present invention has an advantage of having excellent properties having transparency, dimensional stability, mechanical strength, adhesion, and the like.

  In the present invention, usually, the above silica particles, particularly the silica particles formed as described above, are highly polar and compatible with water, alcohol, etc., and the monomer or / and oligomer thereof described later have compatibility. Often not. For this reason, there is a possibility that aggregation or white turbidity may occur when the monomer and / or oligomer thereof is added. To prevent this, the silica particles protect the particle surface by surface treatment as necessary. be able to.

  That is, the surface of the silica particles is made hydrophobic by adding a surface treatment agent having a hydrophilic functional group and a hydrophobic functional group, etc., and has compatibility with the monomer or / and its oligomer to prevent aggregation and cloudiness. As the surface treatment method, a method of modifying the surface with a dispersant or a surfactant or a silane coupling agent is preferably used.

  The dispersant may be selected from polymer dispersants used in fine particle dispersions such as various inks, paints, and electrophotographic toners. As such a polymer dispersant, an acrylic polymer dispersant, a urethane polymer dispersant and the like are appropriately selected and used. Specific examples include “EFKA” (manufactured by Efka Additives), “Disperbyk” (manufactured by BYK Chemy (BYK)), “Disparon” (manufactured by Enomoto Kasei), and the like. The amount of the dispersant used is preferably 10 to 500% by weight, more preferably 20 to 300% by weight, based on the silica particles.

  The surfactant is not particularly limited, but can be selected from cationic, anionic, nonionic, or amphoteric polymers or low molecular weight non-aqueous surfactants. Specifically, sulfonic acid amide (Avesia Pigments & Additives "Solsperse 3000"), hydrostearic acid (Abesia Pigments & Additives "Solsperse 17000"), fatty acid amine, ε-caprolactone Examples include "Solsperse 24000" manufactured by Avecia Pigments & Additives, 1,2-hydroxystearic acid multimer, beef tallow diamine oleate ("Duomine TDO" manufactured by Lion Akzo), and the like. The amount of the surfactant used is preferably 10 to 500% by weight, more preferably 20 to 300% by weight, based on the silica particles.

  In particular, the silica particles are preferably surface-treated with a silane coupling agent. A silane coupling agent is a compound having a structure in which an alkoxy group and an alkyl group having a functional group are bonded to a silicon atom, and has a role of making the surface of silica particles hydrophobic. The silane coupling agent is not particularly limited as long as it achieves the object, but trialkoxysilane having a radiation curable functional group is particularly preferable. Specific examples include epoxycyclohexylethyltrimethoxysilane, glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, acryloyloxypropyltrimethoxysilane, methacryloyloxypropyltrimethoxysilane, mercaptopropyltrimethoxysilane. And mercaptopropyltriethoxysilane.

In the surface treatment with the silane coupling agent, basically, a Si—O—Si bond is generated through a dealcoholization reaction between the alkoxy group of the silane coupling agent and the hydroxy group on the surface of the silica particles. However, the silane coupling agent may be partially hydrolyzed during the surface treatment of the silica particles. Accordingly, the composition after the surface treatment of the silica particles with the silane coupling agent includes a surface selected from a compound selected from the group consisting of a silane coupling agent, a hydrolysis product of the silane coupling agent, and a condensate thereof. Containing silica particles being treated. In addition, there may be a condensate of silane coupling agents and / or a silane coupling agent and a hydrolysis product thereof. Here, the hydrolysis product of the silane coupling agent is a product in which part or all of the alkoxysilane group contained in the silane coupling agent has undergone a hydrolysis reaction to become a hydroxysilane, that is, a silanol group. When the silane coupling agent is epoxycyclohexylethyltrimethoxysilane, epoxycyclohexylethylhydroxydimethoxysilane, epoxycyclohexylethyldihydroxymethoxysilane, and epoxycyclohexylethyltrihydroxysilane are the examples. The silane coupling agents and / or the condensate of the silane coupling agent and its hydrolysis product are those in which an alkoxy group undergoes a dealcoholization reaction with a silanol group, or a Si-O-Si bond, or A silanol group is a group in which a Si—O—Si bond is produced through a dehydration reaction with another silanol group.

  In the present invention, the amount of the silane coupling agent used is preferably 1% by weight or more of the silica particles, more preferably 3% by weight or more, and still more preferably 5% by weight or more. When the amount of the silane coupling agent used is too small, the surface of the silica particles is not sufficiently hydrophobized, which may hinder uniform mixing with the monomer and / or its oligomer. On the other hand, if the amount is too large, a large number of silane coupling components that do not bind to silica particles are mixed in, and this tends to adversely affect the transparency, mechanical properties, and the like of the resulting cured product. Preferably it is 400 weight% or less, More preferably, it is 350 weight% or less, More preferably, it is 300 weight% or less.

  In addition, in this invention, other inorganic components other than a silica particle can also be contained. Although there is no restriction | limiting in particular in another inorganic component, For example, a colorless metal or a colorless metal oxide is used. Specific examples include silver, palladium, alumina, zirconia, aluminum hydroxide, titanium oxide, zinc oxide, calcium carbonate, and clay mineral powder. Alumina, zinc oxide, or titanium oxide is preferable. A method for producing these other inorganic components is not particularly limited, but a method of pulverizing a commercially available product with a pulverizer such as a ball mill or a method of producing by a sol-gel method is preferable because the particle size can be reduced. More preferably, it is a method of producing by a sol-gel method. Moreover, also in these inorganic components other than a silica particle, the particle | grain surface can be protected by surface treatment as needed.

  In the present invention, the other inorganic components are preferably ultrafine particles, and the number average particle diameter is preferably 0.5 nm or more, more preferably 1 nm or more. When the number average particle size is too small, the cohesiveness of the ultrafine particles is extremely increased, and the transparency and mechanical strength of the cured product tend to be extremely decreased, and the characteristics due to the quantum effect tend not to be remarkable. is there. Further, it is preferably 50 nm or less, more preferably 40 nm or less, further preferably 30 nm or less, particularly preferably 15 nm or less, and most preferably 12 nm or less.

  The other inorganic components are preferably other inorganic components having a particle size of more than 30 nm, more preferably other inorganic components having a particle size of more than 15 nm, preferably 1% by weight based on the radiation curable composition. Hereinafter, it is more preferably 0.5% by weight or less. Or it is 1 volume% or less preferably with respect to hardened | cured material, More preferably, it is 0.5 volume% or less. If it is contained in a large amount, light scattering increases, which is not preferable because the transmittance decreases. Examples of the method for determining these number average particle diameters include the same methods as described above.

  The content of the silica particles and other inorganic components in the radiation curable composition of the present invention is preferably included in a large amount within the range that can be contained in order to improve the dimensional stability and hardness characteristics of the cured product. It is preferable to contain 5 weight% or more with respect to a curable composition. More preferably, it is 10% by weight or more. Or it is preferable to contain 2 volume% or more with respect to a radiation hardened | cured material. More preferably, it is 5 volume% or more.

  However, in order to keep the transparency and mechanical strength of the cured product high, it is preferably not too much, and preferably 60% by weight, more preferably 40% by weight or less, more preferably based on the radiation curable composition. 30 wt% or less. Alternatively, it is preferably 30% by volume or less, more preferably 20% by volume or less, and still more preferably 15% by volume or less with respect to the radiation cured product. Among these, the content ratio of the silica particles with respect to the total amount of the silica particles and other inorganic components is usually 50% by weight or more, preferably 60% by weight or more, and more preferably 70% by weight or more. The upper limit is 100% by weight.

(2) Monomer having urethane bond or hydroxyalkylene group or / and oligomer thereof In the radiation curable composition of the present invention, as the monomer having urethane bond, for example, a method of reacting chloroformate with ammonia or amine, Compounds obtained by reacting a compound having an isocyanate group with a compound having a hydroxyl group, a method obtained by reacting urea with a compound having a hydroxyl group, etc., and if the compound has a reactive group, oligomerizes it Can be mentioned. Of these, it is generally easy to use a urethane oligomer, and this urethane oligomer is usually an addition reaction between a compound having two or more isocyanate groups in the molecule and a compound having a hydroxyl group by a conventional method. Manufactured.

  Examples of the compound having two or more isocyanate groups in the molecule include tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, bis (isocyanatomethyl) cyclohexane, cyclohexane diisocyanate, bis (isocyanatocyclohexyl) methane, isophorone diisocyanate, And polyisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, naphthalene diisocyanate. Of these, one or a combination of two or more of bis (isocyanatomethyl) cyclohexane, cyclohexane diisocyanate, bis (isocyanatocyclohexyl) methane, and isophorone diisocyanate is used in that the hue of the resulting urethane oligomer is good. Is preferred.

  As the compound having a hydroxyl group, polyols having two or more hydroxyl groups are preferably used. Specific examples thereof include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol, sorbitol. And alkyl polyols such as mannitol and glycerin, polyether polyols which are multimers thereof, polyester polyols synthesized from these polyols and polyhydric alcohols and polybasic acids, and polyester polyols such as polycaprolactone polyols.

  It is preferable that the urethane oligomer obtained by these contains the polyether polyol as a compound having a hydroxyl group, and the average content of the structural units derived from the polyether polyol in one molecule of the urethane oligomer is 20 It is preferably at least wt%, more preferably at least 25 wt%, particularly preferably at least 30 wt%. Further, it is preferably 90% by weight or less, more preferably 80% by weight or less, and particularly preferably 70% by weight or less. If the content ratio of this polyether polyol is too small, it becomes brittle as a cured product of the composition containing the urethane oligomer obtained by this, and it tends to cause internal stress due to its high elastic modulus, which tends to cause deformation. On the other hand, if it is too large, the surface hardness of the cured product is lowered, and problems such as easy scratching tend to occur.

  Moreover, a urethane acrylate oligomer can be manufactured by using a part of the said compound containing a hydroxyl group as a compound which has a hydroxyl group and a (meth) acryloyl group together. The amount of the compound having the (meth) acryloyl group is usually 30 to 70% in the total hydroxyl group-containing compound, and the molecular weight of the resulting oligomer can be controlled according to the ratio.

  Examples of compounds having both a hydroxyl group and a (meth) acryloyl group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, an addition reaction product of a glycidyl ether compound and (meth) acrylic acid, Examples include mono (meth) acrylates of glycol compounds.

  Furthermore, it has a (meth) acryloyl group at both ends by addition reaction of one compound having two or more isocyanate groups in the molecule and two compounds having both a hydroxyl group and a (meth) acryloyl group. Urethane oligomers can be produced. In particular, urethane oligomers having (meth) acryloyl groups at both ends have the advantage that the adhesiveness and surface curing degree of the resulting resin cured product are further increased.

  The addition reaction between these isocyanate group-containing compounds and hydroxyl group-containing compounds is carried out by a known method, for example, in the presence of an isocyanate group-containing compound, a mixture of a hydroxyl group-containing compound and an addition reaction catalyst such as dibutyltin laurate. It can carry out by dripping on -90 degreeC conditions.

  Examples of the monomer having a hydroxyalkylene group include compounds obtained by reacting an epoxy compound and an unsaturated monobasic acid in the presence of a specific esterification catalyst and a polymerization inhibitor. .

