TW200906873A - Active energy ray curable composition, coating composition, coating member, and optical material - Google Patents

Abstract

The purpose of the present invention is to provide a composition for active energy ray curable optical material which may give a cured product having a high refractive index, especially an active energy ray curable composition which may form a cured product having excellent adhesiveness to a cycloolefin polymer. The active energy ray curable composition of the present invention comprises the following components (A) to (D): Component (A): a urethane (meth)acrylate having a weight average molecular weight of 2, 000 to 10, 000 and is a reaction product of a polyether diol, a polyisocyanate having no aromatic group, and a hydroxyl-containing(meth) acrylate, Component (B): a di(meth)acrylate of diol of specific structure which has a triphenyl methane skeleton or a diphenyl cyclohexane skeleton, Component (C): a compound having no phenyl skeleton or having one phenyl skeleton and having one (meth)acryloyl group.

Description

200906873 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to an active energy ray-curable composition, a coating composition, a covering member, and an optical member. [Prior Art] In general, liquid-based curable coating materials are widely used in various fields such as packaging materials, display materials such as labels, electronic parts, precision machines, and construction materials. In recent years, in order to increase the speed and productivity of the process, not only the conventional thermosetting type but also the coating material which is cured by active energy rays such as ultraviolet rays or electron beams has been widely used (Patent Document 1). With the development of the field of use and the demand for high performance, the demand for high performance is enhanced even for active energy ray-curable coating materials. For example, in the laminating adhesive for PET film, high heat resistance is required in addition to high adhesion. It has been reported to contain (a) urethane (meth) acrylate having a number average molecular weight of 5,000 to 1 5,000, (b) acryloyl morpholine, dimethyl methacrylate, diethyl acrylamide And a compound selected from diisopropylacrylamide and (c) a phenolic polyethylene glycol (PEG = 1 to 5) acrylate liquid curable adhesive composition, which has a PVC or PET Excellent adhesion (Patent Document 1). Since the composition described in Patent Document 1 can be cured by an active energy ray such as ultraviolet rays, it is excellent in productivity and excellent in adhesion to a glass substrate or polyvinyl chloride. On the other hand, there are disclosed that the (A) number average molecular weight is 1〇, 〇〇〇~200906873 4〇,000 of the urethane (meth) acrylate, (B) the cyclic ether has no suspicion The composition of the saturated monomer can be hardened by the active energy ray, and exhibits a good rate of the olefin polymer film (Patent Document 2) 专利 [Patent Document 1] JP-A-07-3 In the recent years, a cycloolefin polymer film is used as an optical member system such as a liquid crystal display or a portable telephone. Become more. For example, when light is incident on the cycloolefin film and the light penetrating the coating film is taken out, if the refractive index of the coating layer or the lens layer is lower than that of the cycloolefin polymer film, the light extraction efficiency is deteriorated. problem. Therefore, it is required that not only the adhesion to the cycloolefin polymer film is high, but also the composition of the coating layer or the lens layer having a refractive index can be formed. However, when the composition described in the above Patent Document 1 is used, the present inventors have found that the cured product is insufficient in adhesion to the cycloolefin polymer film. Further, according to the knowledge of the inventors of the present invention, the composition described in Patent Document 2 uses a urethane (meth) acrylate having a high average molecular weight, so that the viscosity of the composition tends to be high, and the composition tends to be thin. When the film thickness is formed to form a cured layer, the control of the film thickness becomes difficult. Further, the cured product obtained from the disclosed blend has a relatively low refractive index. SUMMARY OF THE INVENTION An object of the present invention is to provide a composition for a 200906873 active energy ray-curable optical material having a high refractive index of a cured product obtained, particularly having excellent adhesion to a cycloolefin polymer, and capable of forming a copolymer having a higher specific gravity than a cycloolefin polymer An active energy ray-curable composition of a cured product having a high refractive index, a coated composition, a coated member, and an optical material. Means for Solving the Problem The above problem is solved by the following means <1>, <11>, <12>, and <1 4 >. The preferred embodiments of <2 >~ <10>, <13> and <15> are also listed below. < 1 > An active energy ray-curable composition containing the following components (A) to (D), (A) component: polyether diol, aromatic group-free polyisocyanate, and hydroxyl group-containing (A) A reaction product of an acrylate having a weight average molecular weight of 2,000 to 1,000,000, a urethane (meth) acrylate, (B) a component: the following formula (1) and/or formula (2) ) the di(meth)acrylate shown,

Here, R1 and R3 each independently represent a hydrogen atom or a methyl group, and R2 and R4 each independently represent an alkylene group having a carbon number of 2 to 4, wherein R5 represents a hydrogen atom or a methyl group, and R6 represents a hydrogen atom, a halogen atom or a group. The group, R7 and R8 each independently represent a halogen atom or a methyl group, and mi and m2 each independently represent an integer of 0 to 4, and m3 and ra4 each independently represent an integer of 〇~2, 200906873

OR10 12-〇fCC=CH2 '巾6 (2) where 'R9 and R1G each independently represent a hydrogen atom or a methyl group, and r11 and R12 each independently represent an alkylene group having 2 to 4 carbon atoms, and Ri4 is independently The ground atom represents a halogen atom or a methyl group, and m5 and m6 each independently represent an integer of 〇~4, and m7 and ms each independently represent an integer of 〇~2, and (C) component: has two phenyl skeletons and has one ( A compound of a methyl group, a propylene group, and a component (D): a compound having no phenyl skeleton or having one phenyl skeleton and having one methacrylinyl group. [2] The active energy ray-curable composition according to the above [1], wherein the polyether diol has ethylene glycol, propylene glycol, 1,4-butanediol, or the like. The constituent unit selected from the group consisting of 1,5-pentanediol and 1,6-hexanediol. &lt; 3 &gt; The active energy ray-curable composition as described in <2>, wherein the polyether diol-based polytetramethylene glycol is in the above (Α) component. The active energy ray-curable composition according to any one of the above formula (3), wherein the component (C) is a (meth) group which is not represented by the following formula (3). Acrylate, R15 Ο H2C =C —C -^O-R1

