KR20000022550A - Radiation curable resin composition - Google Patents

Abstract

PURPOSE: A radiation curable resin composition having a high productivity and showing high transparency is provided, to produce molded articles exhibiting minimal coloration upon exposure to light, superior dimensional precis ion, high heat resistance, only slight adhesion to substrates under high temperature conditions. CONSTITUTION: A radiation curable composition comprises: (A) at least one compound containing a (meth)acrylate group represented by formula (1), wherein R1 is a hydrogen atom or a methyl group, R2 is an alkylene group or a hydroxyalkylene group having 2 to 6 carbon atoms, R3 is a divalent organic group, n is a number of 1 to 10, m is an integer of 0 or 1, and Ar1 and Ar2 are independently a group comprising an aromatic ring; (B) at least one compound derived from trishydroxyethyl isocyanurate, and containing at least one (meth)acrylate group; and (C) at least one radiation polymerization initiator.

Description

Radiation curable resin composition

As an active energy ray, the method of manufacturing a plastic lens etc. by irradiating UV-curable resin with a ultraviolet-ray from a mercury lamp is proposed (Japanese Patent Laid-Open No. 194401/1986, 207632/1988). According to the above method, the resin has the advantage of curing in a short time by irradiation of ultraviolet rays, but the color and transparency of the lens produced by curing with irradiation of ultraviolet rays is generally polymethyl methacrylate, polycarbonate or diethylene glycol bis Inferior to those prepared from polymers such as arylcarbonate. In addition, the coloring of the molded product by exposure to ultraviolet rays is a problem. In addition, in molding by polymerization in a die of conventional UV curable resins, deformation at curing time tends to remain in the molded product after molding, so that the molded product impairs the dimensional accuracy of the product and is removed from the die. Bend or contract

Japanese Patent Laid-Open No. 174910/1995 discloses a prism sheet for improving the front brightness of a backlight unit used in a liquid crystal display device. The prism sheet is molded into a specific shape from a transparent material having a specific refractive index. In the method of manufacturing a prism sheet, the patent proposes a method of forming a composite using transparent glass having a specific range of refractive index and a method of forming a prism shape from a UV curable resin composition.

As recognized by Japanese Patent Laid-Open No. 174910/1995, the plastic material reproduced by the UV curable resin can be used only in a limited use for applications requiring heat resistance. That is, if a representative lens sheet of a prism sheet obtained from a conventional UV curable resin is used in a high temperature environment, part of the lens sheet is soluble on the surface of the backlight, leaving a sticky trace. This is a fatal flaw affecting the optical performance of the product.

In addition, attention is paid to the liquid crystal display device using a plastic film as a substrate instead of a conventional glass substrate at the time of producing a thin and large liquid crystal display cell having a curved display surface. However, when a plastic film is used as the substrate, the outer surface of the substrate is easily damaged, damaging its appearance, and causing irregular reflections, which are damaged. As a result, the optical characteristics of the liquid crystal display device have an adverse effect. For this reason, the coating layer of the UV curable resin is provided on the surface of the substrate in order to increase the hardness of the substrate surface to obtain a liquid crystal display element which is hard to be damaged.

However, if the coating layer is formed using a conventional UV curable resin, the obtained image is dark and of poor quality compared to that obtained from a liquid crystal display device using a glass substrate due to insufficient transparency, coloring obtained by exposure to light, and the like.

The present invention eliminates the above drawbacks of the prior art, exhibits high productivity and high transparency, and provides high refractive index, high surface hardness, minimal coloring due to light, good dimensional accuracy, good heat resistance and release from adhesion to surfaces in high temperature environments. An object of the present invention is to provide a molded article having a radiation curable resin composition suitable for molding.

