KR20170125076A - Active energy ray-curable composition, cured product, optical component and method for producing active energy ray-curable composition - Google Patents

Abstract

An object of the present invention is to provide an active energy ray curable composition having a high refractive index and excellent transparency and capable of producing a cured product having excellent scratch resistance and high adhesion to a plastic substrate do.
The active energy ray curable composition of the present invention is an active energy ray curable composition (D) containing a metal oxide (A), a (meth) acrylate (B) having an aromatic ring skeleton and a photopolymerization initiator (C) Wherein the energy ray-curable composition (D) has a refractive index of 1.56 to 1.70 at 25 占 폚 and a total light transmittance of the active energy ray-curable composition (D) of 90% or more.

Description

TECHNICAL FIELD [0001] The present invention relates to an active energy ray-curable composition, a cured product, an optical component, and a method for producing an active energy ray-

The present invention relates to an active energy ray curable composition, a cured product thereof, various optical components obtained from a cured product, and a process for producing the active energy ray curable composition. To an active energy ray curable composition having high refractive index and excellent transparency.

BACKGROUND ART An optical lens such as a prism sheet used for a liquid crystal display, a Fresnel lens used for a projection TV, and a lenticular lens has conventionally been produced by pouring an active energy ray curable composition into a mold with a resin base set on the inner surface thereof, And then curing it.

In recent years, attempts have been made to improve the brightness of an optical lens as the brightness of a display increases. For this purpose, a technology (Patent Document 1) in which fine particles of metal oxide are dispersed in a high refractive index resin, for example, Is under review.

In the method of dispersing the metal oxide fine particles of Patent Document 1, it is necessary to include a dispersant and an organic solvent in the high refractive index resin. The cured product produced by curing the high refractive index resin produced by this method is preferably an organic solvent . If the organic solvent remains in the cured product, there is a problem that scratches are generated by contact with other members during transportation when assembled. Including fine particles of metal oxide inhibits the transparency of the cured product, so that it is difficult to achieve both high refractive index and transparency.

Japanese Patent Application Laid-Open No. 2010-248505

An object of the present invention is to provide an active energy ray curable composition which is high in refractive index and excellent in transparency and which is capable of producing a cured product having excellent scratch resistance and excellent adhesion to a plastic substrate do.

Means for Solving the Problems The present inventors have conducted studies to achieve the above object, and as a result, they have reached the present invention.

That is,

(1) An active energy ray curable composition (D) comprising a metal oxide (A), a (meth) acrylate (B) having an aromatic ring skeleton and a photopolymerization initiator (C) Wherein the active energy ray curable composition (D) has a total light transmittance of 90% or more and a refractive index at 25 占 폚 of 1.56 to 1.70.

(2) a cured product obtained by curing the active energy ray-curable composition of the present invention;

(3) an optical component using the cured product of the present invention;

(4) In the method for producing the active energy ray-curable composition of the present invention, the molar ratio of the metal alkoxide (a1) and water is adjusted so that the molar ratio of the metal alkoxide (a1) / water = (a1) and water are added to a (meth) acrylate (B) having an aromatic ring skeleton to form a reaction liquid; and a step of reacting the metal alkoxide (a1) A reaction step of forming a metal oxide (A), and a step of adding a photopolymerization initiator (C) to the reaction solution to add the photopolymerization initiator (C).

The active energy ray curable composition of the present invention has an effect of high refractive index, excellent transparency, excellent scratch resistance of the cured product, and high adhesion to a plastic substrate.

The active energy ray curable composition of the present invention is an active energy ray curable composition (D) containing a metal oxide (A), a (meth) acrylate (B) having an aromatic ring skeleton and a photopolymerization initiator (C) Wherein the energy ray-curable composition (D) has a refractive index of 1.56 to 1.70 at 25 占 폚 and a total light transmittance of the active energy ray-curable composition (D) of 90% or more.

In the present specification, the refractive index means a refractive index of light at a wavelength of 589 nm at 25 占 폚.