(3) Here, r15 represents a hydrogen atom or a methyl group 'r16 represents a carbon number of 1 to 6, and R!7 represents a phenyl group or an alkyl group having a phenyl group having a carbon number of 10 or less. η 200906873 represents 0~ An integer of 4. <5> The active energy ray-curable composition as described in <4>, wherein the component (c) is a (meth) acrylate represented by the following formula (4),

H2c=c—C—(〇_R16)&quot; (4) Here, R15, R16 and η are synonymous with the above formula (3). <6> The active energy ray-curable composition as described in <5> wherein the compound of the formula (4) in the component (C) is η = 0 ' &lt; 7 &gt;&lt; 1 &lt; 1 The active energy ray-curable composition according to any one of the above-mentioned, wherein the component (D) is a methacrylate having one phenyl skeleton. The active energy ray-curable composition according to any one of (1) to (1), further comprising a bivalent unsaturated compound other than the components (A) to (D). . The active energy ray-curable composition according to any one of the above-mentioned, wherein the photopolymerization initiator is further contained in the active energy ray-curable composition. &lt;1 0 &gt; The active energy ray-curable composition as described in &lt;1&gt; wherein the cured product obtained from the composition has a refractive index at 150 ° C of 1.54 or more and 1.62 or less. The active energy ray-curable coating composition is a composition according to any one of <1> to <10>. &lt;12&gt; A coated member obtained by coating a plastic film with a cured film of the composition described in &lt;11&gt;. The covering member according to <12>, wherein the plastic film is a cycloolefin polymer film. &lt;14&gt; An optical material obtained by curing the composition according to any one of the above items. &lt;15&gt; The optical material described in <14>, which is a lens sheet. Further, in the present specification, acrylate or methacrylate is represented by (meth) acrylate. EFFECTS OF THE INVENTION The cured product of the active energy ray-curable composition of the present invention has high refraction, has excellent adhesion to a cycloolefin polymer, and can form a cured product having a higher refractive index than the film substrate. Further, this cured product or cured film can be used as an excellent covering member and an optical member. [Embodiment] The best shaped bear of the invention is described. (A) Component Hereinafter, the active energy ray-curable composition is simply referred to as "the composition of the present invention". The component (A) of the present invention is a reaction product of a polyether diol, an aromatic group-free polyisocyanate, and a hydroxyl group-containing (meth) acrylate, and a carbamate having a weight average molecular weight of 2,000 to 10,000 (A) Base) acrylate. The reaction product of the component (A), a polyether diol, an aromatic group-free polyisocyanate, and a hydroxyl group-containing (meth) acrylate can be produced by various methods. For example, the following two processes can be mentioned. Process 1 : A method of introducing a diol compound, a polyisocyanate, and a hydroxyl group-containing (meth) 200906873 acrylate into a reaction, Process 2: reacting a diol compound with a polyisocyanate, followed by a hydroxyl group-containing (methyl group) The method of acrylate reaction. Preferably, it reacts with a diisocyanate which is slightly more than a molar amount of a diol compound, and reacts both terminal groups into a diisocyanate group to react with a trans group-containing (meth) acrylate to synthesize a polyamine of the object. Acid ester (meth) acrylate. Among them, the method obtained by Process 2 is preferable because the component (A) having an average molecular weight of a narrow molecular weight distribution can be obtained. The polyether diol which is a raw material of the component (A) is preferably an aliphatic polyether diol, preferably ethylene glycol, propylene glycol '1,4-butanediol' 1,5-pentanediol and/or Or 1,6-hexanediol is used as a constituent unit. Specific examples of such polyethylene include polyethylene glycol, 1,2-polypropylene glycol, 1,3-polypropylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, polyisobutylene glycol, and rings. a copolymer diol of oxypropane and tetrahydrofuran, a copolymer diol of ethylene oxide and tetrahydrofuran, a copolymer diol of ethylene oxide and propylene oxide, or the like. Such aliphatic polyether diols are commercially available, and examples thereof include Unisafe DC1100, Unisafe DC 1 8 00 'Unisafe DCB1100 'Unisafe DCB1800 [manufactured by Sakamoto Oil Co., Ltd.]; PPTG4000, PPTG2000, PPTG1000, PTG2000, PTG650 , PTGL2000, PTGL1000 [above is Baotu Valley Chemical (share) system]. The polyether diol preferably has a weight average molecular weight of from 500 to 6,000, more preferably from 1,000 to 3,000. Among these diols, polybutylene glycol is preferred from the viewpoint of the adhesion to the obtained component (A) and the effect of exhibiting a small amount. When the weight average molecular weight of the diol is 500 or more, the Young's modulus of the cured product at a high temperature and low temperature of 200906873 is increased, and sufficient adhesion can be obtained to prevent tearing, which is preferable. On the other hand, when the weight average molecular weight is 6,000 or less, the composition can be made to have a low viscosity, and when the composition is applied to a substrate, the coating property is excellent and the adhesion is excellent, which is preferable. Further, in the present invention, the weight average molecular weight means that the molecular weight measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) is converted into polystyrene. Examples of the hydroxyl group-containing (meth) acrylate which is a raw material of the component (A) include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid. 2-hydroxybutyl ester, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 1,4-butanediol mono(meth)acrylate, 2-hydroxyalkyl(meth)acryloyl group Phosphate ester, 4-hydroxycyclohexyl (meth)acrylate, 1,6-hexanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, trimethylolpropane di(a) Acrylate, trimethylolethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and the like. Further, examples of the glycidyl group-containing compound and (meth)acrylic acid such as alkyl glycidyl ether, allyl glycidyl c. oleyl ether, and glycidyl (meth)acrylate may be mentioned. The resulting compound is reacted. Among these hydroxyl group-containing (meth) acrylates, 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate are particularly preferred from the viewpoint of reactivity or compatibility. Wait. As the polyisocyanate which is a raw material of the component (A), a compound having no aromatic group is used. Thereby, the yellowing of the obtained cured product can be prevented. Specific examples of the polyisocyanate include hydrogenated diphenylmethyl-13-200906873 alkyl diisocyanate, hydrogenated dimethyl diisocyanate, tetramethyl dimethyl diisocyanate, and norbornane diisocyanate. The polyisocyanate compound is preferably hydrogenated dimethyl diisocyanate, isophorone diisocyanate or 2,2,4-trimethylhexamethylene diisocyanate. These polyisocyanates may be used singly or in combination of two or more. On the other hand, when a polyisocyanate having an aromatic group is used, the obtained cured product tends to be yellowish, and it is less suitable for optical use. The weight average molecular weight of the component (A) is 2, 〇〇〇~1,000. When the weight average molecular weight is 2,000 or more, the adhesion to the substrate can be excellent, and cracking of the cured product can be prevented or deformation of the polymer film can be prevented when the polymer film is coated. On the other hand, when the weight average molecular weight is 1,000,000 or less, the composition is low in viscosity and excellent in workability, and excellent in adhesion. The component (A) may be used alone or in combination of two or more. The proportion of the component (A) is preferably from 2 to 30 parts by weight, more preferably from 3 to 20 parts by weight, based on the total amount of the composition. The blending in this range is preferred from the viewpoints of coatability of the composition, adhesion after curing, workability, flexibility, and long-term reliability. (B) Component The component (B) of the present invention is a di(meth)acrylate represented by the following formula (1) [hereinafter referred to as "(B-1) component"] and/or the following formula ( 2) The di(meth)acrylate shown [hereinafter referred to as "(B - 2) component"]. By blending the component (B) in the present invention, the strength of the cured product can be increased, and deterioration due to the presence of stress or high temperature can be prevented. 200906873