Summary of the Invention

The above object of the present invention has been achieved in the present invention by providing a radiocurable composition composed of:

(A)-at least one compound containing a (meth) acrylate group of the formula (1);

(In Formula 1, R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group or a hydroxyalkylene group having 2 to 6 carbon atoms, R ³ is a divalent organic group, n is a number of 1 to 10 , m is an integer of 0 or 1, Ar ¹ and Ar ² are each an aromatic ring constituent group)

(B) at least one compound composed of (tri) ethylisocyanurate, further composed of at least one (meth) acrylate group, and

(C) at least one radiation polymerization initiator.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a radiation curable resin composition which is useful for producing optical components such as lenses that are cured rapidly by irradiation with ultraviolet light, particularly lenses that are molded by polymerization in lenses, optical discs, prisms and dies. It is about. The resin composition is also suitable for use as a surface coating material for plastic film substrates used in optical materials such as liquid crystal display device substrates.

Component (A) is represented by Formula 1 and is at least one compound containing a (meth) acrylate group, consisting of two aromatic groups, one of which is one (meth) acryl through an alkylene or hydroxyalkylene group It is connected to the rate group. Preferred examples of the (hydroxy) alkylene group are 1,2-ethylyl, 1,3-propylyl, 1,2-propylyl, 1,4-butylyl, 1,2-butylyl, 1,4- Pentylyl, 1,4- (2-methyl) -butylyl, 1,5-pentylyl and 2-hydroxy-1,3-propylyl.

In particular, 1,2-ethylyl, 1,2-propylyl, 1,4-butylyl, 1,2-butylyl, 1,4- (2-methyl) -butylyl or 2-hydroxy-1, 3-propylyl is preferred.

Preferably the number of alkoxy groups is in the range of 1-5, more preferably 1-3.

When two phenyl groups are connected to each other via a bridging group, the bridging groups are preferably 2,2'-propylyl, 2,2'-hexafluoropropylyl, methylyl or sulfoxy groups. Among these, 2,2'-propylyl is especially preferable.

Examples of compounds in which m is 1 in formula (1) are (meth) acrylic acid esters of ethylene oxide added p-cumylphenol and (meth) acrylic acid esters of propylene oxide added p-cumylphenol. The compounds may be obtained by the addition of ethylene oxide or propylene oxide to p-cumylphenol, and then the reaction of the obtained compound with (meth) acrylic acid. Among the above, particularly preferred are (meth) acrylic acid esters of ethylene oxide added p-cumylphenol. Aronix M110 (Doagosei Chemical Industry Co., Ltd.) can be provided as an example of a commercially useful product that can be used.

Examples of compounds in which m is 0 in Formula 1 include 2-hydroxy-3- (O-phenylphenoxy) propyl acrylate, 2- (O-phenylphenoxy) ethyl acrylate, 2- [2- (O- Phenylphenoxy) -ethoxy] ethyl acrylate and the like can be provided. The compounds can be obtained by addition of alkylene oxide to phenylphenol followed by reaction with (meth) acrylic acid. TO-1317 (Doagosei Chemical Industry Co., Ltd.) can be used as an example of a commercially useful product.

The amount of component (A) in the composition of the present invention is usually 10 to 70 wt%, preferably 10 to 60 wt% and more preferably 10 to 50 wt%. Wt% when used above is defined as relating to the total amount of the composition unless otherwise indicated. Cured products having a suitable refractive index and good heat resistance can be obtained by incorporating component (A) in an amount in the above range.

At least one (meth) acrylate group-containing compound composed of triethyl isocyanurate is used as component (B) in the composition of the present invention. Trisethylisocyanurate is derived from trishydroxyethyl isocyanurate. The (meth) acrylate group can be bonded directly to the alkyl group of the hydroxyalkyl of hydroxy-ethylisocyanurate via a hydroxy acid-like ring opening caprolactone.

Preferably, since the crosslinking density and characteristics of the cured product are optimized, at least one (meth) acrylate group is directly bonded to the alkyl of hydroxyalkyl-isocyanurate.

Preferably, the (meth) acryl functionality of the compound is preferably at least about 2, 3 since one group or less than one hydroxy alkyl group on average remains unreacted. On average, if the (meth) acryl functionality of the compound is 1 or less, the crosslinking density of the cured product is relatively low.