  As an epoxy compound, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, di (6-hydroxyhexyl) ether, 1,8-octanediol, di (8-hydroxyoctyl) ether, 1,10-decanediol, di (10-hydroxydecyl) ether, trimethylolpropane, propylene oxide-added trimethylolpropane, glycerin, polyglycerol, pentaerythritol, propylene oxide-added pentaerythritol, hydrogenated bifphenol A, hydrogenated bisphenol Polyols such as F, bisphenol A, ethylene oxide-added bisphenol A, brominated bisphenol A, bisphenol F, ethylene oxide-added bisphenol F Di- or polyglycidyl ethers, and novolak-type epoxy compounds such as phenol novolak-type epoxy compounds and cresol novolak-type epoxy compounds, and diglycidyl esters of carboxylic acids such as hexahydrophthalic acid, tetrahydrophthalic acid and phthalic acid Etc. These epoxy compounds can be used alone or in admixture of two or more.

  The unsaturated monobasic acid to be reacted with such an epoxy compound is not particularly limited, and examples thereof include (meth) acrylic acid, crotonic acid, cinnamic acid, and (meth) acrylic acid dimer. These acids can be used alone or in combination of two or more.

  The compounding ratio of the epoxy compound and the unsaturated monobasic acid is usually in a range where the carboxyl group in the unsaturated monobasic acid is 0.9 to 1.2 equivalents relative to the epoxy group in the epoxy compound, Among these, a range of 1 ± 0.05 equivalent is preferable in that a resin having excellent curability and storage stability can be obtained. When the blending ratio is smaller than this range, the remaining amount of the epoxy group increases, so that a side reaction product of the epoxy group and the secondary hydroxyl group generated by the ring opening of the epoxy group is generated, and the storage property is also greatly reduced. . When the blending ratio is larger than this range, the unsaturated monobasic acid remaining after the reaction is not preferable because the curing time becomes extremely long.

  As the monomer or / and oligomer thereof containing a urethane bond or a hydroxyalkylene group as described above, a highly transparent material is preferable, for example, a compound having no aromatic ring is preferable. A curable composition and a cured product using a monomer containing an aromatic ring or / and an oligomer thereof are colored products, or even if they are not initially colored, they may be colored or strengthened during storage. There is so-called yellowing. It is thought that this is because the double bond part forming the aromatic ring irreversibly changes its structure by energy rays. For this reason, the monomer or / and oligomer thereof has a structure that does not have an aromatic ring, so that the hue is not deteriorated and the light transmittance is not lowered, so that it is required to be colorless and transparent, such as for optoelectronic applications. There are advantages that make it particularly suitable for application.

  In the monomer having a urethane bond or / and the oligomer thereof, the monomer having no aromatic ring or / and the oligomer thereof are the above-mentioned isocyanate group-containing compound not containing an aromatic ring and hydroxyl group-containing compound not containing an aromatic ring. Can be produced by addition reaction. For example, as the isocyanate compound, it is preferable to use one or more of bis (isocyanatomethyl) cyclohexane, cyclohexane diisocyanate, bis (isocyanatocyclohexyl) methane, and isophorone diisocyanate in combination.

  The monomer having a hydroxyalkylene group and / or the oligomer thereof having no aromatic ring is obtained by combining the epoxy compound having no aromatic ring and the unsaturated-basic acid having no aromatic ring in the above production method. It can manufacture by making it react. The epoxy compound having no aromatic ring does not have an aromatic ring such as hydrogenated bisphenol A type epoxy compound, hydrogenated bisphenol F type epoxy compound, or 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate. It is preferable to use an epoxy compound obtained by a reaction between an epoxy compound and epichlorohydrin.

In the present invention, a monomer having a urethane bond or a hydroxyalkylene group or / and an oligomer thereof are, for example, a carboxyl group, phosphoric acid in that a cured product that does not cause metal corrosion under high temperature and high humidity can be provided. Group, sulfonic acid group, and tertiary amine compound neutralized salts or metal salts thereof are preferably substantially free of acidic groups, and even if they have, the content of these acidic groups is 0.1 × 10 ^It is preferably less than ^-4 eq / g. If the content of acidic groups in the monomer having a urethane bond or hydroxyalkylene group and / or oligomer thereof is more than this range, it is considered that the monomer component to which the acidic group is bonded is released over time, Corrosion is likely to occur in the metal layer under high temperature and high humidity.

  In the radiation curable resin composition of the present invention, the monomer containing a urethane bond or a hydroxyalkylene group or / and the oligomer thereof usually have a radiation curable functional group. Thereby, since the monomer and oligomer which have a urethane bond or a hydroxyalkylene group are integrated and integrated in a radiation hardening network structure, cohesiveness increases, as a result, cohesive failure does not occur easily and there exists an advantage which adhesiveness improves. Moreover, since the effect of restricting the free movement of oxygen is enhanced, there is an advantage that the degree of surface hardening is improved.

  The radiation curable group is not particularly limited as long as it is a group capable of being polymerized by radiation, but is a radical reactive group, a group having a photocation reactivity such as a photocation curable glycidyl group, or a photoanion reaction. And a group having photo-thiol-ene reactivity such as a thiol group, among which a group having radical reactivity is preferable.

  Examples of such a functional group having radical reactivity include (meth) acryloyl group and vinyl group. Among them, (meth) acryloyl group is particularly preferred from the viewpoint of polymerization reaction rate, transparency, and coatability. preferable. When a (meth) acryloyl group is used, 50% or more of the total number of radiation-curable functional groups may be a (meth) acryloyl group.

  Furthermore, it is preferable that the monomer or / and oligomer thereof is mainly composed of a compound having two or more radiation curable groups in one molecule. Here, “mainly” means to occupy 50% by weight or more of all monomers and / or oligomers thereof. In this case, a three-dimensional network structure can be formed by a polymerization reaction by radiation, and an insoluble and infusible cured resin can be obtained. In the present invention, the radiation-curable functional group is polymerized with radiation such as active energy rays (for example, ultraviolet rays) and electron beams, so that it can be cured at a high speed while the ultrafine particles are highly dispersed. Radiation curing generally proceeds at a very high rate in seconds. Accordingly, it is possible to prevent an undesirable phenomenon such that the ultrafine particles move or aggregate in the curing process, and thus a cured product having a high degree of transparency can be obtained. On the other hand, thermal polymerization takes several tens of minutes to several hours, which is not preferable because the ultrafine particles may move and aggregate during polymerization and become cloudy.

  In the present invention, only a monomer containing a urethane bond or a hydroxyalkylene group may be used, only an oligomer containing a urethane bond or a hydroxyalkylene group may be used, or a mixture of both may be used. . Since many of the monomers are liquids having a lower viscosity than the oligomers, they are advantageous when mixed with other components. Moreover, there exists an advantage which is easy to shape | mold, such as coating and cast molding. However, some of them are toxic and need attention. On the other hand, oligomers are generally high in viscosity and may be difficult to handle. However, there are advantages that the degree of surface curing is excellent, the curing shrinkage tends to be small, and the cured product has many excellent mechanical properties, particularly tensile properties and bending properties.

  In the present invention, the monomer or oligomer containing a urethane bond or a hydroxyalkylene group may be hydrophilic, but is preferably hydrophobic. Moreover, as a monomer or / and its oligomer containing a urethane bond or a hydroxyalkylene group, it is preferable to use an oligomer having a relatively high molecular weight. The molecular weight is preferably 1000 or more, more preferably 2000 or more. Further, it is usually 50,000 or less, preferably 30,000 or less, more preferably 20,000 or less, more preferably 10,000 or less, and particularly preferably 5,000 or less.

  By using such an oligomer having a relatively high molecular weight, there is a tendency that the degree of surface curing and adhesion of the cured product are improved. The reason for this is not clear, but the composition containing the oligomer tends to reduce curing shrinkage. Therefore, the functional group density is relatively small, and the curing reaction is efficiently performed. It is presumed that the residual strain is related to the degree of surface hardening and the improvement of adhesion. Such high molecular weight oligomers may be used alone or in a mixture of two or more. Moreover, you may use together with other monomer and oligomer of lower molecular weight. When oligomers with extremely high molecular weight are used, the viscosity of the composition may increase, and moldability and workability may deteriorate.In this case, the amount of low molecular weight oligomers and monomers and reactive diluent added may be reduced. It can be improved by increasing it.

  When the monomer which has a urethane bond or a hydroxyalkylene group or / and its oligomer are used for the radiation-curable composition of this invention, there exists an advantage that the time-dependent adhesiveness and surface-hardening degree of the hardened | cured material obtained increase. The phenomenon that adhesion improves when a monomer having a urethane bond or hydroxyalkylene group or / and an oligomer thereof is used is that the interaction with the adherend is strengthened by the electrical polarity of the urethane bond or hydroxyalkylene group. It is thought to be derived from. In addition, the reason why the surface curing degree is improved when using a monomer having a urethane bond or a hydroxyalkylene group or / and an oligomer thereof is not clear, but the monomer having a urethane bond or a hydroxyalkylene group or / and an oligomer thereof are fixed. In the composition containing more than the amount, since the intramolecular hydrogen bond and intermolecular hydrogen bond derived from the electrical polarity of the urethane bond or hydroxyalkylene group are easily formed, the cohesion of the organic molecule is enhanced, and as a result It is presumed that the main reason is that free movement of oxygen in the composition is inhibited, and inhibition of radical polymerization is suppressed.

  The content of the monomer or / and oligomer thereof is usually preferably 40% by weight or more in the radiation curable composition, more preferably 50% by weight or more, and preferably 95% by weight or less. More preferably, it is 90% by weight or less. If the amount is too small, moldability and mechanical strength when forming a cured product are lowered, and cracks are likely to occur, which is not preferable. On the other hand, if the amount is too large, the surface hardness of the cured product decreases, which is not preferable.

(3) (Meth) acrylates other than the monomer or / and oligomer thereof The radiation curable composition of the present invention includes the monomer or / and oligomer thereof having the urethane bond or hydroxyalkylene group, and the monomer or / and oligomer thereof. It is essential that the (meth) acrylate other than the above and the (meth) acrylate contain an acidic group. Examples of the acidic group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and tertiary amine compound neutralized salts or metal salts thereof.

  Here, examples of the (meth) acrylate having a carboxyl group include those represented by the following general formula (I).

[In formula (I), R ¹ represents a hydrogen atom or a methyl group, and X represents a divalent group. ]

In the general formula (I), examples of the divalent group of X include an alkylene group, an arylene group, an alkylene arylene group, and an -A ^1- (OOC-A ² ) _m -group (provided that A ¹ and A ² are , An alkylene group, an arylene group, an alkylene arylene group, and m is an integer of 1 or more. These (meth) acrylates are usually 2-20 mer oligomers.

  Specific examples of these (meth) acrylates represented by the general formula (I) include (meth) acrylates represented by the following formulas (Ia) to (Id).

[In formulas (Ia) to (Id), R ¹ represents a hydrogen atom or a methyl group, and n is an integer of 1 to 10. ]

  As the (meth) acrylate in the present invention, specifically, for example, “Aronix M-5300”, “Aronix M-5400”, “Aronix M-5500”, “Aronix M-5600” manufactured by Toa Gosei Chemical Co., Ltd., etc. Shin-Nakamura Chemical Co., Ltd. “NK Ester SA” (β-methacryloyloxyethyl hydrogen succinate), “NK Ester A-SA” (β-acryloyloxyethyl hydrogen succinate), etc. “Biscoat #” manufactured by Osaka Organic Chemical Co., Ltd. 2000 ”,“ Biscoat # 2100 ”,“ Biscoat # 2150 ”,“ Biscoat # 2180 ”, etc.,“ HOA-MS ”(2-acryloyloxyethyl succinic acid),“ HO-MS ”(2- Methacryloyloxyethyl succinic acid), “HOA-MPL” (2-acrylic acid) Royloxyethylphthalic acid), “HO-MPL” (2-methacryloyloxyethylphthalic acid), “HOA-MPE” (2-acryloyloxyethyl-2-hydroxyethylphthalic acid) and the like, and pentaerythritol tri (meta) ) Maleic esters of hydroxyl group-containing (meth) acrylates such as acrylate maleic esters.