Here, R1 and R3 each independently represent a hydrogen atom or a methyl group, and r2 and R4 each independently represent an alkylene group having a carbon number of 1 to 6 'R5 represents a hydrogen atom or a methyl group, and R6 represents a hydrogen atom, a halogen atom or a group. The radicals 'R7 and R8 each independently represent a halogen atom or a methyl group, and mi and m2 each independently represent an integer of 0 to 4, and m3 and m4 each independently represent an integer of 〇2.

Here, R9 and R1Q each independently represent a hydrogen atom or a methyl group, and R11 and Rl2 each independently represent an alkylene group having 1 to 6 carbon atoms, and R13 and R14 each independently represent a halogen atom or a methyl group, and m5 and 1116 are each independently The integers of 0 to 4 are independently indicated, and the integers of 〇2 are independently indicated. First, the component (B-1) will be described. In the formula (1), R1 and R3 are excellent in the curability of the composition. Preferably, it is a hydrogen atom. As the alkylene group of R2 and R4, a lower alkylene group having a carbon number of i to 6 is more preferably an alkylene group having a carbon number of 2 to 4, and specifically may be mentioned. Methyl, ethyl, propyl and butyl, etc. Among them, Ethylethyl is preferred because the raw material is easily obtained, and the obtained cured product has excellent refractive index. R5 is preferably The methyl group is a hardened material having a low coloration. -15-200906873 The halogen atom in R6 to R8 is preferably a bromine atom. As R6 and 1η3 and m4, it is preferred that the composition is excellent in curability. R6 is a hydrogen atom, and m3 and m4 are each a compound of 0. As 11^ and m2, it is preferably 0 to 3 because of the obtained hardened substance. The (B-1) component is more preferably a di(meth)acrylate in which R5 is a methyl group in the formula (1), R6 is a hydrogen atom, and m3 and m4 are 0, because of the hardenability of the composition. Excellent, the cured product is low in coloration. Preferred examples of the component (B-1) include bis(4-propenyloxyphenyl)phenylmethane and bis(4-methylpropenyloxybenzene). Phenylmethane, bis(4-propenyloxyethoxyphenyl)phenylmethane, bis(4-methylpropenyloxyethoxyphenyl)phenylmethane, bis(4-propene oxime) Oxydiethoxyphenyl) phenylmethane, bis(4-methylpropenyloxydiethoxyphenyl)phenylmethane, bis(4-propenyloxytriethoxyphenyl)benzene Methane, bis(4-methacryloxytriethoxyphenyl)phenylmethane, bis(4-propenyloxyphenyl)methylphenylmethane, bis(4-methylpropene oxime) Phenylphenyl)methylphenylmethane, bis(4-propenyloxyethoxyphenyl)methylphenylmethane, bis(4-methylpropenyloxyethoxyphenyl)methylphenyl Methane, bis(4-propylene oxydiethoxy) Phenyl)methylphenylmethane, bis(4-methylpropenyloxydiethoxyphenyl)methylphenylmethane, bis(4-propenyloxytriethoxyphenyl)methylbenzene Methane, bis(4-methylpropenyloxytriethoxyphenyl)methylphenylmethane, etc. Next, the component (B-2) will be described. In the formula (2), R9 and Rl() In order to obtain a hardening property of the composition of 200906873, it is preferably a hydrogen atom. As the alkylene group of R11 and R12, a lower alkylene group having a carbon number of 1 to 6 is preferred, and a carbon number of 2 to 4 is more preferred. The lower alkylene group may specifically be a methylene group, an ethylidene group, a propyl group or a butyl group. Among them, it is preferably an ethyl group because the raw material is easily obtained, and the obtained product is obtained. The cured product has an excellent refractive index. The halogen atom in R13 and R14 is preferably a bromine atom. As m7 and m8, in order to make the composition excellent in curability, it is preferable to use a wide range of compounds. As m5 and m6, 〇~3 is preferable because the obtained cured product has excellent refractive index. Preferable specific examples of the component (B-2) include bis(4-propenyloxyphenyl)cyclohexane, bis(4-methacryloxyphenyl)cyclohexane, and bis ( 4-propenyloxyethoxyphenyl)cyclohexane, bis(4-methylpropenyloxyethoxyphenyl)cyclohexane, bis(4-propenyloxydiethoxyphenyl) Cyclohexyl, bis(4-methylpropenyloxydiethoxyphenyl)cyclohexane, bis(4-propenyloxytriethoxyphenyl)cyclohexane and bis(4-methyl) Acryl methoxyoxytriethoxyphenyl)cyclohexane or the like. As the component (B), among the above, from the viewpoint of excellent curability, it is more preferably bis(4-acryloxyethoxyphenyl)methylphenylmethane or bis(4-propionyloxy). Diethoxyphenyl)methylphenylmethane, bis(4-propenyloxyphenyl)methylphenylmethane, bis(4-propenyloxyethoxyphenyl)cyclohexyl, double ( 4-propenyloxydiethoxyphenyl)cyclohexane, bis(4-propenyloxyphenyl)cyclohexane. -17- 200906873 (B) The ingredients may be used alone or in combination of two or more. The ratio of the component (B) is preferably 5 to 60 parts by weight, more preferably 10 to 30 parts by weight, based on the total amount by weight of the composition. When the ratio is 5 parts by weight or more, the composition can be excellent in adhesion, and the refractive index of the cured product can be made high, which is preferable. On the other hand, by setting it to 60 parts by weight or less, the viscosity of the composition near room temperature can be lowered, and it is easy to handle, and it is preferable since the plastic substrate has no deformation. 3. (Component 0) The component (C) of the present invention has two phenyl skeletons and a compound having one (meth) acryloyl group. The composition can be obtained by blending the component (C) in the present invention. It is possible to increase the refractive index of the cured product. The component (C) may be any compound having two phenyl skeletons and one (meth)acryl fluorenyl group. The component (C) is preferably a compound represented by the following formula (3).