The proportion of component (B) in the composition is usually 10 to 70 wt%, and preferably 30 to 60 wt%. If the ratio is less than 10 wt%, the hardness and mar resistance of the cured product are impaired, and if it is 70 wt% or more, the shrinkage sometimes increases when the obtained composition is cured.

TEICA (Daiichi Kogyo Seiyaku Co., Ltd.), FA731A (Hitachi Chemical Co., Ltd.), Aronix M215, M315, M325 (Doagosei Chemical Industry Co., Ltd.) and the like are provided as examples of commercially useful products of the compounds. Can be.

In the present invention, any compound can be used as a radiation polymerization initiator of component (C) as long as the compound can be decomposed by irradiation, generate radicals, and initiate polymerization. Optionally, a photosensitizer can be used with component (C). Herein, the radiation includes radiation such as, for example, infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α-rays, β-rays, and γ-rays. Ultraviolet light is preferred among them.

Examples of radiopolymerization initiators include acetophenone, acetophenone benzyl ketan, anthraquinone, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone compound, triphenylamine, carbazole , 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, 2-hydroxy-2-methyl-1-phenylpropa-1- Non, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropano-1-non, carbazole, xanthone, 1,1-dimethoxy-deoxybenzoin, 3,3'- Dimethyl-4-methoxybenzophenone, thioxanthone compound, diethyl thioxanthone, 2-isopropyl thioxanthone, 2-chlorothioxanthone, 1- (4-dodecylphenyl) -2-hydroxy- 2-methylpropano-1-non, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropano-1-non, triphenylamine, 2,4,6-trimethylbenzoyl Diphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide, bisacylphosphine oxide, ben Vaginal methyl ketan, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropa-1-non, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoin propyl ether, Benzophenone, Michler's ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-non, 3-methylacetophenone and 3,3 ', 4,4 '-Tetra (t-butyl peroxycarbonyl) benzophenone (BTTB).

In addition, coloring sensitisers such as xanthene, thioxanthene, coumarin and ketocoumarin may be used as component (C).

And the compound represented by following formula (2) can be used.

(In Formula 2, R ⁴ and R ⁵ is an alkyl group having 1 to 5 carbon atoms, in particular a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-pentyl group Or i-pentyl groups, each of which is preferably an alkyl group having from 1 to 3 carbon atoms, wherein r represents a number from 2 to 50, preferably from 2 to 20)

Among these compounds, benzyl methyl ketan, 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4- Trimethylpentyl phosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-non and the like are particularly preferable.

Irgacure 184, 651, 500, 907, 369, 784, 2959 (made by Ciba Gauge), Lucirin TPO (made by BASF), Darocur 1116, 1173 (made by Merk Co.), Ubecryl P36 (made by UCB Co.), ESCACURE KIP150, ESCACURE KIP100F (manufactured by Lamberti Co.) and the like can be provided as an example of a commercially useful product.

Examples of photosensitizers include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, 4-methyl dimethylaminobenzoate, 4-ethyl dimethylaminobenzoate, 4-isoamyl dimethylamino Commercially useful products such as benzoate and Ubecryl P102, 103, 104, 105 (manufactured by UCB Co.).

The amount of said radiation polymerization initiator added to the composition of the present invention as component (C) is usually 0.01 to 10 wt%, preferably 0.5 to 7 wt% and particularly preferably 1 to 5 wt%. The amount of component (C) in excess of 10 wt% adversely affects the storage stability of the composition and the characteristics of the cured product. If the amount is 0.01 wt% or less, the curing rate is reduced.

In addition to the above-mentioned components (A) and (B), polymerizable monomers containing (meth) acrylate groups or vinyl groups can be used as optical components in the present invention. The polymerizable monomer is a mono- or multi-functional monomer.