In the present specification, the total light transmittance means the total light transmittance measured in accordance with JIS-K 7105.

The metal oxide (A) contained in the active energy ray-curable composition of the present invention is preferably a metal oxide having excellent compatibility with (meth) acrylate (B) having an aromatic ring skeleton.

When the metal oxide (A) is excellent in compatibility with the (meth) acrylate (B) having an aromatic ring skeleton, the refractive index of the active energy ray curable composition (D) becomes high.

Examples of the metal oxide (A) from the viewpoint of the refractive index include oxides of zirconium, titanium, hafnium, zinc, aluminum, gallium, indium, germanium and tin.

It is preferable that the metal oxide (A) is obtained by reacting the metal alkoxide (a1) with water.

Examples of the metal alkoxide (a1) include titanium alkoxides, zirconium alkoxides, hafnium alkoxides, zinc alkoxides, aluminum alkoxides, gallium alkoxides, indium alkoxides, germanium alkoxides, tin alkoxides, .

The zirconium alkoxide includes, for example, zirconium tetra-n-butoxide, and the titanium alkoxide includes, for example, titanium tetra-n-butoxide.

In the active energy ray-curable composition of the present invention, the metal oxide (A) is a metal alkoxide (a1) and water in such a manner that the molar ratio of the metal alkoxide (a1) / water is 2.0 to 200, (Meth) acrylate (B).

If the molar ratio is less than 2.0, the transparency of the active energy ray curable composition (D) becomes insufficient.

When the molar ratio exceeds 200, the refractive index of the active energy ray curable composition (D) is lowered.

In the active energy ray-curable composition of the present invention, the average particle diameter of the metal oxide (A) is preferably 10 nm or less, more preferably 1 to 5 nm.

When the average particle diameter of the metal oxide (A) is 10 nm or less, the total light transmittance is increased.

In the present specification, "the average particle diameter of the metal oxide (A) is 10 nm or less" means that the average particle diameter of the metal oxide (A) is 10 nm or less as measured by the dynamic light scattering method , Or that the average particle size of the metal oxide (A) is analyzed to be a size smaller than the detection limit in the measurement by the dynamic light scattering method.

The active energy ray-curable composition of the present invention comprises a (meth) acrylate (B) having an aromatic ring skeleton. By using the (meth) acrylate (B) having an aromatic ring skeleton, the refractive index of the active energy ray-curable composition (D) of the present invention is preferably high.

The (meth) acrylate (B) having an aromatic ring skeleton is preferably a (meth) acrylate having an oxyalkylene group in the molecule. Further, the oxyalkylene group is more preferably an oxyethylene group. Examples of the (meth) acrylate (B) having such an aromatic ring skeleton include mono (meth) acrylates of benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, o-, m- or p- Mono (meth) acrylate of 3,3'-diphenyl-4,4'-dihydroxybiphenyl, nonylphenoxypolyethylene glycol (meth) acrylate, ethylene oxide adduct of bisphenol A (Meth) acrylate, di (meth) acrylate of an ethylene oxide adduct of fluorene, and the like.

Of the (meth) acrylates (B) having these aromatic ring skeletons, more preferred are mono (meth) acrylates of phenoxyethyl (meth) acrylate, o-, m- or p- (meth) acrylates of ethylene oxide adducts of m- or p-phenylphenoxy (oxyalkyl) adducts, (meth) acrylates of ethylene oxide adducts of fluorene and di (meth) acrylates of ethylene oxide adducts of fluorene.

Of these, more preferred are phenoxyethyl acrylate, o-phenylphenoxyethyl acrylate, 6 moles of ethylene oxide fluorene acrylate, and 10 moles of ethylene oxide fluorene acrylate.

If the (meth) acrylate (B) having an aromatic ring skeleton is a compound of these, the refractive index of the active energy ray curable composition (D) is preferably high.

The active energy ray curable composition of the present invention comprises a photopolymerization initiator (C).