  Moreover, as (meth) acrylate which has a phosphoric acid group, (meth) acryloyl oxyethyl phosphate (Kyoeisha Oil Chemical Co., Ltd. product "light acrylate P-1M") etc., (meth) acrylic-acid hydroxyalkyl (C2-C2), for example. 8) Phosphates of esters, phosphoric acid diesters of (meth) acryloyloxyalkyl (carbon number 2 to 8) esters such as phenyl-2- (meth) acryloyloxyethyl phosphate, and the like.

  Examples of the (meth) acrylate having a sulfonic acid group include 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxypropanesulfonic acid, and 2-hydroxy-3- (meth) acryloyloxypropane. Sulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid, 2- (meth) acryloylamino-2-methylpropanesulfonic acid, 3- (meth) acryloylamino-2-hydroxypropanesulfonic acid, And sulfonic acid esters of (meth) acrylic acid alkyl esters.

  As the (meth) acrylate having these acidic groups, a (meth) acrylate having a carboxyl group is preferable, and a (meth) acrylate represented by the general formula (I) is particularly preferable.

  The content of the (meth) acrylate having these acidic groups is preferably 3% by weight or more, and preferably 30% by weight or less in the radiation curable composition. If the amount is too small, the interlaminar adhesion tends to decrease, and if the amount is too large, metal corrosion tends to occur.

(4) Other monomer or / and oligomer thereof In the radiation-curable composition of the present invention, the monomer having a urethane bond or a hydroxyalkylene group and / or its oligomer, and the above-mentioned other than the monomer and / or its oligomer ( In addition to (meth) acrylate, other radiation-curable monomers or / and oligomers thereof, preferably bifunctional or trifunctional (meth) acrylate compounds may be mixed and used.

Examples of the bifunctional or trifunctional (meth) acrylate compound include alicyclic poly (meth) acrylate, alicyclic poly (meth) acrylate, and aromatic poly (meth) acrylate. Specifically, polyethylene glycol di (meth) acrylate, 1,2-polypropylene glycol di (meth) acrylate, 1,3-polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 1,2 -Di (meth) of alkylene oxide adducts such as ethylene oxide, propylene oxide or butylene oxide of bisphenol such as polybutylene glycol di (meth) acrylate, polyisobutylene glycol di (meth) acrylate, bisphenol A, F, or S Di (meth) acrylate of hydrogenated derivatives of bisphenol such as acrylate, bisphenol A, F, or S, block of various polyether polyol compounds and other compounds, or random copolymer (Meth) acrylates having a polyether skeleton such as (meth) acrylate, and hexanediol di (meth) acrylate, 2,2-bis [4- (meth) acryloyloxyphenyl] propane, 2,2-bis [ 4- (2- (meth) acryloyloxyethoxy) phenyl] propane, bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = dimethacrylate, p-bis [β- (meth) acryloyloxy Divalent (meth) acrylates such as ethylthio] xylylene, 4,4′-bis [β- (meth) acryloyloxyethylthio] diphenylsulfone, trimethylolpropane tris (meth) acrylate, glycerin tris (meth) acrylate , Trivalent (meth) pentaerythritol tris (meth) acrylate, etc. ) Acrylates, indeterminate polyvalent (meth) acrylates such as tetravalent (meth) acrylates such as pentaerythritol tetrakis (meth) acrylate and the like. Of these, the above divalent (meth) acrylates are preferably used because of the controllability of the cross-linking reaction.

Of these, (meth) acrylates having a polyether skeleton are preferred because they are excellent in dimensional stability of the resulting cured product. Specific examples of the commercially available products include, for example, “NK Ester A” series, “NK Ester G” series, “NK Ester APG” series, “NK Ester PG” series, “NK Ester A-BPE” manufactured by Shin-Nakamura Chemical Co., Ltd. ”Series,“ NK ester A-GLY ”series,“ NK ester A-TMPT03EO ”,“ NK ester ATM-4E ”, etc.,“ Aronix M-200 ”series manufactured by Toa Gosei Co., Ltd. DA ”series,“ Blemmer PDE-400 ”series manufactured by NOF Corporation,“ New Frontier PE ”series,“ New Frontier BPE ”series manufactured by Daiichi Kogyo Kagaku Co., Ltd. and the like. In this invention, these can be used individually or in combination of 2 or more types.

  Furthermore, a (meth) acrylate compound containing a hydroxyl group is preferably added for the purpose of improving adhesiveness and adhesion. Specific examples of the compound include hydroxyethyl (meth) acrylate.

  Among the (meth) acrylates exemplified above, it is particularly preferable to add and use the following component A and the following component B in terms of achieving a balance between transparency and low optical distortion of the resulting polymer. . Component A is a bis (meth) acrylate having an alicyclic skeleton represented by the following general formula (II).

[In the formula (II), R ^a and R ^b each independently represent a hydrogen atom or a methyl group, R ^c and R ^d each independently represent an alkylene group having 6 or less carbon atoms, x is 1 or 2 and y represents 0 or 1, respectively. ]

Specific examples of the component A represented by the general formula (II) include bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane diacrylate, bis (hydroxymethyl) tricyclo [5.2. .1.0 ^2,6] decane = dimethacrylate, bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6] decane = acrylate methacrylate and mixtures thereof, bis (hydroxymethyl) pentacyclo [6.5 1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane diacrylate, bis (hydroxymethyl) pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane = dimethacrylate, bis (hydroxymethyl) pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . ^0,13 ] pentadecane = acrylate methacrylate and mixtures thereof. These tricyclodecane compounds and pentacyclodecane compounds may be used in combination.

  Component B is a bis (meth) acrylate having a sulfur atom represented by the following general formula (III).

[In the formula (III), R ^a and R ^b may be the same as R ^a and R ^b in the general formula (II), and each R ^e represents an alkylene group having 1 to 6 carbon atoms. Each Ar represents an arylene group or aralkylene group having 6 to 30 carbon atoms, and these hydrogen atoms may be substituted with a halogen atom other than a fluorine atom. Each X represents an oxygen atom or a sulfur atom, and when each X is an oxygen atom, at least one of each Y represents a sulfur atom or a sulfone group (—SO ₂ —), and at least one of each X represents sulfur. In the case of an atom, each Y is a sulfur atom, a sulfone group, a carbonyl group (—CO—), and an alkylene group, an aralkylene group, an alkylene ether group, an aralkylene ether group, an alkylene thioether group and an aralkyl having 1 to 12 carbon atoms, respectively. Any one of xylene thioether groups, j and p each independently represent an integer of 1 to 5, and k represents an integer of 0 to 10; When k is 0, X represents a sulfur atom. ]

  Specific examples of the component B represented by the general formula (III) include α, α′-bis [β- (meth) acryloyloxyethylthio] -p-xylene, α, α′-bis [β- (Meth) acryloyloxyethylthio] -m-xylene, α, α′-bis [β- (meth) acryloyloxyethylthio] -2,3,5,6-tetrachloro-p-xylene, 4,4 ′ -Bis [β- (meth) acryloyloxyethoxy] diphenyl sulfide, 4,4'-bis [β- (meth) acryloyloxyethoxy] diphenylsulfone, 4,4'-bis [β- (meth) acryloyloxyethylthio ] Diphenyl sulfide, 4,4′-bis [β- (meth) acryloyloxyethylthio] diphenylsulfone, 4,4′-bis [β- (meth) acryloyloxyethylthio] di Phenyl ketone, 2,4′-bis [β- (meth) acryloyloxyethylthio] diphenyl ketone, 5,5′-tetrabromodiphenyl ketone, β, β′-bis [p- (meth) acryloyloxyphenylthio] Examples include diethyl ether, β, β′-bis [p- (meth) acryloyloxyphenylthio] diethylthioether, and the like.

Among the components A and B, bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = dimethacrylate has excellent transparency and heat resistance and is particularly preferably used. The amount of these other radiation curable monomers or / and oligomers thereof used is preferably 50% by weight or less, more preferably 30% by weight or less based on the composition other than the inorganic component.

(5) Reactive Diluent A reactive diluent may be added to the radiation curable composition of the present invention for the purpose of adjusting the viscosity of the composition. In the present invention, the reactive diluent is a low-viscosity liquid compound and is usually a monofunctional low-molecular compound. For example, the compound which has a vinyl group or a (meth) acryloyl group, mercaptans, etc. are mentioned. Specific examples of such compounds include aromatic vinyl monomers, vinyl ester monomers, vinyl ethers, (meth) acrylamides, (meth) acrylic esters, di (meth) acrylates and the like. From the viewpoint of hue and light transmittance, a compound having a structure having no aromatic ring is preferred. Among them, (meth) acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylate having an alicyclic skeleton such as (meth) acrylate having a tricyclodecane skeleton (Meth) acrylamides such as N, N-dimethylacrylamide, aliphatic (meth) acrylates such as hexanediol di (meth) acrylate and neopentylglycol di (meth) acrylate have good hue and viscosity. Are particularly preferably used.

  A compound having both a hydroxyl group and a (meth) acryloyl group, such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate, can also be used for this purpose. The adhesiveness of the composition to glass may be improved, which is preferable.

  The usage-amount of these reactive diluents is 0.5 to 80 weight% with respect to compositions other than an inorganic component, Preferably it is 1 to 50 weight%. If the amount is too small, the diluting effect is small. On the other hand, if the amount is too large, the cured product tends to become brittle, and the mechanical strength tends to be lowered.

(6) Polymerization initiator In the radiation-curable composition of the present invention, it is usually preferable to add a polymerization initiator in order to initiate a polymerization reaction that proceeds by active energy rays (for example, ultraviolet rays). As such a polymerization initiator, a radical generator that is a compound having a property of generating radicals by light is generally used, and known such compounds can be used. Examples of the radical generator include benzophenone, 2,4,6-trimethylbenzophenone, 4,4-bis (diethylamino) benzophenone, 4-phenylbenzophenone, methyl orthobenzoyl benzoate, thioxanthone, diethylthioxanthone, isopropylthioxanthone, chlorothioxanthone. 2-ethylanthraquinone, t-butylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, benzoin ethyl ether , Benzoin isopropyl ether, benzoin isobutyl ether, methyl benzoyl formate, 2-methyl-1- [4- ( Tilthio) phenyl] -2-morpholinopropan-1-one, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4 Examples include 4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and a plurality of these may be used in combination. Among these, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and benzophenone are preferable, and the combined use of 1-hydroxycyclohexyl phenyl ketone and benzophenone is more preferable.

  Among these radical generators, when the cured product of the radiation curable composition of the present invention is used in an optical recording medium using a laser having a wavelength of 380 to 800 nm as a light source, the laser beam necessary for reading is sufficient. It is preferable to select and use the type and amount of the radical generator so as to pass through the cured product layer. In this case, it is particularly preferable to use a short wavelength photosensitive radical generator in which the obtained cured product layer hardly absorbs laser light. Examples of such a short wavelength photosensitive radical generator include benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, methylorthobenzoylbenzoate, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane. Examples include -1-one, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and methyl benzoyl formate.