Examples of monofunctional monomers include vinyl groups containing monomers such as N-vinyl caprolactam, N-vinyl pyrrolidone, N-vinylcarbazole, N-vinyl formamide, vinyl pyridine; And acrylamide, acryloyl morpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, isobornyloxyethyl (meth) acrylate, isobornyl ( Meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate , Diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate , N, N-dimethyl (meth) acrylamide tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydroperryl (meth) acrylate, tetrabromophenyl (meth) Acrylate, 2-tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (meth) acrylate, tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl (meth ) Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, phenoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, pentachlorophenyl (meth) Acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, bornyl (meth) acrylate, methyltriethylene diglycol (meth) acrylate And a (meth) acryl group composed of monomers such as (meth) acrylate group-containing monomers represented by the following Chemical Formulas 3-6.

CH ₂ = C (R ⁶ ) COO (R ⁷ O) _m (R ⁸ )

(In Formula 3, R ⁶ is a hydrogen atom or a methyl group, R ⁷ is an alkylene group having 2 to 6, preferably 2 to 4 carbon atoms, R ⁸ is 1 to 12, preferably 1 to 9 An alkyl group or hydrogen atom having a carbon atom, and m is an integer of 1 to 12, preferably 1 to 8)

CH ₂ = C (R ⁶ ) CO- (OR ⁹ ) _p -O-CH ₂ -R ¹⁰

(In Formula 4, R ⁶ is the same as that of Formula 3, R ⁹ is an alkylene group having 2 to 8, preferably 2 to 5 carbon atoms, R ¹⁰ is a tetrahydrofuryl group, and p Is an integer of 1 to 8, preferably 1 to 4)

CH ₂ = C (R ⁶ ) -COO- (R ⁹ O) _p -R ¹¹

(In Formula 5, R ⁶ , R ⁹ and p are as defined above, R ¹¹ is a phenyl group optionally substituted with an alkyl group having 1 to 12, preferably 1 to 9 carbon atoms.)

(In Chemical Formula 6, R ⁶ and R ⁹ are as defined above, q is an integer of 0 to 8; and R ¹² and R ¹³ are each an alkyl group containing 1 to 6 carbon atoms, a hydrogen atom,- R ¹⁴ -A group, wherein R ¹⁴ is an alkylene group containing 1 to 6 carbon atoms, and A is a (meth) acrylateoxy group)

Among these, N-vinyl caprolactam, N-vinyl pyrrolidone, acryloyl morpholine, N-vinylcarbazole, isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, etc. are preferable. Particularly preferred among these are N-vinyl caprolactam, N-vinyl pyrrolidone and acryloyl morpholine. Acryloyl morpholine is an ideal monofunctional monomer.

Examples of commercially useful products of such mono-functional monomers include Aronix M-111, M-113, M-117 (manufactured by Toagosei Chemical Industry Co., Ltd.), KAYARAD TC110S, R-629, R-644 (Nippon Kayaku Co., Ltd.). Limited) and Viscoat 3700 (Osaka Organic Chemical Industries Limited).

Examples of multi-functional monomers include (meth) acrylate group-containing monomers such as ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, tetra ethylene glycol di (Meth) acrylate, tricyclodecanediyl-dimethylene di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tripropylene diacrylate, neopentyl Glycol di (meth) acrylate, two ends (meth) acrylic acid ester of ethylene oxide added bisphenol A, two ends (meth) acrylic acid ester of propylene oxide added bisphenol A, two ends of ethylene oxide added tetrabromobisphenol A (Meth) acrylic acid ester, two-terminal (meth) acrylic acid of propylene oxide-added tetrabromobisphenol A Ester, two terminal (meth) acrylic acid addition product of bisphenol A diglycidyl ether, two terminal (meth) acrylic acid addition product of tetrabromo bisphenol A diglycidyl ether, 1,4-butanediol di (meth) acrylate , 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate and polyethylene glycol di (meth) acrylic There is a rate.

In the above, two terminal (meth) acrylic acid esters of ethylene oxide-added bisphenol A, two terminal (meth) acrylic acid esters of propylene oxide-added bisphenol A, tricyclodecanediyldimethylene di (meth) acrylate, tetraethylene glycol di ( Particular preference is given to meth) acrylate, tripropylene glycol (meth) acrylate, neopentyl glycol di (meth) acrylate, and polyethylene glycol di (meth) acrylate.

Yupimer UV, SA1002 (Mitsubishi Chemical Company Limited), Viscoat 700 (Osaka Organic Chemicals Limited), KAYARAD R-604, DPCA-60, DPCA-30, DPCA-120, HX-620, D-310, D- 330 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210 (manufactured by Toagosei Chemical Industry Co., Ltd.), and the like can be provided as commercially useful products of multi-functional monomers.

The polymerization monomers may be used in amounts of preferably 40 wt% or less and particularly preferably 30 wt% or less, each or two or more in combination. If the amount is 40 wt% or more, the curing shrinkage rate of the cured product is increased and the refractive index is decreased.

In addition to the above components, various additives may be optionally added to the compositions of the present invention. The additives include, for example, antioxidants, UV absorbers, photosensitizers, silane binders, anti-aging agents, thermal polymerization inhibitors, colorants, leveling agents, surfactants, preservatives, plasticizers, lubricants, solvents, inorganic fillers, organic fillers, fillers, wetting enhancers. And a coating film improver.

Examples of commercially useful antioxidants include Irganox 1010, 1035, 1076 and 1222 (Ciba gauge). Examples of commercially useful UV absorbers include Tinuvin P, 234, 320, 326, 327, 328, 213, 400 (made by Ciba Gauge) and Sumisorb 110, 130, 140, 220, 250, 300, 320, 340, 350, 400 (Sumitomo Chemical Industry Co., Ltd.). Commercially useful products of photosensitizers include Tinuvin 292, 144, 622LD (made by Ciba Gauge), Sanol LS-770, 765, 292, 2626, 1114, 744 (manufactured by Sangyo Chemical Corporation). Examples of silane binders include γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-acryloxypropyltri-methoxysilane and SH6062, SZ6030 (Toray-Dow Corning Silicone Co., Ltd.) and KBE903, Commercially useful products such as KBM803 (Shin-Etsu Silicone Co., Ltd.). Examples of commercially useful products of anti-aging agents include Antigen W, S, P, 3C, 6C, RD-G, FR and AW (Sumitomo Chemical Industry Co., Ltd.).

In addition to the above components, other polymerizable compounds, polymers or oligomers may be incorporated as other additives to the compositions of the present invention. The polymerizable compound, polymer or oligomer may be, for example, an epoxy resin; Polymeric compounds such as urethane (meth) acrylates, vinyl ethers, propenyl ethers and maleic acid derivatives; Polyamide, polyimide, polyamideimide, polyurethane, polybutadiene, chloroprene, polyether, polyester, pentadiene derivative, styrene / butadiene / styrene block copolymer, styrene / ethylene / butene / styrene block copolymer, styrene / Isoprene / styrene block copolymers, petroleum resins, xylene resins, ketone resins, fluorine-containing oligomers, silicon-containing oligomers and polysulfide oligomers.

The radiation-curable resin composition of the present invention can be prepared by mixing the above components by a conventional method. The viscosity of the composition of the present invention prepared is usually adjusted within the range of 100 to 20,000 cps / 25 ° C and preferably 500 to 10,000 cps / 25 ° C.

When the radiocurable resin composition of the present invention is cured, a cured product having a Youngs Modulus at 23 ° C. in the range of 1 to 250 kg / mm 2 is obtained. The refractive index (25 ° C.) of the cured product is preferably 1.54 or more, more preferably 1.55 or more; The amount of shrinkage obtained by curing of the composition is preferably 10% or less and more preferably 6% or less.

The invention will be described in more detail below by means of examples provided for the purpose of explanation of the invention and not in limitation thereof.

Examples 1-6 and Comparative Examples A-D

The component having the composition shown in Table 1 was charged to a reaction vessel equipped with a stirrer, and stirred for 3 hours by adjusting the liquid temperature at 50 to 60 ° C. in order to obtain a uniformly mixed resin composition. This resin composition was used for the following test.

In Table 1, the composition unit of Example 1-6 and Comparative Examples A-D is weight part.

Test Example

Test specimens were prepared from the resin compositions obtained in Examples and Comparative Examples above to evaluate the viscosity, refractive index, pencil hardness, cure shrinkage, resistance to coloration upon exposure to light and substrate adhesion at high temperatures. The results are shown in Table 2.

Viscosity Measurement:

The viscosity in 25 degreeC was measured according to JIS K7117 using the rotational viscometer.

Preparation of test specimens:

The resin composition was added to a glass plate with a thickness of about 200 μm using a 15 μm applicator rod, and irradiated with ultraviolet rays at a dose of 1.0 J / cm 2 under air to obtain a cured film. The cured film was peeled off the glass plate and aged for 24 hours at 23 ° C. and 50% relative humidity to obtain test specimens.

Refractive Index Measurement:

The refractive index of the test specimen at 25 ° C. was measured using an Abbes refractometer.

Pencil Hardness Measurement:

Pencil hardness was measured according to JIS K5400 using a pencil scraping tester.

Hardening Shrinkage Measurement:

The composition was added to a 120 μm thick PET film using a 250 μm applicator rod and irradiated with ultraviolet light at a dose of 1.0 J / cm 2 in air. The PET film was cut to 10 square cm and four corners were measured with a caliper. Warpage averages were measured at four corners. Samples with an average of 10 mm or less were considered acceptable (indicated by O), and samples having an average of 10 mm or more were considered unacceptable (indicated by X).

Resistance to pigmentation upon exposure to light:

The composition was added to the glass plate using a 250 μm applicator rod and irradiated with ultraviolet light at a dose of 1.0 J / cm 2 in air to prepare a cured test specimen having a thickness of 100 μm. The test specimens were exposed to ultraviolet light for 7 days using a photoresist tester (QUV, manufactured by Q-Panel Corporation). The color difference (ΔE) of the test specimens was measured using a color difference meter (CR-300, manufactured by Minolta Camera Co., Ltd.) and a standard whiteboard as a standard. Samples with ΔE of 10 or less were considered acceptable (denoted by O) and samples with ΔE of 10 or greater were considered unacceptable (denoted by X).

Substrate adhesion at high temperature:

The resin composition was filled in the die for the prism sheet having irregularities. A transparent polyethylene terephthalate (PET) sheet having a thickness of 125 μm was attached to the composition. In order to obtain a cured film, ultraviolet rays were irradiated to the side of the PET film at a dose of 1.0 J / cm 2. Five sheets of the cured film were cut into 5 mm x 50 mm each and arranged on a glass plate at intervals of 5 mm. An acrylic plate 2 mm thick was placed on the sheet of cured film. Samples were placed in a thermostat for 1 hour with a load of 20 g / cm 2 on an acrylic plate at 100 ° C. The acrylic plate was then removed to observe the part that was in contact with the test specimen, in order to investigate whether a trace was left by the adhesion of the test specimen. Samples without traces were marked with O, and samples with traces were marked with X.

<Resin Compositions Used in Examples and Comparative Examples> Example Comparative Example One 2 3 4 5 6 A B C D a 30 b 30 30 30 30 30 30 50 50 c 30 d 50 50 50 50 50 e 50 f 50 50 g 20 20 20 20 20 20 50 h 20 i 20 j 50 k 3 3 3 3 3 3 3 3 l 4 m - 2

a: acrylic ester of ethylene oxide-added p-cumylphenol (in formula 1, n = 1)

b: 2-hydroxy-3- (o-phenylphenoxy) propyl acrylate

c: phenoxyethyl acrylate

d: trishydroxyethyl isocyanurate triacrylate

e: trishydroxyethyl isocyanurate diacrylate

f: caprolactone modified dihydroxyethyl isocyanurate triacrylate (1 mol of caprolactone reacted with 1 mol of trishydroxyethyl isocyanurate)