Examples of the photopolymerization initiator (C) include a phosphine oxide compound (C1), a benzoylformate compound (C2), a thioxanthone compound (C3), an oxime ester compound (C4), a hydroxybenzoyl compound The compound (C5), the benzophenone compound (C6), the ketal compound (C7), the 1,3 aminoalkylphenone compound (C8) and the like.

Examples of the phosphine oxide compound (C1) include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

Examples of the benzoylformate compound (C2) include methylbenzoylformate and the like.

Examples of the thioxanthone compound (C3) include isopropyl thioxanthone and the like.

Examples of the oxime ester compound (C4) include 1,2-octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime)], ethanone, 1- [ 2-methylbenzoyl) -9H-carbazol-3-yl] -, 1 (O-acetyloxime).

Examples of the hydroxybenzoyl compound (C5) include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexyl phenyl ketone and benzoin alkyl ether.

Examples of the benzophenone compound (C6) include benzophenone.

As the ketal compound (C7), benzyldimethyl ketal and the like can be mentioned.

(4-methylthiophenyl) -2-morpholinopropane-1-one, 2- (dimethylamino) -2 - [(4 Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone.

Among these photopolymerization initiators (C), preferred from the viewpoint of the curability of the active energy ray-curable composition of the present invention and the curable product prepared by curing the active energy ray-curable composition of the present invention with an active energy ray are phosphine oxide- (C1), and more preferably bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

In the active energy ray-curable composition of the present invention, the content of the metal oxide (A) is preferably 5 to 50 parts by weight, based on the total weight of the metal oxide (A) and the (meth) By weight, more preferably 10 to 40% by weight. When the content of the metal oxide (A) is 5 wt% or more, the refractive index of the active energy ray curable composition (D) becomes sufficiently high.

When the content of the metal oxide (A) is 50% by weight or less, the transparency of the active energy ray curable composition (D) becomes sufficient.

In the active energy ray-curable composition of the present invention, the content of the (meth) acrylate (B) having the above-mentioned aromatic ring skeleton is preferably in the range of (meth) acrylate It is preferably 50 to 95% by weight, more preferably 60 to 85% by weight, based on the total weight. When the content of the (meth) acrylate (B) having an aromatic ring skeleton is within the above range, the refractive index of the active energy ray curable composition (D) becomes sufficiently high.

In the active energy ray curable composition of the present invention, the content of the photopolymerization initiator (C) is preferably 0.1 to 10 parts by weight, based on the total weight of the metal oxide (A) and the (meth) By weight, more preferably 0.2 to 7% by weight.

When the content of the photopolymerization initiator (C) is in the above range, the curability of the active energy ray curable composition (D) becomes good and the transparency of the active energy ray curable composition (D) becomes good.

The active energy ray curable composition of the present invention may contain various additives as needed within a range not to impair the effects of the present invention.

Examples of the additive include plasticizers, organic solvents, dispersants, defoamers, thixotropic agents (thickeners), slip agents, antioxidants, hindered amine light stabilizers and ultraviolet absorbers.

Next, a method for producing a cured product obtained by curing the active energy ray-curable composition of the present invention, which is an example of a method of using the active energy ray-curable composition of the present invention, with an active energy ray will be described.

The method for producing the cured product includes a step of irradiating the active energy ray-curable composition of the present invention with an active energy ray to cure the active energy ray to form a cured product.

Examples of the active energy ray used in the active energy ray irradiation step include ultraviolet rays, electron rays, X rays, infrared rays, visible rays, and the like.

Among these active energy rays, ultraviolet rays and electron beams are preferable in terms of hardenability and resin deterioration.

When ultraviolet rays are used as an active energy ray, various kinds of ultraviolet irradiation devices (for example, an ultraviolet irradiation device (model number: VPS / I600, manufactured by Fusion UV Systems Co., Ltd.) can be used.

Examples of the lamp to be used include a high-pressure mercury lamp, a metal halide lamp, and the like. The irradiation dose of ultraviolet rays is preferably 10 to 10,000 mJ / cm ² , more preferably 100 to 5,000 mJ / cm ² from the viewpoints of the curability of the active energy ray curable composition and the flexibility of the cured product.

The cured product thus produced is also a cured product of the present invention.

The method for producing the cured product may further include the following steps.

That is, before the step of irradiating the active energy ray, a step of arranging the active energy ray-curable composition of the present invention in a flat mold having a fine concavo-convex structure may be included.

After this process, the active energy ray curable composition is cured by performing the active energy ray irradiation process, and the optical lens can be manufactured by releasing the cured product from the mold.

In the above arranging step, it is preferable that the active energy ray-curable composition of the present invention is warmed to 20 to 50 캜 in advance and placed in a mold.

It is preferable to arrange the active energy ray curable composition at a temperature of 20 to 50 占 폚 in advance in the arranging step, and it is more preferable to arrange the active energy ray curable composition at 25 to 40 占 폚.

In the above arranging step, the active energy ray curable composition is coated or filled into a metal mold so that the thickness after curing becomes 20 to 150 탆 by using a dispenser or the like, and a transparent substrate such as a transparent film from the coated film is irradiated with air Pressure lamination.

The active energy ray-curable composition thus arranged becomes a cured product through the subsequent activation energy ray irradiation step, and the cured product is released from the mold to obtain an optical lens sheet.

Examples of the transparent substrate include a resin such as methyl methacrylate (co) polymer, polyethylene terephthalate, polycarbonate, polytriacetyl cellulose, and polycycloolefin.

The optical component such as an optical lens or an optical lens sheet using the cured product of the present invention is also an optical component of the present invention.

That is, the active energy ray curable composition of the present invention can be used as a material for optical parts.

Next, a method for producing the active energy ray curable composition of the present invention will be described.

The method for producing an active energy ray curable composition of the present invention is characterized in that the molar ratio of the metal alkoxide (a1) and water is such that the metal alkoxide (a1) / water = 2.0 to 200, (Meth) acrylate (B) having an aromatic ring skeleton to form a metal oxide (A) by reacting the metal alkoxide (a1) in the reaction liquid with the water to form a metal oxide And a step of adding a photopolymerization initiator (C) to the reaction solution to add the photopolymerization initiator (C).

In the reaction solution producing step, the metal alkoxide (a1) and the water are mixed so that the molar ratio of the metal alkoxide (a1) and water becomes the metal alkoxide (a1) / water = 2.0 to 200, Meth) acrylate (B). The molar ratio of the metal alkoxide (a1) and water is preferably 5.0 to 100 as the metal alkoxide (a1) / water. If the molar ratio is less than 2.0, the transparency of the active energy ray-curable composition produced through the subsequent steps becomes insufficient.

If the molar ratio exceeds 200, the refractive index of the active energy ray-curable composition produced through the subsequent steps becomes low.

Examples of the metal alkoxide (a1) used in the above reaction solution production step include titanium alkoxide, zirconium alkoxide, hafnium alkoxide, zinc alkoxide, aluminum alkoxide, gallium alkoxide, indium alkoxide, germanium Alkoxide, tin alkoxide, and the like.

Examples of the (meth) acrylate (B) having an aromatic ring skeleton used in the above reaction solution production step include benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, o-, m- or mono (meth) acrylate of p-phenylphenol, mono (meth) acrylate of 3,3'-diphenyl-4,4'-dihydroxybiphenyl and nonylphenoxypolyethylene glycol (meth) Di (meth) acrylates of ethylene oxide adducts of A, and di (meth) acrylates of ethylene oxide adducts of fluorene.

In the method for producing an active energy ray-curable composition of the present invention, it is preferable to add an organic amine as the catalyst (a2) to the reaction solution in the step of producing the reaction solution.

Examples of the organic amine include aliphatic amines, alicyclic amines, aromatic amines, and heterocyclic amines.

Examples of the aliphatic amine include aliphatic amines having 1 to 20 carbon atoms such as hexylamine, octylamine, methylhexylamine, methyloctylamine, dimethylhexylamine, dimethyloctylamine, dimethyllaurylamine, dimethylcetylamine, trimethylamine, 18, mono-, di-, and tri-alkylamines.

Examples of the alicyclic amines include cycloalkylamines having 4 to 12 carbon atoms in the cycloalkyl group such as cyclobutylamine, cyclohexylamine, cyclopentylamine, cyclooctylamine, N-methylcyclohexylamine and N-ethylcyclohexylamine; And alkyl (1 to 6 carbon atoms) substituents thereof.

Examples of the aromatic amines include aromatic amines having 6 to 18 carbon atoms such as aniline and diphenylamine.

Examples of the heterocyclic amines include heterocyclic amines having 4 to 10 carbon atoms such as morpholine.

The step of adding the photopolymerization initiator may be carried out at any time. For example, a photopolymerization initiator (C) may be added when the reaction solution is prepared in the reaction solution production step, or a photopolymerization initiator (C) may be added to the reaction solution after the reaction step.

Example

Hereinafter, the present invention will be further described with reference to examples and comparative examples, but the present invention is not limited thereto.

Example 1

(B-1) (trade name: KOMERATE-A011, manufactured by KPX Green Chemical Co., Ltd.) was added to a reaction vessel equipped with a stirrer, a cooling tube and a thermometer. (A1-1) (trade name: TBZR, manufactured by Nippon Soda Co., Ltd.), 80.0 parts of water, 0.01 part of water and 0.05 part of triethylamine (a2-2) ], And reacted at 65 ° C for 2 hours. Then, 2.0 parts of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (C1-1) (trade name "Lucirin TPO", manufactured by BASF) was added and mixed and stirred at 65 ° C. until homogeneous to obtain an active energy Thereby obtaining a precursor composition (D-1).

Example 2

45.0 parts of phenoxyethyl acrylate (B-2) (trade name: Wright acrylate POA, manufactured by Kyowa Chemical Industry Co., Ltd.) and 10.0 parts of ethylene oxide were added to a reaction vessel equipped with a stirrer, a cooling tube and a thermometer Acrylate (B-4) (trade name: KOMERATE-D104, KPX Green Chemical Co., Ltd.). (A1-2) (trade name: B-1, manufactured by Nippon Soda Co., Ltd. (trade name, manufactured by Nippon Shokubai Co., Ltd.), 0.1 part of water and 0.03 part of triethylamine (a2-2) 15.0 parts of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (C1-2) (trade name "Irgacure 819", manufactured by BASF) was added and reacted at 65 ° C for 2 hours, Ltd.) was added and mixed and stirred at 65 캜 until homogeneous to obtain an active energy ray curable composition (D-2).

Example 3

40.0 parts of o-phenylphenoxyethyl acrylate (B-1), 10.0 parts of phenoxyethylacrylate (B-2), 6 parts of ethylene oxide were added to a reaction vessel equipped with a stirrer, a cooling tube and a thermometer, (B-3) (trade name: KOMERATE-D064, manufactured by KPX Green Chemical Co., Ltd.). 20.0 parts of zirconium tetra-n-butoxide (a1-1), 0.05 part of water and 0.05 part of trimethylamine (a2-1) were charged and stirred for 30 minutes. Then, 30.0 parts of zirconium tetra- 2.0 parts of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (C1-1) was added thereto, and the mixture was stirred and mixed at 65 DEG C until homogeneous to obtain an active energy ray curable composition (D-3) .

Example 4

70.0 parts of o-phenylphenoxyethyl acrylate (B-1), 10.0 parts of fluorene acrylate (B-3) in an amount of 6 moles of ethylene oxide, 0.05 parts of water and 10.0 parts of water were added to a reaction vessel equipped with a stirrer, 0.05 part of trimethylamine (a2-1) was added and stirred for 30 minutes, 20.0 parts of titanium tetra-n-butoxide (a1-2) was injected, and the mixture was reacted at 65 ° C for 2 hours. Then, 1-hydroxycyclo 2.0 parts of hexyl phenyl ketone (C5-1) (trade name: Irgacure 184, BASF) were added and mixed and stirred at 65 캜 until homogeneous to obtain an active energy ray curable composition (D-4).

Example 5

70.0 parts of phenoxyethyl acrylate (B-2), 0.1 part of water and 0.05 part of trimethylamine (a2-1) were poured into a reaction vessel equipped with a stirrer, a cooling tube and a thermometer and stirred for 30 minutes. Then, zirconium tetra- 40.0 parts of n-butoxide (a1-1) was charged and reacted at 65 DEG C for 2 hours. Then, 2.0 parts of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (C1-2) was added , And mixed and stirred at 65 캜 until homogeneous to obtain an active energy ray curable composition (D-5).

Comparative Example 1

45.0 parts of phenoxyethyl acrylate (B-2), 40.0 parts of fluorene acrylate (B-4) of 10 mol of ethylene oxide, 0.5 parts of bis (2,4,6 (Trimethylbenzoyl) -phenylphosphine oxide (C1-2) were added, and the mixture was stirred and mixed at 65 DEG C until homogeneous to obtain an active energy ray curable composition (D'-1).

Comparative Example 2

45.0 parts of phenoxyethyl acrylate (B-2), 40.0 parts of fluorene acrylate (B-4) of 10 molar part of ethylene oxide, 0.10 part of titanium oxide fine particles (A-1 2.0 parts of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (C1-2) (trade name: MT-01, manufactured by Teika Corporation) and 2.0 parts of bis Were mixed and stirred to obtain an active energy ray curable composition (D'-2).

Comparative Example 3

45.0 parts of phenoxyethyl acrylate (B-2), 40.0 parts of fluorene acrylate (B-4) of 10 molar part of ethylene oxide, 0.10 part of titanium oxide fine particles (A-1 ) And 2.0 parts of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (C1-1) were added and mixed and stirred at 65 캜 until homogeneous to obtain an active energy ray curable composition (D'-3) .

Comparative Example 4

70.0 parts of o-phenylphenoxyethyl acrylate (B-1), 10.0 parts of fluorene acrylate (B-3) in an amount of 6 moles of ethylene oxide, 5.0 parts of water and 100 parts of water were added to a reaction vessel equipped with a stirrer, After 20 parts of zirconium tetra-n-butoxide (a1-1) was injected, the mixture was reacted at 65 ° C for 2 hours, 2.0 parts of 6-trimethylbenzoyldiphenylphosphine oxide (C1-1) were added and mixed and stirred at 65 캜 until homogeneous to obtain an active energy ray curable composition (D'-4).

Comparative Example 5

70.0 parts of o-phenylphenoxyethyl acrylate (B-1), 10.0 parts of fluorene acrylate (B-3) in an amount of 6 moles of ethylene oxide, 0.003 part of water and 100 parts of water were added to a reaction vessel equipped with a stirrer, 0.05 part of triethylamine (a2-2) was added and stirred for 30 minutes, 20.0 parts of zirconium tetra-n-butoxide (a1-1) was injected and reacted at 65 ° C for 2 hours, 2.0 parts of 6-trimethylbenzoyldiphenylphosphine oxide (C1-1) were added and mixed and stirred at 65 캜 until homogeneous to obtain an active energy ray curable composition (D'-5).

Comparative Example 6

80.0 parts of dimethyloltricyclodecane diacrylate (B'-1), 0.05 part of water and 0.05 part of triethylamine (a2-2) were charged into a reaction vessel equipped with a stirrer, a cooling tube and a thermometer and stirred for 30 minutes , 20.0 parts of titanium tetra-n-butoxide (a1-2) was introduced and reacted at 65 ° C for 2 hours. Thereafter, 2.0 parts of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (C1-1) And mixed and stirred at 65 캜 until homogeneous to obtain an active energy ray curable composition (D'-6).

The refractive indexes of the active energy ray-curable compositions of Examples 1 to 5 and Comparative Examples 1 to 6 at 25 ° C, the total light transmittance (%), and the curing of the active energy ray curable composition of Examples 1 to 5 and Comparative Examples 1 to 6 The adhesion of water and the resilience of scratches were measured and evaluated by the method described below. The results are shown in Table 1.

For Examples and Comparative Examples containing an organic solvent, evaluation was carried out after sufficiently volatilizing the organic solvent with this distributor.

[Evaluation of refractive index]

The refractive indexes of the active energy ray-curable compositions of Examples 1 to 5 and Comparative Examples 1 to 6 were measured using a refractive index meter (trade name: Abbe's refractive index meter 4T, manufactured by Atago Co., Ltd.) under an environment of 25 캜.

[Evaluation of total light transmittance]

Silicone rubber having a thickness of 100 탆 was cut out on a slide glass having a thickness of 1 mm, and the active energy ray curable composition of each example and each comparative example was poured into the cut part. Next, a slide glass having a different thickness of 1 mm was placed on the flowing active energy ray-curable composition, and both ends of each slide glass were fixed with a clip. Thereafter, the total light transmittance (%) was measured in accordance with JIS-K 7105 using a total light transmittance measuring apparatus (trade name "haze-garddual", BYK gardner Co., Ltd.). In addition, the active energy ray curable composition of the present invention needs to have a total light transmittance of 90% or more.

[Production of test pieces]

The active energy ray curable composition was coated on one side of a glass plate with an applicator so as to have a thickness of 20 占 퐉 and then a PET film having a thickness of 100 占 퐉 (trade name: Cosmo Shine A4300 manufactured by Toyama Bunko K.K.) And the roller was pushed from above to push out the air. The active energy ray curable composition was cured by irradiating ultraviolet rays at 1000 mJ / cm ² from the PET film side with an ultraviolet irradiation device. The cured product adhering closely to the PET film was peeled from the glass plate to prepare a test piece.

[Evaluation of adhesion]

The test piece was allowed to stand for 24 hours under an environment of 23 ° C. and a relative humidity of 50%, and then cut with a cutter knife in a 1 mm width according to JIS K 5600-5-6, × 10 pieces) were produced, and a cellophane adhesive tape was stuck on the checkerboard and 90 degrees peeled off. The peeled state of the cured product from the PET film was visually observed and evaluated according to the following criteria.

A: More than 90 of the 100 checkerboard scales remain on the substrate without peeling.

B: 10 to 89 of the 100 checkerboard scales remain on the substrate without being peeled off

C: Of the 100 checkerboard scales, 9 or fewer remain on the substrate without being peeled off.

[Evaluation of recoverability of scratches]

(1) A metal mold made of stainless steel having a groove depth of 50 占 퐉 and a pitch width of 20 占 퐉 was prepared by carving parallel lines and finely rugged.

(2) An active energy ray curable composition was coated on one side of the mold with an applicator so as to have a thickness of 100 占 퐉, and then a PET film having a thickness of 100 占 퐉 (trade name: Cosmo Shine A4300 manufactured by Toyobama Co., Ltd.) And the roller was rolled from above to push out the air. Ultraviolet rays were irradiated at 1000 mJ / cm ² from the PET film side by an ultraviolet irradiation device (model number " VPS / I600 ", manufactured by Fusion UV Systems Co., Ltd.) and cured to prepare a filmy cured product.

(3) The surface of the film-like cured product was subjected to a scratch test in accordance with JIS K 5600-5-4 using a pencil equipped with a chromium cap.

(4) The surface of the film-like cured product after the scratching test was visually observed and judged according to the following criteria.

A: The scratches are completely lost within 3 seconds.

B: Scratches remain after 3 seconds of scratching.

C: All scratches remain after 3 seconds.

All of the active energy ray-curable compositions of Examples 1 to 5 were sufficiently high in refractive index, excellent in transparency, high in adhesion to a plastic substrate, and excellent in scratch resistance.

On the other hand, the active energy ray curable composition of Comparative Example 1 not containing the metal oxide (A) had a refractive index of less than 1.56, poor adhesion, and insufficient scratch resistance.

The active energy ray curable composition of Comparative Example 2 had a refractive index of less than 1.56.

The active energy ray curable composition of Comparative Example 3 had a transparency of less than 90%.

The active energy ray curable composition of Comparative Example 4 had a transparency of less than 90%.

The active energy ray curable composition of Comparative Example 5 had a refractive index of less than 1.56.

The active energy ray curable composition of Comparative Example 6 using a (meth) acrylate not containing an aromatic ring had a refractive index of less than 1.56.

Industrial availability

The active energy ray curable composition of the present invention has a high refractive index and is excellent in transparency. The cured product is excellent as an optical component and an electric / electronic component because of excellent scratch resistance and high adhesion with a plastic substrate Can be used.

The optical component in which the cured product of the present invention is used includes an optical lens, an optical lens sheet or a film, and more specifically, a plastic lens (a prism lens, a lenticular lens, a microlens, , An optical compensation film, a phase difference film, a prism, an optical fiber, a solder resist for flexible printed wiring, a plating resist, an interlayer insulating film for a multilayer printed wiring board, and a photosensitive optical waveguide.

Claims (12)

An active energy ray curable composition (D) comprising a metal oxide (A), a (meth) acrylate (B) having an aromatic ring skeleton and a photopolymerization initiator (C) Wherein the active energy ray curable composition (D) has a total light transmittance of 90% or more, and the refractive index in the active energy ray curable composition (D) is 1.56 to 1.70. The method according to claim 1,
Wherein the content of the metal oxide (A) is 15 to 50% by weight based on the total weight of the metal oxide (A) and the (meth) acrylate (B) having the aromatic ring skeleton. 3. The method according to claim 1 or 2,
The metal oxide (A) is obtained by reacting the metal alkoxide (a1) and water in a (meth) acrylate (B) having an aromatic ring skeleton such that the molar ratio of the metal alkoxide (a1) / water is 2.0 to 200 And the resulting metal oxide. The method of claim 3,
Wherein the metal alkoxide (a1) is at least one selected from the group consisting of titanium alkoxide, zirconium alkoxide, hafnium alkoxide, zinc alkoxide, aluminum alkoxide, gallium alkoxide, indium alkoxide, germanium alkoxide and tin alkoxide Active energy radiation curable composition. 5. The method according to any one of claims 1 to 4,
Wherein the average particle diameter of the metal oxide (A) is 10 nm or less. 6. The method according to any one of claims 1 to 5,
Wherein the (meth) acrylate (B) having the aromatic ring skeleton is a (meth) acrylate having an oxyalkylene group in the molecule. The method according to claim 6,
Wherein the oxyalkylene group is an oxyethylene group. 8. The method according to any one of claims 1 to 7,
Active energy ray curable composition for optical parts. A cured product obtained by curing the active energy ray-curable composition according to any one of claims 1 to 8. An optical component using the cured product according to claim 9. 9. A process for producing the active energy ray-curable composition according to any one of claims 1 to 8,
(Meth) acrylate (B) having an aromatic ring skeleton such that the molar ratio of the metal alkoxide (a1) to water is such that the metal alkoxide (a1) / water = 2.0 to 200, To prepare a reaction solution;
A reaction step of reacting the metal alkoxide (a1) in the reaction solution with the water to form a metal oxide (A)
To the reaction solution is added a photopolymerization initiator (C)
≪ RTI ID = 0.0 > 1, < / RTI > 12. The method of claim 11,
Wherein the organic amine is added as the catalyst (a2) to the reaction solution in the step of producing the reaction solution.