[In the formula (3), R15 represents a hydrogen atom or a methyl group, R16 represents an alkylene group having 1 to 6 carbon atoms, R17 represents a phenyl group or an alkyl group having a phenyl group having 1 or less carbon atoms, and η represents 0 to 4; Integer]. The alkylene group of R16 is preferably a lower alkylene group having 2 to 4 carbon atoms, and specific examples thereof include a methylene group, an exoethyl group, a propyl group and a butyl group. Among these, it is preferred to extend the ethyl group because the raw material is easily obtained, and the obtained cured product has excellent refractive index. -18-200906873 The alkyl group having a phenyl group having 10 or less carbon atoms of R17 may, for example, be a benzyl group or a p-cumylphenyl group. Specific examples of the (meth) acrylate represented by the formula (3) include, for example, phenylphenyl (meth)acrylate and (meth)propene of an ethylene oxide adduct of phenylphenol. (meth) acrylate of a propylene oxide adduct of a phenol, a phenylphenol, a (meth) acrylate of p-cumyl phenol (meth) acrylate, and an ethylene oxide adduct of p-cumyl phenol A (meth) acrylate such as an ester or a propylene oxide adduct of p-cumylphenol. The component (C) is more preferably a compound (wherein rI? is a phenyl group), that is, a (meth) acrylate having a biphenyl group. The (meth) acrylate having a biphenyl group has a neighboring body, an intermediate body, and a counter body. However, it is preferably a neighboring body from the viewpoint that it is easy to handle from a room temperature liquid state. The component (C) is preferably a compound represented by the following formula (4).