  The amount of the radical generator added is usually 0.001 parts by weight or more, preferably 0.01 parts by weight or more, more preferably 100 parts by weight or more of the total of the monomers containing radiation-curable functional groups and / or oligomers thereof. Is 0.05 parts by weight or more, particularly preferably 0.1 parts by weight or more. However, it is usually 10 parts by weight or less, preferably 9 parts by weight or less, more preferably 8 parts by weight or less, and particularly preferably 7 parts by weight or less. If the amount added is too large, the polymerization reaction may proceed rapidly and not only increase the optical distortion but also deteriorate the hue. If the amount is too small, the composition may not be sufficiently cured. . In addition, when starting a polymerization reaction with an electron beam, although the said radical generator can also be used, it is more preferable not to use a radical generator.

  As the polymerization initiator, known radical generators such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone, etc. A sensitizer may be used in combination.

(7) Surface Tension Adjusting Agent A surface tension adjusting agent can be added to the radiation curable composition of the present invention for the purpose of reducing the surface tension of the composition and improving the coating property to the substrate. Specific examples include low molecular weight and high molecular weight surfactants, silicone compounds and various modified products thereof (polyether modified, fluorine modified, etc.), sorbitan esters, other various leveling agents, antifoaming agents, rheology control agents, release agents. Examples include molds. Of these, silicone compounds such as “Polyflow KL510” (manufactured by Kyoei Chemical Co., Ltd.) are preferred, and polyether-modified silicone compounds such as “KF351A” (manufactured by Shin-Etsu Chemical Co., Ltd.) and fluorine-modified surfactants are preferred for surface tension. This is preferable because it exhibits a property that hardly causes coating defects and is excellent in antifouling property, slipperiness, and environmental resistance. The addition amount of the surface tension modifier is usually 5% by weight or less, preferably 3% or less, more preferably 0.01 to 1% by weight based on the composition, although it depends on the type.

(8) Solvent A solvent may be used in the radiation curable composition of the present invention. The solvent is preferably colorless and transparent. Specifically, one or a combination of two or more of alcohols, glycol derivatives, hydrocarbons, esters, ketones, ethers and the like can be used. Specific examples of alcohols include methanol, ethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, octanol, n-propyl alcohol, acetylacetone alcohol and the like. Specific examples of ketones include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Among these, methanol, ethanol, or acetone is particularly preferable. However, the amount of the solvent used is preferably smaller in view of operability during the curing reaction, and is preferably 95% by weight or less, more preferably 30% by weight or less, more preferably based on the composition. It is preferably 20% by weight or less, particularly preferably 10% by weight or less, particularly preferably 5% by weight or less, and most preferably no solvent.

(9) Other auxiliary components To the radiation-curable composition of the present invention, other auxiliary components such as additives are added as necessary, as long as the produced cured product does not significantly depart from the object of the present invention. Also good. Other auxiliary components include, for example, stabilizers such as antioxidants, heat stabilizers, or light absorbers; fillers such as glass fibers, glass beads, mica, talc, kaolin, metal fibers, metal powders; carbon fibers Carbon materials such as carbon black, graphite, carbon nanotubes, fullerenes such as C ₆₀ (fillers and fullerenes are collectively referred to as inorganic filler components); antistatic agents, plasticizers, mold release agents, Modification agents such as antifoaming agents, leveling agents, anti-settling agents, surfactants, thixotropy imparting agents; coloring agents such as pigments, dyes, hue adjusting agents; synthesis of monomers or / and oligomers thereof, or inorganic components Examples of the curing agent, catalyst, and curing accelerator necessary for the above are exemplified. The addition amount of these auxiliary components is not limited as long as the cured product to be produced does not deviate significantly from the object of the present invention, but is usually 20% by weight or less of the radiation curable composition.

In addition, the radiation curable composition of the present invention is further mixed with a monomer other than radiation curable or / and an oligomer thereof for the purpose of improving mechanical properties and heat resistance or balancing various properties. May be. Although the kind of the monomer or / and its oligomer is not specifically limited, Specifically, a thermoplastic resin, a thermosetting resin monomer or / and its oligomer, etc. are used.

  Examples of the thermoplastic resin include polystyrene; polymethyl methacrylate; polyarylate, polyester such as “O-PET” (manufactured by Kanebo); polycarbonate; polyethersulfone; “Zeonex” (manufactured by Zeon Japan), “Arton” (JSR) Alicyclic thermoplastic resins such as “Apel” (manufactured by Mitsui Chemicals), etc., and polycarbonate or polyethersulfone is preferred from the viewpoint of transparency and dimensional stability. The amount of the thermoplastic resin used is preferably 20% by weight or less based on the composition other than the inorganic component. In addition, as the thermosetting resin monomer or / and oligomer thereof, an epoxy resin; “Rigolite” (manufactured by Showa Denko) or the like is used, and a high-purity epoxy resin is preferable from the viewpoint of transparency and dimensional stability. . The amount of the thermosetting resin used is preferably 50% by weight or less based on the composition other than the inorganic component.

[Physical properties of radiation curable composition]
The radiation curable composition of the present invention contains an acidic group derived from containing the (meth) acrylate having an acidic group, and the content thereof is 0.1 × 10 ⁻⁴ eq / g or more. Is preferably 1 × 10 ⁻⁴ eq / g or more, particularly preferably 1.5 × 10 ⁻⁴ eq / g or more. Further, it is preferably 13 × 10 ⁻⁴ eq / g or less, more preferably 10 × 10 ⁻⁴ eq / g or less, and particularly preferably 4 × 10 ⁻⁴ eq / g or less. If the content of the acidic group is less than the above range, the interlayer adhesion tends to decrease as a cured product, while if it exceeds the range, metal corrosion tends to occur as the cured product.

  The radiation curable composition of the present invention preferably has a viscosity at 25 ° C. of 500 centipoises or more, more preferably 1000 poises or more, and particularly preferably 2000 centipoises or more. Moreover, it is preferable that it is 15000 centipoise or less, More preferably, it is 10,000 centipoise or less, Most preferably, it is 10000 centipoise or less. If the thickness is less than 500 centipoise, it is difficult to form a cured product having a thickness of 50 μm or more. Therefore, it cannot be used for applications such as information recording media that require such a thick cured product. . Conversely, if it is larger than 15000 centipoise, it becomes difficult to form a cured product having a smooth surface, which is not preferable. The viscosity may be measured with an E-type viscometer, a B-type viscometer, or a vibration-type viscometer. As a method for adjusting the viscosity, there are techniques such as addition of a diluent, addition of a solvent, molecular weight control of a radiation curable oligomer, addition of a thickener, or addition of a rheology control agent, preferably addition of a diluent, The molecular weight control of the radiation curable oligomer and the addition of a thickener are used, and the addition of a diluent is more preferably used.

  Transparency of the radiation curable composition is not particularly limited as long as the cured product obtained by curing the composition is transparent depending on the application, and the transparency of the composition itself is not particularly limited, but preferably at 550 nm The light transmittance with an optical path length of 0.1 mm is 80% or more, more preferably 85% or more. More preferably, the light transmittance at an optical path length of 0.1 mm at 400 nm is 80% or more, more preferably 85% or more. If the light transmittance is too low, the transparency at the time of curing tends to be greatly impaired, and when the cured product is used in an optical recording medium, a reading error increases at the time of reading recorded information, which is not preferable.

The radiation curable composition preferably has a surface tension at 25 ° C. of 50 mN / m or less. More preferably, it is 40 mN / m or less, more preferably 35 mN / m or less, and particularly preferably 30 mN / m or less. If the surface tension is too high, the spreadability of the composition at the time of coating deteriorates, and not only the amount of the composition required at the time of coating increases, but also a defect is caused, which is not preferable. The smaller the surface tension, the better.
0 mN / m or more. The surface tension may be measured using a surface tension meter (for example, “CBVP-A3 type” manufactured by Kyowa Interface Science Co., Ltd.). Examples of the method for adjusting the surface tension include addition of the surface tension adjusting agent.

  The radiation curable composition preferably contains substantially no solvent. “Contains substantially no solvent” means a state in which the content of a so-called organic solvent having volatility or a low boiling point is very low, and the solvent content in the composition is usually 5% by weight or less. More preferably, it is 3% by weight or less, particularly preferably 1% by weight or less, particularly preferably 0.1% by weight or less. For simplicity, it means a state in which no odor of the organic solvent is observed.

[Production of radiation curable composition]
In the radiation-curable composition of the present invention, silica particles are uniformly dispersed in a mixture of a monomer containing a urethane bond or a hydroxyalkylene group or / and an oligomer thereof and a (meth) acrylate other than the monomer or / and the oligomer. The mixing method is not particularly limited. Specifically, for example, (1a) a monomer or / and an oligomer thereof prepared in an appropriate liquid state after preparing silica particle powder and performing an appropriate surface treatment (1b) A silica particle powder is prepared, subjected to an appropriate surface treatment, and then directly dispersed in a monomer or / and oligomer thereof in an appropriate liquid state, A method of adding (meth) acrylate, (2a) an appropriately liquid monomer or / and oligomer thereof and (meth) A method of synthesizing silica particles in a mixture of acrylates, (2b) a method of synthesizing silica particles in an appropriately liquid monomer or / and oligomer thereof and then adding (meth) acrylate, (3) liquid medium (4a) a monomer and / or an oligomer thereof in a liquid medium (4a) a method in which silica particles are prepared and the monomer and / or oligomer thereof and (meth) acrylate are dissolved in the liquid medium and then the solvent is removed; (4) A method in which the solvent is removed after dissolving the (meth) acrylate and preparing the silica particles in the liquid medium. (4b) The monomer and / or the oligomer thereof is dissolved in the liquid medium, and the silica particles are dissolved in the liquid medium. A method of preparing and then adding (meth) acrylate and then removing the solvent, (5) silica in a liquid medium After adjusting the child and monomer and / or oligomer thereof, and a method of removing the added solvent (meth) acrylate. Of these, (1a), (1b), and (3) are preferable because they are easy to obtain those having high transparency and good storage stability, and more preferably (3).

  Specifically, as the method of (1a) and (1b), (A) a step of modifying silica particles with a surface treatment agent, (B) a monomer having a urethane bond or a hydroxyalkylene group or / and an oligomer thereof, and The method of performing the process of mixing a (meth) acrylate and the process of removing a solvent under the temperature of 10-100 degreeC as needed as needed (C) is mentioned. According to this production method, secondary aggregation of the silica particles and coarsening of the particle diameter can be prevented, and a highly dispersed radiation curable composition can be easily obtained.

  In the step (A), the reaction is allowed to proceed at room temperature, usually for 0.5 to 24 hours, and the reaction is allowed to proceed. When heated, the reaction rate increases and the reaction can be carried out in a shorter time. The step (B) needs to be performed after the reaction in the step (A) is sufficiently completed. If the operation (B) is performed before the reaction (A) sufficiently proceeds, the monomers and oligomers thereof are not mixed uniformly, and the composition becomes unclear in the subsequent step, which is not preferable. The step (B) can be performed at room temperature, but can be performed by heating when the viscosity of the monomer or its oligomer is high or when the melting point of the monomer or its oligomer is at least room temperature. In the step (C), removal of water and solvents such as alcohol and ketone is mainly performed. However, it may be removed within a necessary range, and may not be completely removed. In addition, when temperature is lower than the range described, the removal of a solvent is not fully performed but it is unpreferable. Conversely, when too high, since a composition becomes easy to gelatinize, it is unpreferable.