g: acryloyl morpholine

h: N-vinyl pyrrolidone

i: N-vinyl caprolactam

j: trimethylolpropane triacrylate

k: 1-hydroxycyclohexyl phenylpropanone

l: oligo 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propano-1-non

m: 2,4,6-trimethylbenzoyldiphenylphosphine oxide

Example Comparative Example One 2 3 4 5 6 A B C D Viscosity (cps / 25 ℃) 1100 2500 1100 1200 1500 2200 400 600 4800 300 Refractive index 1.552 1.560 1.557 1.558 1.559 1.556 1.542 1.545 1.569 1.560 Pencil hardness 3H 3H 2H 2H 2H 2H HB 4H H B Curing shrinkage O O O O O O O X X O Resistance to coloring when exposed to light O O O O O O O O O X Attachment to substrate at high temperatures O O O O O O X O X X

The radiation-curable resin composition of the present invention has excellent curing ability, not only provides high manufacturing power in the production of molded articles, but also shows excellent dimensional accuracy and shows very low curing shrinkage. In addition, the compositions produce molded articles that are highly transparent and have high surface hardness and minimal coloration upon exposure to light.

In addition, the composition only slightly adheres to the substrate at elevated temperatures. Radiation-curable resin compositions are very useful as surface coating materials of plastic materials used in optical components such as substrates of liquid crystal display devices, as well as coating materials for wood, plastic, metal, glass, and ceramics.

Claims (18)

(A) at least one compound containing a (meth) acrylate group represented by the following formula (1), (Formula 1) (In Formula 1, R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group or a hydroxyalkylene group having 2 to 6 carbon atoms, R ³ is a divalent organic group, n is a number of 1 to 10 , m is an integer of 0 or 1, and Ar ¹ and Ar ² are each an aromatic ring constituent group) (B) at least one compound consisting of tris-ethyl isocyanurate and containing at least one (meth) acrylate group, and (C) A radiocurable composition comprising at least one radiopolymerization initiator. The method of claim 1, R ² is 1,2-ethylyl, 1,2-propylyl, 1,4-butylyl, 1,2-butylyl, 1,4- (2-methyl) -butylyl or 2-hydroxy-1 , 3-propylyl. The method according to claim 1 or 2, R ¹ is hydrogen, characterized in that the composition. The method according to any one of claims 1 to 3, N is 1 to 5, characterized in that the composition. The method according to any one of claims 1 to 4, M is 0, or m is 1, R ³ is 2,2'-propylyl, 2,2'-hexafluoropropylyl, methylyl or sulfox. The method according to any one of claims 1 to 5, The composition comprises 10 to 70 wt.% Of compound (A), 10 to 70 wt.% Of compound (B), 0.01 to 10 wt.% Of compound (C) and 0 of polymerizable monomer other than (A) or (B). To 40wt.%. The method according to any one of claims 1 to 6, The composition is characterized in that it comprises 10 to 60wt.% Of compound (A). The method according to any one of claims 1 to 7, The composition is characterized in that it comprises 30 to 60wt.% Of compound (B). The method according to any one of claims 1 to 8, At least one (meth) acrylate group of the compound (B) is characterized in that the bond directly to the alkyl group of hydroxylalkyl isocyanurate. The method according to any one of claims 1 to 9, At least one group of the compound (B) is a hydroxyalkyl group. The method according to any one of claims 1 to 10, Compound (A) or compound (B) and other polymerizable monomers are present as being selected from the group consisting of N-vinyl caprolactam, N-vinylpyrrolidone and acryloylmorpholine. The method according to any one of claims 1 to 11, The composition is characterized in that the viscosity in the range of 100 to 20,000cps at 25 ℃. Molding product, characterized in that the composition cured according to any one of claims 1 to 12. The method of claim 13, The product is an optical component. The method according to claim 13 or 14, Said product is a lens, disc, prism or lens sheet. The method according to any one of claims 13 to 15, The product is characterized in that it has a Young's modulus in the range of 1-250 kg / mm2 at 23 ℃. The method according to any one of claims 13 to 16, The product is characterized in that it has a refractive index of 1.54 or more at 25 ℃. The method according to any one of claims 13 to 17, Shrinkage obtained by curing the composition is less than 10%.