Here, 'R15, R16 and η are synonymous with the above formula (3). Specific examples of the compound represented by the above formula (4) include o-phenylphenyl (meth)acrylate and (meth)acrylate of an ethylene oxide adduct of o-phenylphenol. Further, in the above, the (o-phenylphenyl acrylate) of η = 0 is particularly preferable because the viscosity of the composition can be lowered, and the obtained cured product becomes a high refractive index. The component (C) may be used alone or in combination of two or more. 200906873 The ratio of the component (c) is preferably 10 to 70 parts by weight, more preferably 20 to 60 parts by weight, based on the total amount of the composition of 1 part by weight. By setting the ratio to 1 part by weight or more, the composition can be made low in viscosity, workability can be improved, and the cured product can have a high refractive index. On the other hand, when it is 70 parts by weight or less, the obtained cured product can be excellent in heat resistance, and is preferable. 4. (D) component The component (D) in the present invention is a compound having no phenyl skeleton or one phenyl fluorene skeleton and having one methacryl fluorenyl group. The purpose of the component (D) is to adjust the curing rate of the composition to prevent accumulation of excessive stress in the carbide. The component (D) may be any compound as long as it has a phenyl skeleton or a phenyl skeleton and has one methacryl fluorenyl group. The component (D) is preferably a methacrylate having one phenyl skeleton because it can make the cured product of the composition a high refractive index. Examples of the phenyl ί skeleton include a phenyl group, a tribromophenyl group, a benzyl group, and a phenyl group such as a tolyl group and a fluorenyl phenyl group. Specific examples of the component (D) include a methacrylate of an alkylene oxide adduct of phenol such as benzyl methacrylate or phenoxyethyl methacrylate, and an alkylene oxide of nonylphenol. The methacrylate of the adduct, and the like. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide. The number of additions of the alkylene oxide is exemplified by 1 to 4, more preferably methacrylic acid having an addition number of 1, because the refractive index of the cured product is high. -20- 200906873 As an example of the component (D) having no phenyl skeleton, a methacrylate having an alicyclic structure such as isobornyl methacrylate or cyclohexyl methacrylate is preferable because Tg can be imparted. Highly good hardened material. The component (D) may be used alone or in combination of two or more. The proportion of the component (D) is preferably from 0.5 to 30 parts by weight, more preferably from 5 to 20 parts by weight, per part by weight of the total amount of the composition. By setting the ratio to 0.5 parts by weight or more, the adhesion to the substrate can be excellent, which is preferable. On the other hand, by setting the ratio to 30 parts by weight or less, the curing rate of the composition can be made excellent, which is preferable. 5. Other components The components of the present invention are indispensable for the above components (A) to (D), and may contain other components as necessary. The composition of the present invention may contain an ethylenically unsaturated compound other than the above components (A) to (D) (hereinafter referred to as component (E)). As the component (E), a (meth) acrylate is preferred. Specific examples thereof include phenoxyethyl acrylate, tribromophenoxyethyl acrylate, tetramethyl decyl acrylate, carbitol acrylate, propylene decylmorpholine, glycidyl (meth)acrylate, and acrylic acid. 2-hydroxyethyl ester, 2-hydroxypropyl acrylate, acrylate having maleimide group, and monopropanoic acid ester of oxime, 4-butanediol monoacrylate, etc.; 1,6-hexanediol II (Meth) acrylate, decanediol diacrylate vinegar 'polyethylene glycol di(meth) acrylate, ethylene glycol di(meth) acrylate vinegar, trimethyl methacrylate tri (meth) acrylate, Pentaerythritol tris(methyl) acrylate, pentaerythritol tetra(meth) acrylate, dipentaerythritol penta(methyl) propylene oleate, dipentaerythritol hexa(meth) acrylate, tris(2-(methyl) 200906873 (meth) acrylate oligomer such as propylene methoxyethyl) isocyanurate or polyester poly(meth) acrylate epoxy (meth) acrylate. A preferred example of the (meth) acrylate as the component (E) is N-vinylcaprolactone or the like. When the composition is a visible light curing type or an ultraviolet curing type group, it is preferred to contain a photopolymerization initiator [Frequent (F) component] in addition to the above components. When the electron beam is used as the active energy ray, there is no need for the (F) component. Specific examples of the component (F) include benzoin such as benzoin, benzoin A, and benzoin propyl ether; acetophenone and 2,2-dimethoxyacetophenone; 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroketone, 1-hydroxycyclohexyl phenyl ketone, 2-methylmethylthio)benzene 3 morpholinyl-propane _ Benzenes such as ketone and N,N-dimethylaminoacetophenone; 蒽醌2,4-dimethyl group such as 2-methyl hydrazine, 1-chloroindole and 2-pentyl hydrazine Thioxanthone such as thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and diisopropylthioxanthone; acetophenone dimethyl ketal and dimethyl ketal Such ketals; benzophenone, methylbenzophenone, dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's benzhydrazin-4 a benzophenone such as a -methyldiphenyl sulfide; a 2,4,6-trimethylbenzimidyldiphenylphosphine oxide or the like. The component (F) may be used singly or in combination of two or more. The component (F) is preferably used in an amount of from 0.05 to 10 parts by weight based on the amount of the (meth)propionic acid ester contained in the composition. Other sensitizing additives may be added to enhance the photoester, and the compound is referred to as the ether-2, phenyl phenyl I]-2-ethyl ketone; 2,4-. benzyl 4, 4 5 - and 4 - and . Total i polymerization -22 - 200906873 sensitivity. As the photosensitizer, there are triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, 4-dimethyl Ethyl benzyl benzoate, isoamyl 4-dimethylaminobenzoate, etc., such photo sensitizers are preferably blended in the composition of 〇.;!~ 10 parts by weight. Further, in the composition of the present invention, in addition to the above components, various additives such as a photostabilizer, a decane coupling agent, an antioxidant, a thermal polymerization inhibitor, a leveling agent, a surfactant, and a storage stability may be blended as needed. Agents, plasticizers, lubricants, solvents, skimmers, anti-aging agents, wettability improvers, coating improvers, etc. 6. Active energy ray-curable composition The present invention is indispensable for the above components (A) to (D). As a method for producing the composition of the present invention, the components (A) to (D) and optionally other components may be produced by stirring and mixing in accordance with a usual method. Since the component (A) has a very high viscosity at room temperature, when the composition is difficult to handle at room temperature, it can be heated after stirring and mixing the composition. In this case, the heating and stirring temperature is preferably 5 〇~1 〇 〇. The composition 'of the present invention' is hardened by irradiation with an active energy ray. Here, the 'active energy line' means visible light, ultraviolet light, electron beam, X-ray, or the like. In this case, since it is not required to be a special device and is simple, it is preferably visible light or ultraviolet light. As the ultraviolet irradiation device, a high pressure mercury lamp or the like can be given. The irradiation amount and irradiation time of the active energy ray can be appropriately set according to the composition and use of -23 - 200906873 used. The composition of the present invention is preferably hardened by ultraviolet rays from the viewpoint of convenience and low cost. In the ultraviolet irradiation, an ultrahigh pressure mercury lamp, a high lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc, a xenon lamp, or the like which is generally used in the hardening of the hardened composition can be used. A high-pressure or metal halide lamp with a wavelength of 365 nm as a center is used. When the irradiation amount of ultraviolet rays is 2 〇〇 mJ/cm 2 , it can be hardened, and more preferably 300 2 2, 0 〇〇 mj/em 2 . The composition of the present invention can give a cured product having a refractive index (25 〇c ) of usually: upper, preferably 1.55 or more. The refractive index is particularly limited, and is preferably 1 · 6 2 or less. Further, the cured property is also excellent. As described above, the cured product of the composition of the present invention is suitable for use in optical materials because of its availability and transparency. That is, the wire-curable resin composition of the present invention can be applied to an optical material after curing, and the composition of the present invention is used in the manufacture of various optical materials such as a Fresnel lens, a lenticular lens, a prism sheet lens, and a plastic lens. , a coating agent, an adhesive, a lens itself, and the like. More specifically, the lens sheet may be used for a video projector or a liquid crystal display. The active energy ray-curable composition of the present invention is particularly preferably a coating agent and a lens sheet which can be used for such optical materials. As a method of using the composition of the present invention, it can be applied to a plastic film substrate by using a coating rod or the like, and the use of ultraviolet pressure mercury is preferably a mercury lamp or more, [•54 to limit the Transparent high refractive activity can be used. It is used as a method for video TV. Cloth composition -24- 200906873 The object 'cures the active energy line to harden. When a plurality of plastic substrates are bonded and formed into a member, the film can be applied to the applied composition by using a film or a sheet substrate, and then irradiated with an active energy ray to be cured. Preferably, the light source illuminating the active energy ray is a high pressure mercury lamp, a xenon lamp or the like. Preferably, uniform exposure is used, but ultraviolet lasers can also be used to perform scanning exposure in a desired shape. The method for producing a covering member of the present invention comprises the steps of applying the composition of the present invention to a substrate, and irradiating the composition with an active energy ray to cure. The substrate is preferably a transparent substrate comprising a plastic plate, a plastic film or the like. The thickness of the substrate can be arbitrarily selected to be '50 to 150 μm thick. The thickness of the composition of the present invention applied to the substrate may also be appropriately selected, and is preferably 5 to 50 μm. The method for producing an optical material of the present invention comprises the steps of applying the composition of the present invention to a substrate in a desired shape or