  Specifically, as the method (3), (a) an alkoxysilane oligomer is hydrolyzed at a temperature of 10 to 100 ° C. in a liquid medium such as a solvent, a surface treatment agent or a diluent to synthesize silica particles. (B) a step of protecting the surface of silica particles, (c) a step of mixing a monomer or / and oligomer thereof containing a urethane bond or a hydroxyalkylene group, and (meth) acrylate, and (d) 10 to 75. The step of removing the solvent at a temperature of 0 ° C. is preferably performed by sequentially performing the steps. According to this production method, a radiation curable resin composition in which ultrafine silica particles having a uniform particle size are highly dispersed can be obtained more easily.

In the step (a), an alkoxysilane oligomer, a catalyst and water are added in a liquid medium to hydrolyze the alkoxysilane oligomer to synthesize silica particles. The liquid medium is not particularly limited, but is preferably compatible with the monomer and / or its oligomer. Specifically, a solvent, a surface treatment agent or a diluent is used. The surface treatment agent and diluent are the same as described above. As the solvent, preferably used are alcohols or ketones, particularly preferably an alcohol of C ₁ -C _4, acetone, methyl ethyl ketone or methyl isobutyl ketone is used. The amount of the liquid medium is preferably 0.3 to 10 times that of the alkoxysilane oligomer.

  Catalysts include organic acids such as formic acid and maleic acid; inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid; and hydrolysis catalysts such as metal complex compounds such as acetylacetone aluminum, dibutyltin dilaurate and diztiltin dioctaate. . The amount used is preferably 0.1 to 3% by weight based on the oligomer of the alkoxysilane. The water is preferably added in an amount of 10 to 50% by weight based on the oligomer of alkoxysilane. The hydrolysis temperature is 10 to 100 ° C. If it is lower than this, the reaction for forming silica particles does not proceed sufficiently, which is not preferable. On the other hand, if it is too high, an oligomer gelation reaction tends to occur, which is not preferable. The hydrolysis time is preferably 30 minutes to 1 week.

  The reaction (b) is a step of protecting the surface of silica particles, and examples of the surface protective agent include surfactants, dispersants, silane coupling agents and the like. In the case of using a surfactant or a dispersant, a surface protective agent is added, and the reaction is performed by stirring at a temperature of room temperature to 60 ° C. for about 30 minutes to 2 hours. And aging for several days. When adding, it is important not to select a solvent with a very high solubility of the surface protecting agent. When a solvent having a very high solubility of the surface protective agent is used, it is not preferable because the protection to the inorganic component is not sufficiently performed or a long time is required for the protection process. In the case of a solvent having a very high solubility of the surface protective agent, for example, when a solvent having a difference in solubility value (SP value) between the solvent and the surface treatment agent of 0.5 or more is used, the protection to the inorganic component is achieved. Often done well.

  When a silane coupling agent is used, the surface protection reaction proceeds at room temperature (25 ° C.). Usually, stirring is performed for 0.5 to 24 hours to allow the reaction to proceed, but heating may be performed at a temperature of 100 ° C. or lower. When heated, the reaction rate increases, and the reaction can be carried out in a shorter time. However, since polymerization between silane coupling agents may occur and the solution may become cloudy, the heating temperature is preferably 90 ° C. or less, more preferably Is 80 ° C. or lower, more preferably 70 ° C. or lower.

When a silane coupling agent is used, it is preferable not to add water to the system, but water may be added. However, if the amount of water to be added is excessively large at that time, hydrolysis and dehydration condensation reactions proceed in a state where the surface protection of the silica particles is not sufficiently performed, causing the composition to become cloudy or gelled. In particular, when the concentration of the silica particles in the composition is large, care must be taken because the composition becomes noticeably cloudy or gelled. The preferred amount of water added is 30 mol% or more, more preferably 50 mol% or more, and more preferably 50 mol% or more, based on the amount required for hydrolysis of the alkoxy group derived from the silane coupling agent and the remaining alkoxy group derived from alkoxysilane. The amount is preferably 70 mol% or more, and 130 mol% or less, more preferably 120 mol% or less, and still more preferably 110 mol% or less. The silane coupling agent may be added in multiple portions. In the case of using a silane coupling agent, it is preferable to add a catalyst in order to promote hydrolysis of alkoxy groups and generation of silanol bonds. As the catalyst, a known catalyst used in a dehydration condensation reaction can be used. Among them, tin compounds such as dibutyltin dilaurate and dibutyltin dioctoate are preferable.

  The step (c) needs to be performed after the reaction (b) is sufficiently completed. The confirmation can be performed by measuring the residual amount of the silane coupling agent in the reaction solution. Usually, it is when the residual amount of the silane coupling agent in the reaction solution becomes 10% or less with respect to the charged amount. If the operation (c) is performed before the reaction (b) sufficiently proceeds, the monomers and oligomers are not mixed uniformly, and the composition becomes unclear in the subsequent step, which is not preferable. The step (c) can be performed at room temperature (25 ° C.). However, when the viscosity of the monomer or oligomer is high, or when the melting point of the monomer or oligomer is room temperature (25 ° C.) or higher, the temperature is 30 to 90 ° C. You may carry out by heating. The mixing time is preferably 30 minutes to 5 hours.

  In the step (d), the solvent such as the solvent used as the liquid medium or the solvent produced by hydrolysis of the alkoxysilane oligomer is mainly removed. However, it may be removed within a necessary range, and may not be completely removed. It is preferably removed to the extent that the composition does not substantially contain a solvent. In addition, when temperature is lower than the range described, the removal of a solvent is not fully performed but it is unpreferable. Conversely, when too high, since a composition becomes easy to gelatinize, it is unpreferable. The temperature may be controlled step by step. The removal time is preferably 1 to 12 hours. Moreover, it is preferable to remove by reducing the pressure to 20 kPa or less, more preferably 10 kPa or less. Moreover, it is preferable to remove at 0.1 kPa or more. The pressure may be gradually reduced.

  According to the preferable manufacturing method described above, the particle size is larger than that of the method in which a filler (such as silica particles) or a surface treatment agent such as a silane coupling agent is added to the resin composition later to disperse the filler. There is an advantage that small ultrafine particles can be dispersed in a large amount without agglomeration. Therefore, the obtained radiation-curable composition is obtained by dispersing a sufficient amount of silica particles to increase the dimensional stability and mechanical strength of the cured product without impairing the radiation transmission. The radiation-cured product obtained by curing it has the advantages of transparency, high surface hardness and low cure shrinkage, combined with adhesiveness, and suppressed metal corrosion under high temperature and high humidity. There is.

[Production of radiation-cured product]
The cured product of the radiation curable composition is obtained by so-called “radiation curing” in which a polymerization reaction is started by irradiating the composition with radiation (active energy rays or electron beams). There is no restriction | limiting in the form of a polymerization reaction, For example, well-known polymerization forms, such as radical polymerization, anionic polymerization, cationic polymerization, and coordination polymerization, can be used. Among these polymerization modes, the most preferable polymerization mode is radical polymerization. The reason for this is not clear, but it is presumed to be due to the homogeneity of the product due to the initiation of the polymerization reaction being homogeneous and proceeding in a short time within the polymerization system.

The radiation is an electromagnetic wave (gamma ray, X-ray, ultraviolet ray, visible ray, infrared ray, microwave, etc.) that acts on a polymerization initiator that initiates a necessary polymerization reaction to generate a chemical species that initiates the polymerization reaction. ) Or particle beam (electron beam, α-ray, neutron beam, various atomic beams, etc.). An example of radiation preferably used in the present invention is preferably ultraviolet rays, visible rays, and electron beams, and most preferably ultraviolet rays and electron beams because energy and a general-purpose light source can be used.

  When ultraviolet rays are used, a method is employed in which a photoradical generator (see the above example) that generates radicals by ultraviolet rays is used as a polymerization initiator and ultraviolet rays are used as radiation. At this time, you may use a sensitizer together as needed. The wavelength of the ultraviolet rays is usually in the range of 200 to 400 nm, and this wavelength range is preferably 250 to 400 nm. As a device for irradiating ultraviolet rays, a known device such as a high-pressure mercury lamp, a metal halide lamp, or an ultraviolet lamp having a structure for generating ultraviolet rays by microwaves can be preferably used. A high-pressure mercury lamp is preferable. The output of the apparatus is usually 10 to 200 W / cm, and when the apparatus is installed at a distance of 5 to 80 cm with respect to the irradiated object, the light deterioration, thermal deterioration, thermal deformation, etc. of the irradiated object are caused. Less and preferred.

  The composition of the present invention can also be cured preferably by an electron beam, and a cured product excellent in mechanical properties, particularly tensile elongation properties can be obtained. When using an electron beam, although the light source and irradiation device are expensive, the addition of an initiator can be omitted, and the polymerization is not inhibited by oxygen. There is. An electron beam irradiation apparatus used for electron beam irradiation is not particularly limited, and examples thereof include a curtain type, an area beam type, a broad beam type, and a pulse beam type. The acceleration voltage during electron beam irradiation is preferably 10 to 1000 kV.

These radiation, the irradiation intensity, usually 0.1 J / cm ² or more, preferably irradiated as 0.2 J / cm ² or more. The irradiation is usually performed at 20 J / cm ² or less, preferably 10 J / cm ² or less, more preferably 5 J / cm ² or less, more preferably 3 J / cm ² or less, and particularly preferably ² J / cm ² or less. If irradiation intensity is in this range, it can select suitably by the kind of radiation-curable composition. In the case of a radiation curable composition containing a monomer having a urethane bond or a hydroxyalkylene group or / and an oligomer thereof and a polyether (meth) acrylate, the irradiation intensity is preferably ² J / cm ² or less. In the case of a radiation curable composition containing a monomer comprising a condensed alicyclic acrylate and / or an oligomer thereof, the irradiation intensity is preferably ³ J / cm ² or less.

  When the irradiation energy and irradiation time of such radiation are extremely small, the heat resistance and mechanical properties of the radiation-cured product may not be sufficiently exhibited due to incomplete polymerization. The irradiation time is usually 1 second or longer, preferably 10 seconds or longer. However, when the amount is excessively large, deterioration such as yellowing due to light such as yellowing may occur. Therefore, the irradiation time is usually 3 hours or less, and preferably about 1 hour or less in terms of reaction acceleration and productivity.

  The radiation irradiation may be performed in one step or in a plurality of steps. As the radiation source, a diffusion radiation source in which the radiation spreads in all directions is usually used. Irradiation is performed with the liquid composition in a stationary state or a state in which the liquid composition is conveyed by a conveyor, and a radiation source in a stationary state. It is also possible to use the polymerizable liquid composition as a coating liquid film on a suitable substrate (for example, resin, metal, semiconductor, glass, paper, etc.) and then irradiate radiation to cure the coating liquid film. .