flowing into a desired mold, and irradiating the composition with an active energy ray to harden it. . As the mold ‘preferably a material which can penetrate the active energy ray, a release agent can also be used as needed. The composition of the present invention can give a cured product having a high refractive index of a refractive index (25) of 15 4 or more as described above. Therefore, when the conventional composition is coated on the cycloolefin polymer film or when the lens sheet is formed, the refractive index of the cured product is lower than that of the cycloolefin polymer, so that the light transmittance is lowered. . The above-mentioned ring-like hydrocarbon polymer is a general term for a resin obtained from a cyclic olefin such as a raw borneol, a tetracyclic or a tetracyclic or a derivative such as the -25 to 200906873, and the like, for example, No. 3-148882 Japanese Patent Publication No. Hei 3-122137, and the like. Specifically, a ring-opening polymer of a cyclic olefin, an addition polymer of a cyclic olefin, a random copolymer of a cyclic olefin and an α-olefin of ethylene or propylene, or the like, or an unsaturated carboxylic acid or A graft modified product modified by a derivative or the like. Further, these hydrides can be mentioned. As a product, Zeonox manufactured by Sakamoto Co., Ltd., Arton manufactured by Zeonor' JSR Co., Ltd., and Topas manufactured by TICONA Co., Ltd., and the like are exemplified. These refractive indices are about 1.51 to 1.54. Next, an example in which a lens sheet is produced using the composition of the present invention will be described. When a lens sheet having a relatively thin film thickness is produced, the composition of the present invention is applied onto a mold called a stamp having a desired lens shape, and a layer aposing the composition is adhered to the transparent substrate. Next, the active energy ray was irradiated from the side of the transparent substrate to harden the composition, and then peeled off from the mold. On the other hand, when a lens sheet having a relatively large film thickness is produced, a composition of the present invention flows into between a mold having a desired lens shape and a transparent substrate. Then, the active energy ray is irradiated from the side of the transparent substrate to harden the composition, and then the mold is released from the mold. The transparent substrate 'preferably a resin substrate, and a specific example thereof may be a sheet of the above-mentioned cycloolefin polymer', a methacrylic resin, a polycarbonate resin, a methyl methacrylate-styrene resin, and a styrene resin. By. -26 - 200906873 The material of the mold is not particularly limited, and examples thereof include metals such as brass and nickel, and resins such as epoxy resins. From the point of view of the long life of the mold, it is preferably a metal mold. Next, an example of manufacturing a plastic lens using the composition of the present invention will be described. For example, a method in which the composition of the present invention is injected into a mirror-honed mold having at least one surface transparent, and an active energy ray is irradiated to harden the mold is released. C. Examples of the mold in this case include two mirror-honed molds of glass, plastic, or the like, and a thermoplastic resin such as plasticized vinyl chloride and ethylene-vinyl acetate copolymer. The gasket, and the combination of two molds and a lock mold, etc. The irradiation of the active energy ray in this case can be carried out on one or both sides of the mold. Further, irradiation and heating of the active energy ray may be combined. EXAMPLES Hereinafter, the present invention will be more specifically illustrated by the examples, but the present invention is not limited by the examples. In addition, the "part" in the following means the weight part. 〇Synthesis Example 1 (Production of urethane acrylate) In a 3 liter flask in which an oxygen/nitrogen mixed gas was previously blown, 533 parts of isophorone diisodecanoate (hereinafter referred to as IPDI) was charged. After bubbling an oxygen/nitrogen mixed gas for 1 hour at room temperature, 2 parts of dibutyltin dilaurate (hereinafter referred to as DBTL) and 0.6 parts of di-tert-butylhydroxytoluene were charged at a bath temperature. After the temperature was raised at 60 ° C, a dropping funnel was used, and 1,234 parts of polybutanediol [weight average molecular weight of 1,000; preserved gluten -27 - 200906873 by PTG- 1 000] was dropped into the flask. in. Next, 27 8 parts of 2-hydroxyethyl acrylate (hereinafter referred to as HEA) was dropped into the flask over a period of one hour. After the completion of the dropwise addition, the bath temperature was raised to 80 ° C, and the reaction was further carried out for 3 hours. When the isocyanate-based peak is reached, the reaction is terminated. The obtained urethane acrylate is referred to as UA 1. The refractive index (25 °C) of UA1 is 1.48, the viscosity (25 °C) is 123,500 mPa·s, and the average molecular weight coefficient obtained by GPC is an average molecular weight (hereinafter referred to as Μη): 3,200, weight molecular weight (hereinafter referred to as Mw)·· f ' 4,2 0 0. ◦Synthesis Example 2 (Production of urethane acrylate) In a 1 liter flask in which an oxygen/nitrogen mixed gas was previously blown, 26 parts of IPDI was charged, and an oxygen/nitrogen mixed gas was further added at room temperature for 1 hour. After bubbling, 0.3 part of DBTL and 0.1 part of di-tert-butylhydroxytoluene were charged, and the temperature was raised at 60 ° C at the bath temperature, and then diluted with 115 parts of phenoxyethyl acrylate using a dropping funnel. A portion of polypropylene glycol [average molecular weight: 3,00 00] was added to the flask over a period of one hour. (Next, 9 parts of HEA was dropped into the flask, and after the completion of the dropwise addition, the bath temperature was raised to 80 ° C, and the reaction was further carried out for 3 hours. When the isocyanate-free peak was not detected in IR, the reaction mixture was terminated. 83.8 wt% of urethane acrylate (hereinafter referred to as UA2) and 16.2 wt% of phenoxyethyl acrylate. The refractive index of UA2 (25 ° C) is 1.48,9, viscosity (25 °C) The average molecular weight obtained by GPC is 38,100 mPa·s, Μ η : 1 0,000, Mw : 1 2,200 ° -28- 200906873 Furthermore, in Comparative Example 2, 5 parts of the reaction mixture were blended. Example 3 (Production of urethane acrylate) In addition to using a 2 liter flask 'using 70 parts of IPDI, 〇.8 parts of DBTL, 0.3 parts of di-tert-butyl hydroxytoluene', using 500 parts of Hiplex HX -205 0 [A diol of Toho Chemical Co., Ltd., which is prepared by repeating hexamethylene glycol and phthalic acid; the average molecular weight of 2 = 000] is carried out by the same method as in Synthesis Example 1. Next, in addition to using 250 parts of tetrahydrofurfuryl acrylate as a diluent and 18 parts of The mixture of HEA was subjected to the same reaction as in Synthesis Example 1 except that the temperature of the bath was raised to 80 ° C and the reaction was further carried out for 2 hours. The reaction mixture contained 70.2% by weight of a carbamate-containing acid vinegar ( Hereinafter referred to as UA3) and 29.8% by weight of tetrahydrofurfuryl acrylate. The refractive index of UA3 (25. (3) is 1.490, and the viscosity (25 ° C) is 143,300 mPa. s, the average obtained by GP C Molecular weight Mn ·· 1 3,3 00, Mw : 25,700 ° Further, in Comparative Example 3, 5 parts of the reaction mixture were blended. 〇 Examples 1 to 5, Comparative Examples 1 to 5 Table 1 and Table The compound shown in 2 and its ratio are stirred and mixed according to a usual method to produce an active energy ray-curable composition. Using the obtained composition, the viscosity of the cured product and the refractive index of the cured product are carried out according to the following method. Evaluation of the adhesion of the cycloolefin polymer film. The results are shown in Table 3. • Viscosity -29 - 200906873 The viscosity of the composition at 25 ° C was measured using an E-type viscometer. With a high-pressure mercury lamp to illuminate around 3 65nm The composition is cured under the condition that the amount is 50 OmJ/cm2. For the cured product obtained from the composition, the refractive index of the sodium D line is measured by the Abe refractometer DR-M2 made of ATAG 0. (25 ° C) • Adhesiveness Arton (film thickness ΙΟΟ μπι) made of JSR (strand) was used as the substrate. '/ coating the composition on the substrate with a film thickness of 30 μm, using a coating bar or the like, under the same curing conditions as the sample for refractive index measurement, ultraviolet irradiation, and the obtained coating film On the top, 100 squares of 1 mm square were produced, and the number of the residual cells after the tape peeling test was evaluated. Further, the adhesion of the PET film which had been subjected to surface treatment for comparison was evaluated, and the results are also shown in Table 3. As the PET film, Cosmoshine (film thickness: 50 μm) manufactured by Toyo Co., Ltd. was used. [Table 1] Example 1 (8) (Β) (C) (D) (E) (F) UA1 5 BisPAP BisZ TO-2344 TO-1463 BzMA POMA M-309 | THFA Ir 20 55 10 i 5 j 5 3 2 5 20 55 10 5 ! 5 3 3 5 20 55 10 5丨5 3 4 15 20 15 20 5 | 25 3 5 5 20 55 10 5 l 5 3 The numbers of the components in Table 1 mean the number of parts. The abbreviations in Table 1 mean the following. -30 - 200906873 • UA1: urethane acrylate manufactured by Synthesis Example 1. BisPAP: bis(4-acryloxyethoxyphenyl)methylphenylmethane [in formula (1) 'R1 R3, R5 and R6 are a hydrogen atom, R2 and R4 are a pendant ethyl group, and mi and m2 are 1, and m3 and m4 are 0]] BisZ: bis(4-acryloxyethoxyphenyl) ring Hexane [In the formula (2), R9 and R1Q are hydrogen atoms, R11 and R12 are exoethyl, m5 and m6 are 1, and m7 and ms are oxime compounds] • TO-2344: o-phenylphenyl acrylate , East Asia Synthetic (Shared) Aronix f.. TO-2344 [In the formula (4), R15 is a hydrogen atom, R16 is a compound having an ethyl group and η is 0] • ΤΟ-1463: O-phenylphenoxy acrylate Ethyl ester, Aronix ΤΟ-1463 manufactured by East Asia Synthetic Co., Ltd. [In the formula (4), R15 is a hydrogen atom 'R16 is a compound having an ethyl group and η is 1]. BzMA: benzyl methacrylate • POMA: methyl group Phenyloxyethyl acrylate • M-309: Tri-propyl methacrylate triacetate, East Asian synthesis (stock) I Aronix M-309 • ΤΗ FA: tetrahydroxy decyl acrylate. Ir: 1-hydroxyl ring Hexyl phenyl ketone, Ciba Specialty Chemicals Irgacure 184 2 00906873 [Table 2] (A) (A), (B) (B)' (C) (D) (E) (F) Comparative Example UA1 UA2 UA3 BisZ M-211B TO-1463 BzMA M-309 THFA POA Ir 1 5 25 40 10 10 5 2 4.2 30 50 10 5 0.8 5 3 3.5 20 55 10 5 5 1.5 5 4 80 20 5 5 42 50 8 5 The numbers of the components in Table 2 mean the parts. The abbreviations in Table 2 are synonymous with those in Table 1. Abbreviations other than the abbreviations of Table 1 mean the following. • UA2: urethane acrylate produced in Synthesis Example 2. U A 3 : urethane acrylate produced in Synthesis Example 3

.M-211B: Modified diacrylate of 4 molar bisphenol A ethylene oxide, Aronix M-211B manufactured by East Asian Synthetic Co., Ltd. • POA: phenoxyethyl acrylate [Table 3] Viscosity (mPs-S Refractive index refractive index - _ honey mate 25 ° C (liquid) - _ (hardened) Arton PET _ Example 1 101 1. 557 1.591 80 100 Example 2 112 1.555 1.590 100 100 Example 3 118 1.553 1.587 60 100 Example 4 32 1.509 1.547 80 100 Example 5 115 1.554 A 1.587 100 100 - Comparative Example 1 89 1.538 1.572 15 100 Comparative Example 2 217 1.549 1.579 0 60 Comparative Example 3 134 1.551 1.585 0 80 Comparative Example 4 250 1.535 1.560 0 15 Comparative Example 5 110 1.505 1.532 10 80 200906873 It is apparent from the examples of the present invention that the use of the composition of the present invention is good for the plastic substrate, especially for the cycloolefin polymer, and a base can be obtained. The material also has a high refractive index covering member. Further, among the acrylates having an o-phenylphenyl skeleton of the component (c), 'the composition using n = ( (Examples 1, 2, 4, 5), and the same amount of n = 0 are used. In the case of comparison, the viscosity is low and the adhesion to the cycloolefin polymer can be made higher, and the system is more preferable. On the other hand, in the case where the diacrylate having a bisphenol A skeleton is contained in place of the component (B) instead of the component (B) (Comparative Example 1), the adhesion to the cycloolefin polymer is lowered. . In the case of the composition of UA-2 having a weight average molecular weight of more than 10,0 0 (Comparative Example 2) containing the same structure as the component of the present invention, the viscosity became high' and The adhesion of the cycloolefin polymer is greatly reduced. The same applies to the case of the composition containing the urethane acrylate UA-3 having different diol structures (Comparative Example 3). In the case of a composition containing a diacrylate having a bisphenol A skeleton as a composition containing no component (c) and containing a monoacrylate having one phenyl skeleton (Comparative Example 4), Since the refractive index is increased, the blending of the component (A), the component (D), and the component (E) does not cause the composition to have a desired refractive index, and as a result, the adhesion between the PE τ and the cycloolefin polymer is lowered. In the case of a composition containing no (Β) component and (C) component (Comparative Example 5), the ratio of the component (A) is increased, but the adhesion to PET is excellent, but the cycloolefin polymerization is carried out. The adhesion of the object is lowered and the refractive index cannot be increased. ◦ Application Example (Manufacture of Lens Sheet) 200906873 The composition obtained in the example was used to flow into a mold having a lens shape, and then the Arton used in the example was used as a transparent substrate. From the side of the transparent substrate, an ultraviolet ray having a conveyor belt was used, and a high-pressure mercury lamp was used as a light source, and ultraviolet rays of a UV-A irradiation amount of 800 mJ/cm 2 were irradiated to cure the composition. The cured product after hardening was peeled off from the mold, and as a result, the compositions of Examples 1 to 5 were easily peeled off, and a lens sheet having a desired shape was obtained. Further, in the compositions of Examples 1 to 5, a lens sheet excellent in optical properties such as the above can be obtained. Use of the device of the present invention The composition of the present invention can be used in various applications for use in optical materials such as coated materials and lens sheets. Among these, in particular, a cycloolefin polymer which is difficult to obtain good adhesion has excellent adhesion, and can have a higher refractive index than the polymer, and is suitable for use in opticals produced using the polymer. The manufacture of the covering material and the lens sheet of the member is suitable for use in various fields such as display materials, motor electronic component materials, optical component materials, and liquid crystal panels. [Simple description of the diagram] None. [Main component symbol description] None. -34-