[Physical properties of radiation-cured product]
The radiation-cured product of the present invention usually exhibits insoluble and infusible properties in a solvent and the like, has properties advantageous for the use of optical members even when it is thickened, and has excellent adhesion and surface curing. Preferably it is. Specifically, it exhibits low optical distortion (low birefringence), high light transmittance, dimensional stability, high adhesion, and high surface hardness, and does not cause metal corrosiveness at high temperatures and high humidity. preferable. Further, the smaller the curing shrinkage, the better.

  The radiation-cured product of the present invention usually has a thickness of 5 cm or less. Preferably it is 1 cm or less, More preferably, it is 1 mm or less, More preferably, it is 500 micrometers or less. The film thickness is usually 1 μm or more, preferably 10 μm or more, more preferably 20 μm or more, more preferably 30 μm or more, particularly preferably 70 μm or more, and most preferably 85 μm or more.

And as for the radiation hardened | cured material of this invention, it is preferable that the hardened | cured material obtained by irradiating with an irradiation intensity | strength of 0.1-3 J / cm < ² > has the following physical property of (a) and (b).
(A) The surface hardness of a laminate in which a cured product layer having a thickness of 100 ± 15 μm is formed on a polyethylene terephthalate film having a thickness of 100 ± 15 μm is 2B or more.
(B) A laminate in which a cured product layer having a thickness of 100 ± 15 μm is formed on a polycarbonate plate having a thickness of 1.2 ± 0.2 mm is placed in an environment of 80 ° C. and 85% RH for 100 hours. The ratio of the close contact area to the polycarbonate plate should be 50% or more of the initial close contact area.

The surface hardness of the above (a) is a surface hardness by a pencil hardness test in accordance with JIS K5400, and the cured product of the present invention preferably has a surface hardness of 2B or more, and further has a surface hardness of HB or more. Is more preferably F or more, and particularly preferably H or more.

  Further, the adhesiveness of (b) is a laminate having a cured product layer with a film thickness of 100 ± 15 μm by applying and curing the radiation curable composition of the present invention on the surface of a 10 cm square polycarbonate plate, The laminate was placed in a thermo-hygrostat set at 80 ° C. and 85% RH for 100 hours, and then a transparent film depicting a 2 cm square was superimposed on the taken-out laminate, and the peel area from the polycarbonate plate was less than half. The number of squares is counted, the percentage of the total number is calculated as 25, and the percentage of the adhesion area to the polycarbonate plate is calculated, and the cured product of the present invention holds 50% or more. Is more preferable, 80% or more is more preferable, and 100% is particularly preferable.

  The radiation cured product of the present invention preferably has a light transmittance of 80% or more per optical path length of 0.1 mm at a wavelength of 550 nm, more preferably 85% or more, and 89% or more. Particularly preferred. More preferably, the light transmittance per optical path length of 0.1 mm at 400 nm is preferably 80% or more, more preferably 85% or more, and particularly preferably 89% or more. The light transmittance may be measured at room temperature using, for example, an HP8453 ultraviolet / visible absorptiometer manufactured by Hewlett-Packard Company.

Furthermore, the radiation-cured product of the present invention has a small curing shrinkage, for example, preferably 3% by volume or less, more preferably 2% by volume or less. Moreover, thermal expansion is small, for example, using a plate-shaped test piece of 5 mm × 5 mm × 1 mm, a weight of 1 g, temperature rise by compression method thermomechanical measurement (TMA; SSC / 5200 type; manufactured by Seiko Instruments Inc.) The range from 40 ° C. to 100 ° C. was measured in increments of 10 ° C. at a rate of 10 ° C./min, and the linear expansion coefficient calculated as the average value was preferably 13 × 10 ⁻⁵ / ° C. or less, more preferably 12 × It is 10 ⁻⁵ / ° C. or less, more preferably 10 × 10 ⁻⁵ / ° C. or less, and particularly preferably 8 × 10 ⁻⁵ / ° C. or less. Moreover, it is excellent in heat resistance, and the glass transition temperature of hardened | cured material becomes like this. Preferably it is 120 degreeC or more, More preferably, it is 150 degreeC or more, More preferably, it is 170 degreeC or more. Moreover, it is excellent also in solvent resistance, for example, has favorable solvent resistance with respect to toluene, chloroform, acetone, tetrahydrofuran, etc. As another index of the curing yield, there is used a method in which a radiation resin composition is applied on a substrate and the concave warpage generated after curing is measured. Specifically, the composition was formed on a circular polycarbonate substrate having a diameter of 130 mm and a thickness of 1.2 ± 0.2 mm using a spin coater to a thickness of 100 ± 15 μm, and a prescribed amount of radiation. And then left on a surface plate for 1 hour. After standing, the concave warpage of the polycarbonate plate caused by the curing shrinkage of the composition is measured. The concave warpage is preferably 1.0 mm or less, more preferably 0.5 mm or less, more preferably 0.1 mm or less, and still more preferably 0.05 mm or less. If the curing shrinkage is too large, it tends to be difficult to use in applications such as optical members that require dimensional stability.

The cured product of the present invention contains inorganic fine particles such as silica particles. However, since the fine particles are substances having optical properties different from those of the organic resin matrix, the cured product is realized as a whole by the organic material alone. In some cases, it has a characteristic of having a balance between a specific refractive index and an Abbe number that cannot be achieved. Such a balance between the specific refractive index and the Abbe number may be useful in applications where it is desirable that the birefringence is small, utilizing the refraction of light such as a lens or a prism. This refers to the case where the constant term C in the following formula representing the relationship between the refractive index n _D and the Abbe number ν _D measured at ° C. deviates from the range of 1.70 to 1.82.
n _D = 0.005ν _D + C

  In a molded body of a resin material, birefringence generally increases as the thickness increases. In the present invention, by using the above silica particles, the cured product of the present invention may acquire the characteristic that the increase rate of birefringence becomes smaller than the conventional one for the increase in thickness. Therefore, when the cured product of the present invention is used as a relatively thick molded body having a thickness of 0.1 mm or more as in the optical member of the present invention described later, it is advantageous in terms of lowering the birefringence.

[Uses of radiation cured products]
The radiation cured product of the present invention is excellent as an optical material because it has small optical distortion represented by birefringence, good transparency, and excellent functional properties such as dimensional stability and surface hardness. The optical material here refers to the optical characteristics of the material constituting it, for example, transparency, light absorption and emission characteristics, refractive index difference from the outside, small birefringence, and balance between the above specific refractive index and Abbe number. It refers to general molded articles used for applications that use the above. Specific examples include display panels, touch panels, lenses, prisms, waveguides, optical amplifiers and other optics, and optoelectronic members.

  As a use of the radiation-cured product of the present invention, it is also preferable to use a metal layer, and more preferably a laminate including an easily corrosive metal layer that easily undergoes alteration such as oxidation due to the action of moisture in the air or a small amount of ions Is preferable from the viewpoint that the effects of the present invention can be effectively expressed. These easily corrosive metals include Ag, Al, etc., and these metals, Au, Cu, Pb, Pt, Zn, Ta, Ti, Cr, Mo, Mg, V, Nb, Zr, Si, Ge, etc. And alloys with these metals. In addition, it is preferable that the thickness of this metal layer is 20-300 nm.

  The optical material of the present invention is roughly classified into two types. The first optical material is an optical material that is a molded body of the cured product, and the second optical material is an optical material that is a molded body having a thin film of the cured product as a partial layer. In other words, the former is the one in which the main component of the optical material is the cured product and may have an arbitrary thin film (coat layer) made of a material other than the cured product, while the latter is the main component of the optical material. It is comprised with the material which may not be hardened | cured material, and has a thin film of this hardened | cured material as a one part layer. Any optical material may be formed in close contact with an arbitrary solid material substrate such as resin, glass, ceramics, inorganic crystal, metal, semiconductor, diamond, organic crystal, paper pulp, and wood.

Although there is no restriction | limiting in the dimension of the said 1st optical material, The optical path length of the part of the said hardened | cured material is 0.01 mm normally at the point of the mechanical strength of an optical material, Preferably it is 0.1 mm, More preferably, it is 0.2 mm. On the other hand, the upper limit is usually 10,000 mm, preferably 5000 mm, and more preferably 1000 mm in terms of attenuation of light intensity. The shape of the first optical material is not limited, but examples thereof include a plate shape, a curved plate shape, a lens shape (concave lens, convex lens, concavo-convex lens, half-concave lens, half-convex lens, etc.), prism shape, fiber shape, and the like. Is done.

  Although there is no restriction | limiting in the dimension of the said 2nd optical material, The film thickness of the said hardened | cured material thin film is 0.05 micrometer normally in terms of mechanical strength or an optical characteristic, Preferably it is 0.1 micrometer, Furthermore, Preferably it is 0.5 micrometer. On the other hand, the upper limit value of the film thickness is usually 3000 μm, preferably 2000 μm, more preferably 1000 μm, from the viewpoint of thin film moldability and cost-effectiveness balance. The shape of the thin film is not limited, but it is not necessarily flat, and may be formed on a substrate having an arbitrary shape such as a spherical shape, an aspherical curved surface shape, a cylindrical shape, a conical shape, or a bottle shape. Good.

  The optical material of the present invention has an optional coating layer, for example, a protective layer that prevents mechanical damage to the coated surface due to friction or wear, and an undesirable wavelength that causes deterioration of semiconductor crystal particles or a substrate. A light-absorbing layer that absorbs light, a transmission shielding layer that suppresses or prevents the transmission of reactive low molecules such as moisture and oxygen gas, an antiglare layer, an antireflection layer, a low refractive index layer, Arbitrary additional function layers such as an undercoat layer and an electrode layer for improving the adhesion may be provided to form a multilayer structure. Specific examples of such an optional coating layer include a transparent conductive film and gas barrier film made of an inorganic oxide coating layer, a gas barrier film made of an organic coating layer, a hard coat, and the like. A known coating method such as a sputtering method, a dip coating method, or a spin coating method can be used.

  Specific examples of the optical material of the present invention are illustrated in more detail. Various lenses such as spectacle lenses, optical connector microlenses, and light-emitting diode condensing lenses, optical switches, optical fibers, optical branches in optical circuits, junction circuits, Optical communication parts such as optical multi-branch circuits, luminous intensity adjusters, various display members such as liquid crystal substrates, touch panels, light guide plates, retardation plates, storage / recording applications including optical disk substrates and optical film coatings, and more Are optical adhesives and other optical communication materials, functional films, antireflection films, optical multilayer films (selective reflection films, selective transmission films, etc.), super-resolution films, ultraviolet absorption films, reflection control films, optical waveguides, and Examples include various optical films and coating applications such as an identification function printing surface.

[Optical recording medium]
Although it does not specifically limit with the optical recording medium as used in the field of this invention, Preferably the next generation high-density optical recording medium using a blue laser is preferable. As this optical recording medium, an optical recording medium in which a protective film is formed on a surface on which a dielectric film, a recording film, a reflective film, etc. (hereinafter, these layers are collectively referred to as a recording / reproducing functional layer) is formed on a substrate. It means an optical recording medium that uses laser light with a wavelength of 380 to 800 nm, preferably laser light with a wavelength of 450 to 350 nm.

  Next, the substrate will be described. An uneven groove for use in recording / reproducing optical information is provided on one main surface of the substrate, and is formed, for example, by injection molding of a light-transmitting resin using a stamper. The material of the substrate is not particularly limited as long as it is a light-transmitting material. For example, thermoplastic resins such as polycarbonate resin, polymethacrylate resin, and polyolefin resin, and glass can be used. Of these, polycarbonate resin is most preferred because it is most widely used in CD-ROMs and is inexpensive. The thickness of the substrate is usually 0.1 mm or more, preferably 0.3 mm or more, more preferably 0.5 mm or more, on the other hand, 20 mm or less, preferably 15 mm or less, more preferably 3 mm or less. .2 ± 0.2 mm or so. The outer diameter of the substrate is generally about 120 mm.

The recording / reproducing functional layer is a layer configured to exhibit a function capable of recording / reproducing an information signal or reproducing the information signal, and may be a single layer or a plurality of layers. The recording / reproducing functional layer is a rewrite that can repeatedly perform recording and erasure when the optical recording medium is a reproduction-only medium (ROM medium), or a write-once medium that can be recorded only once (Write Once medium). Depending on the case of a possible type medium (Rewritable medium), it is possible to adopt a layer structure corresponding to each purpose.

  For example, in a read-only medium, the recording / reproducing functional layer is usually composed of a single layer containing a metal such as Al, Ag, Au, etc. For example, the recording / reproducing functional layer is formed of Al, Ag, Au by sputtering. It is formed by forming a reflective layer on a substrate.

  In the write-once type medium, the recording / reproducing functional layer is generally configured by providing a reflective layer containing a metal such as Al, Ag, Au, etc. and a recording layer containing an organic dye on the substrate in this order. As such a write-once medium, a medium in which a reflective layer is provided by a sputtering method and then an organic dye layer is formed on a substrate by a spin coating method can be exemplified. As another specific example of the write-once medium, the recording / reproducing functional layer includes a reflective layer containing a metal such as Al, Ag, Au, a dielectric layer, a recording layer, and a dielectric layer. A structure in which the dielectric layer and the recording layer contain an inorganic material is also provided. In such a write-once medium, a reflective layer, a dielectric layer, a recording layer, and a dielectric layer are usually formed by sputtering.

  In a rewritable type medium, the recording / reproducing functional layer is usually formed of a reflective layer containing a metal such as Al, Ag, or Au, a dielectric layer, a recording layer, and a dielectric layer in this order on the substrate. In general, the dielectric layer and the recording layer contain an inorganic material. In such a rewritable medium, a reflective layer, a dielectric layer, a recording layer, and a dielectric layer are usually formed by sputtering. Another specific example of the rewritable medium is a magneto-optical recording medium. A recording / reproducing area is set in the recording / reproducing functional layer. The recording / reproducing area is usually provided in an area having an inner diameter larger than the inner diameter of the recording / reproducing functional layer and an outer diameter smaller than the outer diameter of the recording / reproducing functional layer.

  FIG. 1 is a cross-sectional view for explaining an example of the recording / reproducing functional layer 5 in the rewritable optical recording medium 10. The recording / reproducing functional layer 5 is provided so as to sandwich the reflective layer 51 formed of a metal material directly provided on the substrate 1, the recording layer 53 formed of a phase change material, and the recording layer 53 from above and below. And two dielectric layers 52 and 54.

The material used for the reflective layer 51 is preferably a substance having a high reflectivity, and in particular, a metal such as Au, Ag, or Al that can be expected to have a heat dissipation effect. A small amount of metal such as Ta, Ti, Cr, Mo, Mg, V, Nb, Zr, or Si may be added to control the thermal conductivity of the reflective layer itself or to improve the corrosion resistance. The amount of metal added in a small amount is usually 0.01 atomic% or more and 20 atomic% or less. Among them, an aluminum alloy containing 15 atomic% or less of Ta and / or Ti, particularly an alloy of Al _1-x Ta _x (0 <x ≦ 0.15) has excellent corrosion resistance, and is an optical recording medium. The reflective layer material is particularly preferable for improving the reliability of the reflective layer. In addition, Ag alloy containing any one of Mg, Ti, Au, Cu, Pd, Pt, Zn, Cr, Si, Ge, and rare earth elements in the range of 0.01 atomic% to 10 atomic% is a reflectance. High thermal conductivity and excellent heat resistance are preferable.

  The thickness of the reflective layer 51 is usually 40 nm or more, preferably 50 nm or more, and is usually 300 nm or less, preferably 200 nm or less. If the thickness of the reflective layer 51 is excessively large, the shape of the tracking groove formed in the substrate 1 changes, and further, it takes time to form a film and the material cost tends to increase. Further, if the thickness of the reflective layer 51 is excessively small, not only does light transmission occur and it does not function as a reflective layer, but also an influence of an island-like structure formed in the initial stage of film growth tends to occur on a part of the reflective layer 51, Reflectance and thermal conductivity may decrease.

  The materials used for the two dielectric layers 52 and 54 are used to prevent evaporation / deformation accompanying the phase change of the recording layer 53 and to control thermal diffusion at that time. The material of the dielectric layer is determined in consideration of the refractive index, thermal conductivity, chemical stability, mechanical strength, adhesion, and the like. In general, dielectric materials such as oxides, sulfides, nitrides, carbides, and fluorides such as Ca, Mg, and Li, which are highly transparent and have a high melting point, can be used. These oxides, sulfides, nitrides, carbides and fluorides do not necessarily have to have a stoichiometric composition, and it is also effective to control the composition for controlling the refractive index or to use them in combination. is there.

  Specific examples of such a dielectric material include, for example, Sc, Y, Ce, La, Ti, Zr, Hf, V, Nb, Ta, Zn, Al, Cr, In, Si, Ge, Sn, Sb, And oxides of metals such as Te; metals such as Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Zn, B, Al, Ga, In, Si, Ge, Sn, Sb, and Pb Nitride of Ti; Zr, Hf, V, Nb, Ta, Cr, Mo, W, Zn, B, Al, Ga, In, Si, and other metal carbides, or a mixture thereof. Further, a sulfide of a metal such as Zn, Y, Cd, Ga, In, Si, Ge, Sn, Pb, Sb, and Bi; a selenide or a telluride; a fluoride such as Mg or Ca, or a mixture thereof. Can be mentioned.

In consideration of repetitive recording characteristics, a mixture of dielectrics is preferable. For example, a mixture of a chalcogen compound such as ZnS or rare earth sulfide and a heat-resistant compound such as oxide, nitride, carbide, or fluoride can be used. For example, a mixture of a heat-resistant compound containing ZnS as a main component and a mixture of a rare-earth sulfide, particularly a heat-resistant compound containing Y ₂ O ₂ S as a main component are examples of a preferable dielectric layer composition. More specifically, ZnS—SiO ₂ , SiN, SiO ₂ , TiO ₂ , CrN, TaS ₂ , Y ₂ O ₂ S and the like can be mentioned. Among these materials, ZnS—SiO ₂ is widely used because of its high deposition rate, low film stress, small volume change rate due to temperature change, and excellent weather resistance. The thicknesses of the dielectric layers 52 and 54 are usually 1 nm or more and 500 nm or less. By setting the thickness to 1 nm or more, the effect of preventing deformation of the substrate and the recording layer can be sufficiently secured, and the role as a dielectric layer can be sufficiently achieved. Further, when the thickness is 500 nm or less, the role of the dielectric layer is sufficiently fulfilled, and the internal stress of the dielectric layer itself, the difference in elastic characteristics with respect to the substrate, etc. become remarkable, thereby preventing the occurrence of cracks. be able to.

Examples of the material for forming the recording layer 53 include compounds having a composition such as GeSbTe, InSbTe, AgSbTe, and AgInSbTe. Among _{them, {(Sb 2 Te 3)} 1-x (GeTe) x} 1-y Sb y (0.2 ≦ x ≦ 0.9,0 ≦ y ≦ 0.1) alloy or (Sb _x Te _{1- x} ) _y M _1-y (where 0.6 ≦ x ≦ 0.9, 0.7 ≦ y ≦ 1, M is Ge, Ag, In, Ga, Zn, Sn, Si, Cu, Au, Pd, Pt, Pb, Cr, Co, O, S, Se, V, Nb, Ta) The thin film containing an alloy as a main component is stable in both crystalline and amorphous states and both states. Fast phase transitions between are possible. Furthermore, there is an advantage that segregation hardly occurs when repeated overwriting, and it is the most practical material.

The film thickness of the recording layer 53 is usually 5 nm or more, preferably 10 nm or more. With such a range, a sufficient optical contrast between the amorphous state and the crystalline state can be obtained. Further, the film thickness of the recording layer 53 is usually 30 nm or less, preferably 20 nm or less. With such a range, it is possible to obtain an increase in optical contrast due to the light transmitted through the recording layer 53 being reflected by the reflection layer, and the heat capacity can be controlled to an appropriate value, so that high-speed recording is possible. Can also be performed. In particular, if the thickness of the recording layer 53 is 10 nm or more and 20 nm or less, it is possible to achieve both higher speed recording and higher optical contrast. By setting the thickness of the recording layer 53 in such a range, the volume change due to the phase change is reduced, and the recording layer 53 itself and other layers in contact with the upper and lower sides of the recording layer 53 are repeatedly overwritten repeatedly. The effect of volume change can be reduced. Furthermore, accumulation of irreversible microscopic deformation of the recording layer 53 is suppressed, noise is reduced, and repeated overwrite durability is improved.

  The reflective layer 51, the recording layer 53, and the dielectric layers 52 and 54 are usually formed by a sputtering method or the like. In order to prevent oxidation and contamination between layers, it is desirable to form a film with an in-line apparatus in which a target for a recording layer, a target for a dielectric layer, and, if necessary, a target for a reflective layer material are installed in the same vacuum chamber. It is also excellent in terms of productivity.

  The protective layer 3 is made of a cured product obtained by spin-coating the radiation-curable composition of the present invention and radiation-curing the composition. The protective layer 3 is provided in contact with the recording / reproducing functional layer 5 and has a planar annular shape. The protective layer 3 is made of a material that can transmit laser light used for recording and reproduction. The transmittance of the protective layer 3 is usually 80% or more, preferably 85% or more, and more preferably 89% or more at the wavelength of light used for recording / reproduction. Within such a range, loss due to absorption of recording / reproducing light can be minimized. On the other hand, the transmittance is most preferably 100%, but is usually 99% or less because of the performance of the material used.

  Such a protective layer 3 is sufficiently transparent with respect to blue laser light having a wavelength of about 405 nm used for recording / reproducing of an optical disk, and protects the recording layer 53 formed on the substrate 1 from water and dust. It is desirable to have such properties. In addition, the surface hardness of the protective layer 3 is preferably B or more according to the pencil hardness test according to JISK5400. If the hardness is too small, it is not preferable because the surface is easily scratched. Although there is no problem with the hardness being too large, the cured product tends to become brittle, and cracks and peeling are likely to occur, which is not preferable.

  Furthermore, it is preferable that the adhesion between the protective layer 3 and the recording / reproducing functional layer 5 is high. Furthermore, it is preferable that the adhesion with time is higher, and the ratio of the adhesion area between the protective layer 3 and the recording / reproducing functional layer 5 after being placed in an environment of 80 ° C. and 85% RH for 100 hours, more preferably 200 hours is initially It is preferable to hold 50% or more of the contact area, more preferably 80% or more, and particularly preferably 100%.

  The thickness of the protective layer 3 is usually 10 μm or more, preferably 20 μm or more, more preferably 30 μm or more, still more preferably 70 μm or more, and particularly preferably 85 μm or more. When the film thickness is within such a range, the influence of dust and scratches attached to the surface of the protective layer 3 can be reduced, and the thickness is sufficient to protect the recording / reproducing functional layer 5 from moisture of the outside air. can do. On the other hand, it is usually 300 μm or less, preferably 130 μm or less, more preferably 115 μm or less. When the film thickness is within this range, a uniform film thickness can be easily formed by a general coating method used in spin coating or the like. The protective layer 3 is preferably formed with a uniform film thickness in a range covering the recording / reproducing functional layer 5.

  The optical recording medium obtained as described above may be used as a single plate, or two or more may be bonded together. Then, if necessary, a hub may be attached and incorporated into the cartridge.

  Hereinafter, the present invention will be specifically described based on examples. However, the present invention is not limited to these examples as long as the scope of the gist is not exceeded.

Example 1
<Preparation of silica particles>
After 1170 g of tetramethoxysilane and 370 g of methanol were mixed, 111 g of 0.05% hydrochloric acid was added, and a hydrolysis reaction was performed at 65 ° C. for 2 hours. Next, the temperature in the system was raised to 130 ° C., and the produced methanol was removed. Then, the temperature was gradually raised to 150 ° C. while blowing nitrogen gas, and the tetramethoxysilane monomer was removed by keeping it for 3 hours. Silane oligomers were prepared. Subsequently, 225.3 g of methanol was added to 122.8 g of the resulting tetramethoxysilane oligomer and stirred uniformly, and then 24.6 g of a 5% methanol solution of acetylacetone aluminum as a catalyst was added and stirred for 30 minutes. To this solution, 26.0 g of demineralized water was gradually added dropwise with stirring, and the mixture was stirred at 60 ° C. for 2 hours to grow silica particles. Next, 119.6 g of acryloyloxypropyltrimethoxysilane and 0.4 g of dibutyltin dilaurate were added as silane coupling agents, stirred for 2 hours at 60 ° C. and aged, then 53.5 g of demineralized water and acryloyloxypropyltrimethoxysilane 119. .6 g was gradually added and stirred at 60 ° C. for 4 hours to react the silica particle surface with the silane coupling agent to prepare a silica sol.

<Synthesis of urethane acrylate oligomer>
In a 10 L four-necked flask, 1111.5 g of isophorone diisocyanate and 0.3 g of dibutyltin laurate are added, heated to 70-80 ° C. in an oil bath, and gently stirred until the temperature becomes constant. When the temperature became constant, a mixture of 148.0 g of 1,4 butanediol and 1275.0 g of polytetramethylene ether glycol was dropped with a dropping funnel, and the mixture was stirred for 2 hours while maintaining the temperature at 80 ° C. Then, a mixture of 725.0 g of hydroxyethyl acrylate and 1.5 g of methoquinone was dropped with a dropping funnel, and when dropping was completed, the temperature was raised to 80 ° C. and stirred for 10 hours to synthesize a urethane acrylate oligomer.

<Preparation of radiation curable composition>
Into a 2 L flask, put 608.3 g of the urethane acrylate oligomer obtained above, heat to 70 ° C., add 232.1 g of isobornyl acrylate, stir, and further, as a (meth) acrylate having an acidic group 44.0 g of 2-acryloyloxyethyl succinic acid (“HOA-MS” manufactured by Kyoeisha Yushi Chemical Co., Ltd.) was added to prepare a radiation curable composition excluding silica particles.

Subsequently, 79.7 g of the silica sol obtained above in a 500 cc eggplant flask, 96.7 g of the radiation curable composition excluding silica particles obtained above, and 9.7 g of hydroxyethyl acrylate, polymerization initiation As agents, 2.5 g of 1-hydroxycyclohexyl phenyl ketone and 2.5 g of benzophenone were added and stirred at room temperature for 2 hours to obtain a transparent radiation-curable composition. Further, this composition was evaporated under reduced pressure at 50 ° C. for 1 hour to remove low boiling components contained in the composition. The content of acidic groups in the composition was 2.3 × 10 ⁻⁴ eq / g.

<Production of laminate>
As a substrate for surface hardness measurement, a 10 cm square, 100 μm thick polyethylene terephthalate film, a substrate for adhesion evaluation, a 10 cm square, 1.2 mm thick polycarbonate plate, and a substrate for metal corrosion evaluation A spin coater was used to apply the radiation-curable composition obtained above to each surface of a substrate having a silver layer sputtered to a thickness of 100 nm on a 10 cm square, 1.2 mm thick polycarbonate plate. The film thickness after curing is 100 ± 15 μm for surface hardness measurement, and 100 ± 15 μm for adhesion evaluation and metal corrosion evaluation, and installed at a distance of 15 cm from the coating film. was, from the high-pressure mercury lamp of output 80W / cm, by irradiating for 30 seconds ultraviolet irradiation intensity 1 J / cm ^2, have a cured layer That to prepare a laminate. The resulting laminate is 1 at room temperature.
After standing for a period of time, surface hardness, adhesion, and metal corrosivity were measured and evaluated by the methods shown below, and the results are shown in Table 1.

<Surface hardness>
Regarding a laminate of a polyethylene terephthalate film and a cured product layer, JIS K54
It was measured by a pencil hardness test according to 00.
<Adhesion>
After placing the laminate of the polycarbonate plate and the cured product layer in a constant temperature and humidity chamber set at 80 ° C. and 85% RH for 100 hours, a transparent film depicting a 2 cm square is superimposed on the taken out laminate, and the polycarbonate plate The number of squares with a peel area of less than half was counted, and the percentage of the total number of squares was calculated to be the ratio of the adhesion area to the polycarbonate plate.
<Metal corrosivity>
A laminate of a substrate having a silver layer on a polycarbonate plate and a cured product layer is placed in a thermo-hygrostat set at 80 ° C. and 85% RH for 100 hours, and then a cutter knife is placed on the polycarbonate plate surface of the taken-out laminate. The surface of the silver layer at the interface between the polycarbonate plate and the silver layer is exposed by incising and bending the part, and the organic matter present on the surface is analyzed by infrared absorption spectroscopy. evaluated.
◯: When any 10 points have no inherent peak in the infrared absorption spectrum of the stretching vibration of the carboxyl group of 1720 to 1730 cm ⁻¹ at any 10 points ((meth) acrylate does not penetrate into the silver layer).
X: When at least one peak specific to the stretching vibration of the carboxyl group of 1720 to 1730 cm ⁻¹ is observed in the infrared absorption spectrum for any 10 points ((meth) acrylate permeates the silver layer).

Example 2
In the preparation of the radiation curable composition, 572.7 g of urethane acrylate oligomer was used, 244.0 g of isobornyl acrylate was used, and neopentyl glycol triacrylate succinic acid as a (meth) acrylate having an acidic group Except that 79.6 g of monoester was used, a radiation curable composition was prepared in the same manner as in Example 1, and the results of evaluation were shown in Table 1. The content of acidic groups in the radiation curable composition was 2.3 × 10 ⁻⁴ eq / g.

Example 3
In the preparation of the radiation curable composition, instead of 96.7 g of the radiation curable composition excluding silica particles, 81.7 g of the radiation curable composition excluding silica particles and polypropylene glycol diacrylate (“APG400 manufactured by Shin-Nakamura Chemical Co., Ltd.) “) A radiation curable composition was prepared in the same manner as in Example 1 except that 15.0 g was used. The content of acidic groups in the radiation curable composition was 1.9 × 10 ⁻⁴ eq / g.

Comparative Example 1
In the preparation of the radiation-curable composition, 652.3 g of urethane acrylate oligomer, 217.4 g of isobornyl acrylate, and no (meth) acrylate having an acidic group were used. Table 1 shows the results of preparing a radiation curable composition in the same manner as in Example 1 and evaluating the same. The content of acidic groups in the radiation curable composition was 0.01 × 10 ⁻⁴ eq / g or less.

Comparative Example 2
Radiation except for using urethane acrylate oligomer synthesized by the following method, adding 217.4 g of isobornyl acrylate to the urethane acrylate oligomer, and removing silica particles without using (meth) acrylate having an acidic group Except that the curable composition was prepared, the radiation curable composition was prepared in the same manner as in Example 1, and the results of evaluation were shown in Table 1. The content of acidic groups in the radiation curable composition was 2.3 × 10 ⁻⁴ eq / g.
<Synthesis of urethane acrylate oligomer>
Isophorone diisocyanate 222.3 g and dibutyltin laurate 0.06 g are put into a 2 L four-necked flask, heated to 70 to 80 ° C. in an oil bath, and gently stirred until the temperature becomes constant. When the temperature became constant, a mixture of 29.6 g of dimethylolbutanoic acid and 255.0 g of polytetramethylene ether glycol was added dropwise with a dropping funnel, and the mixture was stirred for 2 hours while maintaining the temperature at 80 ° C. until the temperature reached 70 ° C. After being lowered, a mixture of 145.0 g of hydroxyethyl acrylate and 0.3 g of methoquinone was dropped with a dropping funnel, and when dropping was finished, the temperature was raised to 80 ° C. and stirred for 10 hours to synthesize a urethane acrylate oligomer. The content of acidic groups in the urethane acrylate oligomer was 3.1 × 10 ⁻⁴ eq / g.

It is sectional drawing which shows one Example of the laminated body for optical recording media of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1; Substrate 3; Protective layer 5; Recording / reproducing functional layer 51; Reflective layer 52, 54; Dielectric layer 53; Recording layer 10; Optical recording medium

Claims (10)

A radiation curable composition comprising silica particles, a monomer having a urethane bond or a hydroxyalkylene group or / and an oligomer thereof, and a (meth) acrylate other than the monomer or / and the oligomer, the urethane bond or the hydroxyalkylene Radiation curing, wherein the content of acidic groups in the monomer having a group or / and oligomer thereof is less than 0.1 × 10 ⁻⁴ eq / g, and the (meth) acrylate contains an acidic group Sex composition. The radiation curable composition according to claim 1, wherein the content of acidic groups in (meth) acrylate is 0.1 × 10 ⁻⁴ eq / g or more. The radiation curable composition according to claim 1 or 2, wherein the content of acidic groups in the (meth) acrylate is 13 x 10 ^-4 eq / g or less.   The radiation-curable composition according to any one of claims 1 to 3, wherein the monomer having a urethane bond or a hydroxyalkylene group and / or an oligomer thereof has (meth) acryloyl groups at both ends.   The radiation curable composition according to any one of claims 1 to 4, wherein the acidic group contained in the (meth) acrylate is a carboxyl group. The radiation curable composition according to any one of claims 1 to 5, wherein a cured product obtained by irradiation with radiation at an irradiation intensity of 0.1 to 3 J / cm ² has the following physical properties (a) and (b). object.
(A) The surface hardness of a laminate in which a cured product layer having a thickness of 100 ± 15 μm is formed on a polyethylene terephthalate film having a thickness of 100 ± 15 μm is 2B or more.
(B) A laminate in which a cured product layer having a thickness of 100 ± 15 μm is formed on a polycarbonate plate having a thickness of 1.2 ± 0.2 mm is placed in an environment of 80 ° C. and 85% RH for 100 hours. The ratio of the close contact area to the polycarbonate plate should be 50% or more of the initial close contact area.   A cured product obtained by curing the radiation curable composition according to any one of claims 1 to 6 by radiation irradiation.   A laminate comprising the cured product layer according to claim 7.   The laminate according to claim 8, comprising a metal layer.   The laminate according to claim 8 or 9, which is used for an optical recording medium.

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