Claims (1)

200906873 X. Patent application scope: 1. An active energy ray-curable composition 'containing the following components (A) to (D), (A) Component: polyether diol 'aromatic-free polyisocyanate and containing A reaction product of a (meth) acrylate of a hydroxyl group having a weight average molecular weight of 2,000 to 10, a urethane (meth) acrylate of hydrazine, and (B) a component: the following formula (1) And/or a di(meth)acrylate represented by the formula (2), Here, R1 and R3 each independently represent a hydrogen atom or a methyl group, R2 and R4 each independently represent an alkylene group having 1 to 6 carbon atoms, R5 represents a hydrogen atom or a methyl group, and R6 represents a hydrogen atom, a halogen atom or a group. The group, R7 and R8 each independently represent a halogen atom or a methyl group, and "^ and m2 each independently represent an integer of 0 to 4, and m3 and 1114 each independently represent an integer of 〇~2" Here, R9 and R1() each independently represent a hydrogen atom or a methyl group, and R11 and R12 each independently represent an alkylene group having 1 to 6 carbon atoms, and R13 and R14-35 - 200906873 each independently form a halogen atom. Or methyl, Πΐ5 and Π16 each independently represent an integer of 0 to 4, and melons 7 and 1 „8 each independently represent an integer of 0 to 2, (C) component: having two phenyl skeletons and having one ( (meth) propylene fluorenyl compound, (D) component: a compound having no phenyl skeleton or having one phenyl skeleton and having one methacryl fluorenyl group. 2 · Active energy as in claim 1 a wire-hardening composition in which the 'polyether diol" has ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol The constituent unit selected by the group consisting of 3. The active energy ray-curable composition of claim 2, wherein the polyether diol is polybutanediol in the (Α) component. The active energy ray-curable composition of the first aspect of the invention, wherein the component (C) is a (methyl) group represented by the following formula (3) Polyester, R15 〇/=\ R17 H2C=C—C^〇-R16)-〇-h^^ (3) Here, R15 represents a hydrogen atom or a methyl group, and R16 represents a hydrocarbon having a carbon number of 1 to 6. The base 'Rl7' represents a phenyl group or an alkyl group having a phenyl group having a carbon number or less, and η represents an integer of 0 to 4. 5. The active energy ray-curable composition of claim 4, wherein the (C) The component is a (meth) acrylate represented by the following formula (4), -36 - 200906873 Here, R15, R16 and η are synonymous with the above formula (3). 6. The active energy ray-curable composition of claim 5, wherein among the components (C), the compound of the formula (4) is η=0. 7. The active energy ray-curable composition according to claim 1, wherein the component (D) is a methacrylate having one phenyl skeleton. 8. The active energy ray-curable composition according to claim 1, wherein the ethylenically unsaturated compound other than the components (Α) to (D) is further contained. 9. The active energy ray-curable composition of claim 1, wherein the photopolymerization initiator is further contained. The active energy ray-curable composition of claim 1, wherein the cured product obtained from the composition has a refractive index at 150 ° C of 1.54 or more and 1.62 or less. 1 1 An active energy ray-curable coating composition comprising the composition of any one of the first to tenth aspects of the patent application. 12. A coated member' which is formed by coating a plastic film with a cured film of the composition of claim 11 of the patent application. 13. The coated member of claim 12, wherein the plastic film is a cyclic olefin polymer film. 1 4. An optical material' which is obtained by hardening a composition according to any one of claims 1 to 1. 1 5 · An optical material as claimed in claim 14 is a lens sheet. -37 - 200906873 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: