JP2003277451A - Photocurable resin composition and optical member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a liquid curable resin composition which provides a cured material having a high refractive index, excellent adhesivity to a substrate and restoring property and excellent productivity without causing adhesion to a mold in continuous production and is suitable for making an optical member such as a lens sheet, etc. <P>SOLUTION: The photocurable resin composition comprises (A) a urethane (meth)acrylate component obtained by reacting (a) a hydroxy group-containing (meth)acrylate with (b) an organic polyisocyanate and then reacting the reaction product with a diol represented by formula (1) (R<SP>1</SP>s are each a hydrogen atom, a methyl group or an ethyl group and these may exist together in one monomer with the proviso that ≥50 mol % R<SP>1</SP>s in the total R<SP>1</SP>s are the group except a hydrogen atom; R<SP>2</SP>is a hydrogen atom or a methyl group; m and n are each a number of 1-20, respectively), (B) an ethylenic unsaturated group-containing compound except the component (A) and (C) a photopolymerization initiator. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable resin composition, more specifically, a prism lens sheet used for a backlight of a liquid crystal display device, a Fresnel lens sheet used for a screen of a projection television, and the like. The present invention relates to a lens portion of a lens sheet such as a lenticular lens sheet, a photocurable resin composition useful for forming an optical member such as a backlight using such a sheet, and an optical member made of the cured product.

[0002]

2. Description of the Related Art Conventionally, lenses such as Fresnel lenses and lenticular lenses have been manufactured by methods such as a pressing method and a casting method. However, both methods require a long time to manufacture the lenses, resulting in poor productivity. . In order to solve such a problem, in recent years, studies have been made to manufacture a lens using an ultraviolet curable resin. Specifically, a UV-curable resin composition is poured between a lens-shaped mold and a transparent resin substrate, and ultraviolet rays are irradiated from the substrate side to cure the composition to form a lens in a short time. It can be manufactured. Furthermore, with the recent trend toward thinner and larger projection televisions and video projectors, various proposals and studies have been made for the resin forming the lenses, in accordance with various lens characteristics such as high refractive index and mechanical characteristics. There is.
For example, in Japanese Patent No. 3058751, (A) a diol (a) obtained by reacting bisphenol A with an alkylene oxide and an aromatic organic polyisocyanate (b).
Urethane (meth) acrylate, which is a reaction product obtained by reacting (a) with a hydroxyl group-containing (meth) acrylate (c), an ethylenically unsaturated group-containing compound other than the components (B) and (A), and (C). An ultraviolet curable resin composition for a transmissive screen containing a photopolymerization initiator is described.

[0003]

However, such a conventional UV-curable resin composition is required for a lens having a refractive index, adhesion to various plastic substrates, releasability from a mold, and restoration. It was not possible to obtain a cured product that sufficiently satisfies the required characteristics.

[0004]

In order to solve the above problems in the conventional resin composition, the inventors of the present invention have conducted diligent research and, as a result, have made a urethane composed of a diol having a specific structure in a certain process. By producing a cured product using a photocurable resin composition in which a (meth) acrylate, an ethylenically unsaturated group-containing compound other than that, and a photopolymerization initiator are combined, a high refractive index and various plastic groups are obtained. The inventors have found that an excellent optical member exhibiting good adhesion to a material, particularly a transmissive screen such as a Fresnel lens or a lenticular lens, can be obtained, and completed the present invention.

That is, the present invention provides the following component (A),
(B) and (C): (A) (a) hydroxyl group-containing (meth) acrylate and (b)
After reacting the organic polyisocyanate, then (c)
Urethane (meth) acrylate which is a reaction product obtained by reacting the diol represented by the formula (1);

[0006]

[Chemical 3] (In the formula, R ¹ is a hydrogen atom, a methyl group, or an ethyl group, and these may be mixed in R ¹ in one molecule, provided that 50 mol% or more of R ^{1 s} are all R ^{1 s.} Other than a hydrogen atom, R ² represents a hydrogen atom or a methyl group.
m and n each represent a number of 1 to 20)

(B) an ethylenically unsaturated group-containing compound other than the component (A); and (C) a photocurable resin composition containing a photopolymerization initiator.

Further, the present invention provides an optical member comprising a cured product of the above photocurable resin composition.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) used in the photocurable resin composition of the present invention is obtained by reacting (a) a hydroxyl group-containing (meth) acrylate with (b) an organic polyisocyanate, and then ( c) A urethane (meth) acrylate which is a reaction product obtained by reacting the diol represented by the formula (1).

Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2
-Hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl ( (Meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethanedi (meth) acrylate,
Pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, the following formula (3)

[0011]

[Chemical 4]

(In the formula, R ⁸ represents a hydrogen atom or a methyl group, and v represents a number of 1 to 15) and the like (meth) acrylate. Further, a compound obtained by addition reaction of a glycidyl group-containing compound such as alkyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate and (meth) acrylic acid can also be used. These hydroxyl group-containing (meth) acrylates may be used alone or in combination of two or more.

Further, as the organic polyisocyanate,
For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,
5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,
3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate,
4,4'-biphenylene diisocyanate and the like can be mentioned. In particular, 2,4-tolylene diisocyanate, 2,6
Preference is given to using tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate.

Further, the diol is represented by the above formula (1).
It is a thing. In the formula (1), R ¹Is a hydrogen atom,
R group or ethyl group, R in one molecule¹To these
May be mixed, but all R¹50 mol% of
R above¹Is something other than a hydrogen atom. R¹Is a hydrogen atom
The proportion other than is preferably 60 mol% or more,
More preferably 80 mol% or more, and particularly preferably 90 mol%.
Le% or more and all R¹Is most preferably a methyl group
Is also preferable. R¹50 mol% or more of are hydrogen atoms
When the adhesion to the substrate is reduced and a lens is formed,
Defective when the lens peels from the substrate and is used as a lens
There is a risk of conflicts. R²Is a hydrogen atom or a methyl group
And a methyl group is particularly preferred. m and n are 1
Is a number from 20 to 20, and the average value of m + n is from 4 to 30, especially 6
It is preferably -25. m and n are less than 1
And the adhesiveness with the base material deteriorates.
It becomes difficult to obtain the required refractive index. above
Examples of commercially available diols include Uniall DB
-360, DB-400, DB-800, DB-900
(These are products of NOF CORPORATION).

The urethane (meth) acrylate (A)
Is produced by first reacting a hydroxyl group-containing (meth) acrylate with an organic polyisocyanate and then reacting the diol. Other manufacturing methods such as adding all components at once and reacting organic isocyanate with diol first, and then reacting with hydroxyl group-containing (meth) acrylate may increase the viscosity and make it difficult to handle. It is not preferable.

In this case, the use ratio of the diol, the organic polyisocyanate and the hydroxyl group-containing (meth) acrylate is such that the isocyanate group contained in the organic polyisocyanate compound is 1.1 to 2 with respect to 1 equivalent of the hydroxyl group contained in the diol. It is preferable that the equivalent weight of the hydroxyl group-containing (meth) acrylate is 0.1 to 1 equivalent. Furthermore, the isocyanate group contained in the organic polyisocyanate compound is 1.3 to 2 equivalents, and the hydroxyl group of the hydroxyl group-containing (meth) acrylate is 0.3 to 1 equivalent to 1 equivalent of the hydroxyl group contained in the diol. Is particularly preferable. If it deviates from this preferable range, it becomes difficult to handle it in a liquid state because the viscosity becomes high.

In producing the above urethane (meth) acrylate, copper naphthenate, cobalt naphthenate, zinc naphthenate, di-n-butyltin dilaurate, triethylamine, triethylenediamine-2-methyltriethyleneamine and the like are usually used. The urethanization catalyst is used in an amount of 0.01 to 1% by weight based on the total amount of the reaction raw materials. The reaction temperature is usually 10 to 90 ° C., preferably 30 to 80 ° C.

The number average molecular weight of the urethane (meth) acrylate as the component (A) is preferably 500 to 20,000, more preferably 1,000 to 15,000. When the number average molecular weight of the urethane (meth) acrylate of the component (A) is less than 500, the adhesion of the cured product obtained by curing the resin composition to the base material decreases, and conversely the number average molecular weight is When it exceeds 20,000, the viscosity of the resin composition becomes high and it becomes difficult to handle.

The urethane (meth) acrylate as the component (A) is contained in the entire resin composition in an amount of preferably 5 to 70% by weight, particularly preferably 10 to 60% by weight. The lower limit of the compounding amount is preferably within the above range from the viewpoint of imparting appropriate mechanical properties such as toughness to the cured product and imparting adhesion to the substrate. Further, the upper limit of the compounding amount is preferably within the above range in order to prevent the viscosity of the composition from increasing and the workability and coating property from being deteriorated.

The component (B) used in the photocurable resin composition of the present invention is an ethylenically unsaturated group-containing compound other than the component (A) and contains a (meth) acryloyl group or a vinyl group. A compound (hereinafter, referred to as “unsaturated monomer”) can be used. As such an unsaturated monomer, a monofunctional monomer and a polyfunctional monomer can be used, and examples of the monofunctional monomer include N-
Vinyl monomers such as vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinylpyridine; isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclo Pentenyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate,
Acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl ( (Meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth)
Acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, nonyl (meth) acrylate,
Decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate , Butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol ( (Meth) acrylate, methoxy polypropylene glycol (meth) acrylate, diacetone (meth) acrylic De, isobutoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide,
Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,
7-Dimethyloctyl (meth) acrylate, N, N-
Diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, hydroxybutylbiyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether and the following formulas (4) and (5)

[0021]

[Chemical 5]

(In the formula, R ⁹ represents a hydrogen atom or a methyl group, R ¹⁰ represents an alkylene group having 2 to 8 carbon atoms, and w represents 1
~ Indicates the number of 8)

[0023]

[Chemical 6]

(Wherein R ¹¹ and R ¹³ each independently represent a hydrogen atom or a methyl group, R ¹² represents an alkylene group having 2 to 8 carbon atoms, and x represents a number of 1 to 8). Monofunctional monomer or the like represented, or

Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-
Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (Meta)
Acrylate, tris (acryloyloxy) isocyanurate, bis (hydroxymethyl) tricyclodecanedi (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyethylene oxide of bisphenol A or diol di (adduct of propylene oxide). (Meth) acrylate, hydrogenated bisphenol A ethylene oxide or propylene oxide adduct diol di (meth) acrylate, bisphenol A diglycidyl ether epoxy (meth) acrylate added with (meth) acrylate,
Examples thereof include polyfunctional monomers such as triethylene glycol divinyl ether.

Commercially available monofunctional monomers include, for example, Aronix M120, M150, M156 (above,
Toagosei Co., Ltd.), LA, IBXA, 2-MTA, H
PA, Viscoat # 150, # 155, # 158, # 1
90, # 2000, # 2100, # 2150 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), light acrylate BO-
A, EC-A, DMP-A, THF-A, HOP-A,
HOA-MPE, HOA-MPL (above, Kyoeisha Chemical Co., Ltd.), KAYARAD TC110S (Nippon Kayaku Co., Ltd.), FA-511A, 512A, 513A (above Hitachi Chemical Co., Ltd.), VP ( BASF), AC
MO, DMAA, DMAPAA (above, Kojin Co., Ltd.)
Etc.

Commercial products of polyfunctional monomers include
For example, Upimer UV SA1002, SA2007 (above, manufactured by Mitsubishi Chemical Corporation), Viscoat # 195, # 2
30, # 215, # 260, # 335HP, # 295,
# 300, # 360, # 700, GPT, 3PA (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), light acrylate 4EG-A, 9EG-A, NP-A, DCP-A, BP
-4EA, BP-4PA, TMP-A, PE-3A, P
E-4A, DPE-6A (above, Kyoeisha Chemical Co., Ltd.
Made), KAYARAD PET-30, TMPTA, R
-604, DPHA, DPCA-20, -30, -6
0, -120, HX-620, D-310, D-330
(Above, Nippon Kayaku Co., Ltd.), Aronix M20
8, M210, M215, M220, M240, M30
5, M309, M310, M315, M325, M40
0 (above, manufactured by Toagosei Co., Ltd.), Lipoxy VR-77,
VR-60, VR-90 (all manufactured by Showa Highpolymer Co., Ltd.)
Etc.

Among the components (B) of the present invention, it is preferable to use the (meth) acrylate represented by the formula (2) in order to achieve the refractive index required for the lens.

[0029]

[Chemical 7]

(In the formula, R ³ is a hydrogen atom or a methyl group,
R ⁴ is-(OCH ₂ CH ₂ ) _p -,-(OCH ₂ CH (CH ₃ )) _q- , or OCH ₂ CH (O
H) CH _2- , R ⁵ independently represents a hydrogen atom or a halogen atom other than fluorine, R ⁶ represents a hydrogen atom, a halogen atom other than fluorine, or Ph-C (CH ₃ ) _2- , Ph- represents an alkyl group having 1 to 20 carbon atoms, and p and q are each 1
Indicates the number from 10)

For example, phenoxyethyl (meth) acrylate, phenoxy-2-methylethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth).
Acrylate, 2-phenylphenoxyethyl (meth)
Acrylate, 4-phenylphenoxyethyl (meth)
Acrylate, 3- (2-phenylphenyl) -2-hydroxypropyl (meth) acrylate, (meth) acrylate of p-cumylphenol reacted with ethylene oxide, 2-bromophenoxyethyl (meth) acrylate, 2,4- Dibromophenoxyethyl (meth) acrylate, 2,4,6-tribromophenoxyethyl (meth) acrylate, phenoxy (meth) obtained by modifying plural moles of ethylene oxide and propylene oxide.
Acrylate etc. are mentioned. Among them, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, phenoxyacrylate modified with 4 mol of ethylene oxide, and (meth) acrylate of p-cumylphenol reacted with ethylene oxide are particularly preferable.

As a commercially available product, Aronix M10 is used.
1, M102, M110, M111, M113, M11
7, M5700, TO-1317 (above, manufactured by Toagosei Co., Ltd.), Viscoat # 192, # 193, # 220.
(Above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), KAYARAD
R-564, R-128H (above, Nippon Kayaku Co., Ltd.
Manufactured), NK ester AMP-10G, AMP-20G
(Above, Shin-Nakamura Chemical Co., Ltd. product), light acrylate PO-A, P-200A, NP-4EA, NP-8E
A, epoxy ester M-600A (all manufactured by Kyoeisha Chemical Co., Ltd.), PHE, CEA, PHE-2, BR-3.
1, BR-31M, BR-32 (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and the like.

The component (B) is preferably contained in the entire composition in an amount of 10 to 70% by weight, particularly preferably 20 to 60% by weight. The lower limit of the compounding amount is preferably within the above range from the viewpoint of the viscosity of the composition and the refractive index of the cured product. The upper limit of the compounding amount is preferably within the above range from the viewpoint of maintaining sufficient mechanical properties and the coatability.

The photocurable resin composition of the present invention is cured by radiation. Here, the radiation is, for example, infrared rays,
It means visible rays, ultraviolet rays and ionizing radiation such as X-rays, electron rays, α rays, β rays and γ rays. The photocuring reaction requires a photopolymerization initiator which is the component (C), and if necessary,
Further, a photosensitizer is added. The photopolymerization initiator may be any one as long as it can be decomposed by light irradiation to generate radicals to initiate polymerization, and examples thereof include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone and 2,2-dimethoxy-.
2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone,
Triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoinpropyl ether,
Benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-
2-Methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1. -One, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis-
(2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like can be mentioned.

Examples of commercially available photopolymerization initiators include I
rgacure184, 369, 651, 500, 81
9, 907, 784, 2959, CGI-1700,-
1750, -1850, CG24-61, Darocu
rl116, 1173 (above, manufactured by Ciba Specialty Chemicals Co., Ltd.), Lucirin TPO, L
R8893, LR8970 (above, manufactured by BASF), Yubecryl P36 (manufactured by UCB) and the like can be mentioned.

Examples of the photosensitizer include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-ethylaminobenzoate. Examples of the commercially available product include isoamyl dimethylaminobenzoate and the like. Examples of commercially available products include Yubecryl P102, 103, 104, 105 (above, UCB
Manufactured by the company) and the like.

The optimum amount of the photopolymerization initiator for curing the resin composition of the present invention is 0.01 in the total composition.
10 to 10% by weight, particularly 0.5 to 7% by weight is preferable. The upper limit of the compounding amount is preferably in this range from the viewpoint of curing properties of the composition, the mechanical properties and optical properties of the cured product, handling, etc., and the lower limit of the compounding amount is preferably in this range from the viewpoint of preventing a decrease in the curing rate.

When the resin composition of the present invention is cured, a thermal polymerization initiator can be used together if necessary. Examples of preferable thermal polymerization initiators include peroxides and azo compounds. Specific examples include benzoyl peroxide, t-butyl-peroxybenzoate, azobisisobutyronitrile and the like.

In addition to the above-mentioned components, the resin composition of the present invention may contain, if necessary, other curable oligomer or polymer within a range not impairing the properties of the resin composition of the present invention. The other curable oligomer or polymer has, for example, a polyurethane (meth) acrylate other than the component (A), a polyester (meth) acrylate, an epoxy (meth) acrylate, a polyamide (meth) acrylate, or a (meth) acryloyloxy group. Examples thereof include siloxane polymers, copolymers of glycidyl methacrylate and other polymerizable monomers, and reactive polymers obtained by reacting (meth) acrylic acid.

Furthermore, in addition to the above-mentioned components, if necessary, various additives such as an antioxidant, an ultraviolet absorber, a light stabilizer, a silane coupling agent, a coating surface improving agent, a thermal polymerization inhibitor, a leveling agent, If necessary, a surfactant, a colorant, a storage stabilizer, a plasticizer, a lubricant, a release agent, a solvent, a filler, an antiaging agent, a wettability improver and the like can be added. Here, as the antioxidant, for example, Irgano
x1010, 1035, 1076, 1222 (above, manufactured by Ciba Specialty Chemicals Co., Ltd.), Anti
gen P, 3C, FR, GA-80 (manufactured by Sumitomo Chemical Co., Ltd.) and the like, and examples of the ultraviolet absorber include Tinuvin P, 234, 320, 326, 32.
7, 328, 329, 213 (Ciba Specialty Chemicals Co., Ltd.), Seesorb 102,
103, 110, 501, 202, 712, 704 (above, manufactured by Cypro Kasei Co., Ltd.) and the like, and examples of the light stabilizer include Tinuvin 292, 144, 622.
LD (above, Ciba Specialty Chemicals Co., Ltd.)
Made), Sanol LS770 (made by Sankyo Co., Ltd.), Sumi
Sorb TM-061 (manufactured by Sumitomo Chemical Co., Ltd.) and the like can be mentioned. Examples of the silane coupling agent include γ-
Aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, SH606 as a commercial product
2,6030 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.), KBE903, 603, 403 (above,
Shin-Etsu Chemical Co., Ltd.) and the like, examples of the coating surface improver include silicone additives such as dimethylsiloxane polyether, and commercially available products of DC-57,
DC-190 (above, Dow Corning), SH-2
8PA, SH-29PA, SH-30PA, SH-19
0 (above, Toray Dow Corning Silicone Co., Ltd.)
Manufactured), KF351, KF352, KF353, KF35
4 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), L-700, L-
7002, L-7500, FK-024-90 (above,
Nippon Unicar Co., Ltd. etc. are mentioned.

The resin composition of the present invention can be produced by mixing the above-mentioned components by a conventional method. The viscosity of the resin composition of the present invention thus prepared is usually 200-
50,000 mPa · s / 25 ° C., preferably 500-
It is 30,000 mPa · s / 25 ° C. If the viscosity is too high, coating unevenness or waviness may occur during the production of a lens, or it may be difficult to obtain a desired lens thickness, so that the performance as a lens cannot be fully exhibited. On the contrary, if it is too low, it is difficult to control the lens thickness, and it may not be possible to form a uniform lens having a constant thickness.

The refractive index of the cured product at 25 ° C. is preferably 1.53 or more, more preferably 1.54 or more. When the refractive index is less than 1.53, when a transmissive screen is formed using the present resin composition, it may not be possible to secure sufficient front luminance.

[0043]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

Synthesis Example 1 of Urethane (meth) acrylate In a reaction vessel equipped with a stirrer, 24.66% by weight of 2,4-tolylene diisocyanate, 0.08% by weight of di-n-butyltin dilaurate, 2,6 -Di-t-butyl-p-cresol 0.02% by weight was charged and cooled to 5 to 10 ° C. While stirring, keep the temperature below 30 ° C. 2
-Hydroxypropyl acrylate 18.56% by weight was added dropwise. After the dropping was completed, the reaction was carried out at 30 ° C. for 1 hour. Next, 57.9 of the diol described in the above formula (1) (all R ¹ and R ² are methyl groups, m + n = 10; average molecular weight = 800).
1% by weight was added, and the reaction was continued at 50 to 70 ° C. for 2 hours. The reaction was terminated when the residual isocyanate content was 0.1% by weight or less. The urethane acrylate obtained by this method was designated as A-1. Synthesis Example 2 of Urethane (meth) acrylate In a reaction vessel equipped with a stirrer, 20.32% by weight of 2,4-tolylene diisocyanate, 0.08% by weight of di-n-butyltin dilaurate, 2,6-di- 0.02% by weight of t-butyl-p-cresol was charged and cooled to 5 to 10 ° C. While stirring, keep the temperature below 30 ° C. 2
17.29% by weight of -hydroxy-3-phenyloxypropyl acrylate was added dropwise. After the dropping was completed, the reaction was carried out at 30 ° C. for 1 hour. Next, 62.29% by weight of the diol described in the above formula (1) (all R ¹ and R ² are methyl groups, m + n = 10; average molecular weight = 800) was added, and the mixture was added at 50-70 ° C. to 2
The reaction continued for an hour. 0.1% by weight of residual isocyanate
The reaction was terminated when the following was reached. The urethane acrylate obtained by this method was designated as A-2.

Synthesis Example 3 of Urethane (Meth) Acrylate In a reaction vessel equipped with a stirrer, 16.72% by weight of 2,4-tolylene diisocyanate, 0.08% by weight of di-n-butyltin dilaurate, 2,6 -Di-t-butyl-p-cresol 0.02% by weight was charged and cooled to 5 to 10 ° C. While stirring, keep the temperature below 30 ° C. 2
-Hydroxyethyl acrylate 11.14 wt% was added dropwise. After the dropping was completed, the reaction was carried out at 30 ° C. for 1 hour. Next, 7 diols represented by the formula (1) (all R ¹ and R ² are methyl groups, m + n = 22; average molecular weight = 1,500)
2.04% by weight was added, and the reaction was continued at 50 to 70 ° C for 2 hours. The reaction was terminated when the residual isocyanate content was 0.1% by weight or less. The urethane acrylate obtained by this method was designated as A-3.

Synthesis Example 4 of Urethane (Meth) Acrylate In a reaction vessel equipped with a stirrer, 22.15% by weight of 2,4-tolylene diisocyanate, 0.08% by weight of di-n-butyltin dilaurate, 2,6 -Di-t-butyl-p-cresol 0.02% by weight was charged and cooled to 5 to 10 ° C. While stirring, keep the temperature below 30 ° C. 2
-Hydroxyethyl acrylate 9.85% by weight was added dropwise. After the dropping was completed, the reaction was carried out at 30 ° C. for 1 hour. next,
A diol obtained by randomly adding 6 moles of ethylene oxide and 4.5 moles of propylene oxide to 1 mole of bisphenol A (43 mole% of all R ¹ are methyl groups and the remaining R ¹
Is a hydrogen atom, R ² is a methyl group, and the average molecular weight = 800) is added at 67.90% by weight, and the reaction is continued at 50 to 70 ° C. for 2 hours. The reaction was terminated when the residual isocyanate content was 0.1% by weight or less. The urethane acrylate obtained by this method was designated as D-1.

Synthesis Example 5 of urethane (meth) acrylate In a reaction vessel equipped with a stirrer, 22.15% by weight of 2,4-tolylene diisocyanate, 0.08% by weight of di-n-butyltin dilaurate, 2,6 -Di-t-butyl-p-cresol 0.02% by weight was charged and cooled to 5 to 10 ° C. While stirring, keep the temperature below 30 ° C. 2
-Hydroxyethyl acrylate 9.85% by weight was added dropwise. After the dropping was completed, the reaction was carried out at 30 ° C. for 1 hour. next,
67.90% by weight of a diol (R ¹ is all hydrogen atoms, R ² is a methyl group, average molecular weight = 800) obtained by adding 13 mol of ethylene oxide to 1 mol of bisphenol A is added, and the reaction is continued at 50 to 70 ° C. for 2 hours. It was The reaction was terminated when the residual isocyanate content was 0.1% by weight or less. The urethane acrylate obtained by this method is used as D
-2.

Synthesis Example 6 of urethane (meth) acrylate In a reaction vessel equipped with a stirrer, 28.26% by weight of 2,4-tolylene diisocyanate, 0.08% by weight of di-n-butyltin dilaurate, 2,6 0.03% by weight of -di-t-butyl-p-cresol was charged and cooled to 5 to 10 ° C. While stirring, keep the temperature below 30 ° C. 2
-Hydroxyethyl acrylate 18.84% by weight was added dropwise. After the dropping was completed, the reaction was carried out at 30 ° C. for 1 hour. Next, 52.79% by weight of polytetramethylene glycol having an average molecular weight of 650 was added, and the reaction was continued at 50 to 70 ° C. for 2 hours. The reaction was terminated when the residual isocyanate content was 0.1% by weight or less. The urethane acrylate obtained by this method was designated as D-3.

Example 1 A reactor equipped with a stirrer was charged with 38.8% by weight of A-1 as the component (A), 5.8% by weight of phenoxyethoxyethyl acrylate as the component (B), and 4 parts of ethylene oxide. 16. Mol-modified phenoxy acrylate
5% by weight, 24.3% by weight of ethylene oxide-modified p-cumylphenol acrylate, 11.6% by weight of dipentaerythritol hexaacrylate,
3.0 weight% of 1-hydroxycyclohexyl phenyl ketone was charged as the component (C), and the liquid temperature was adjusted to 50-60.
The mixture was stirred for 1 hour while controlling at 0 ° C. to obtain a uniform liquid curable resin composition.

In each of Examples 2 to 5 and Comparative Examples 1 and 2, each component having the composition shown in Table 1 was charged into a reaction container to obtain each liquid curable resin composition.

<Evaluation Method> A test piece was prepared by the following method using the liquid curable resin composition obtained in the above example,
The refractive index, the releasability from the mold, the adhesiveness to the substrate, and the restoring property were measured as described below.

(1) Refractive index measurement: a film thickness of 2 on a glass plate
The resin composition was applied using an applicator bar so as to have a thickness of 00 μm, and 1.0 J / cm ² of ultraviolet rays was irradiated under nitrogen to prepare a test piece. According to JIS K7105, the refractive index at 25 ° C. was measured using an Abbe refractometer manufactured by Atago Co., Ltd.

(2) Mold releasability: A resin composition is applied to a mold having a Fresnel lens shape (hereinafter abbreviated as lens mold), and polymethylmethacrylate (P
The PMMA substrate was covered with a (MAA) substrate (10 cm × 10 cm) so as to prevent air bubbles from entering, and the PMMA substrate was pressed so that the resin composition layer had a constant thickness (50 μm). After that, 1.0J
After the resin layer was cured by irradiating it with ultraviolet rays of / cm 2 from the substrate side, the cured resin (hereinafter abbreviated as a lens substrate) was peeled from the mold by hand. At this time, those that could be easily peeled were judged to be “○”, those that required a little peeling force to be “△”, those that could not be peeled and a part of the resin layer adhered to the mold were judged to be “X”. ,evaluated.

(3) Adhesion to base material: The lens substrate peeled from the above lens mold was evaluated in cross-cut peeling test from the peeled surface side to the PMMA substrate in accordance with JIS K5400. At this time, "○" indicates that the grids were completely adhered without peeling off from the PMMA substrate, "△" indicates that some grids were peeled off from the PMMA substrate, and all the grids were PMMA substrates. The case where it peeled off was marked as "x". In addition, the same evaluation was performed using a methyl methacrylate / styrene copolymer (MS) substrate instead of the PMMA substrate.

(4) Restorability: A mark of a ball left on the lens surface after pressing a 0.4 mmφ metal ball indenter with a load of 30 g for 1 minute on the lens surface of the lens substrate separated from the above lens mold. Disappearance time was measured. At this time, if there is no mark on the ball, or if the mark disappears within 30 minutes, it is "○", if it disappears within 30 minutes or more and 1 hour, it is "△", even if it exceeds 1 hour. The case where the mark did not disappear was marked with "x".

[0056]

[Table 1]

In Table 1, component (B): B-1; phenoxyethyl acrylate: New Frontier PHE B-2 manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Phenoxyethoxyethyl acrylate: New Frontier manufactured by Daiichi Kogyo Seiyaku Co., Ltd. PHE-2 B-3; phenoxy acrylate modified with 4 mol of ethylene oxide: Aronix M manufactured by Toagosei Co., Ltd.
102 B-4; Acrylate of p-cumylphenol modified with 1 mol of ethylene oxide: Aronix M110 B-5 manufactured by Toagosei Co., Ltd .; Acryloylmorpholine: ACM manufactured by Kojin Co., Ltd.
OB-6; Tris (2-acryloyloxyethyl) isocyanurate: Aronix M315 B-7 manufactured by Toagosei Co., Ltd .; Dipentaerythritol hexaacrylate:
Nippon Kayaku Co., Ltd. DPHA B-8; 2-hydroxypropyl acrylate: Kyoeisha Chemical Co., Ltd. light ester HOP-A

Component (C): C-1; 2-hydroxy-cyclohexyl-benzophenone: IRGACURE 184 C-2; 2,2-dimethoxy-1,2-diphenylethane-1 manufactured by Ciba Specialty Chemicals Co., Ltd. -ON: IRGACURE 651 manufactured by Ciba Specialty Chemicals Co., Ltd.

[0059]

EFFECTS OF THE INVENTION The liquid curable resin composition of the present invention gives a cured product having a high refractive index, excellent adhesion to a substrate, and restorability, and also adheres to a mold during continuous production. Since it has good productivity, it is suitable for producing optical members such as lens sheets.

The preferred embodiments of the present invention will be described below. 1. A photocurable resin composition containing 5 to 70% by weight of the component (A), based on 100% by weight of the total resin composition. 2. A photocurable resin composition containing 10 to 70% by weight of the component (B), based on 100% by weight of the total resin composition. 3. A photocurable resin composition containing 0.01 to 10% by weight of the component (C) when the total resin composition is 100% by weight. 4. The resin composition of the present invention has a viscosity at 25 ° C. of 500 to
A photocurable resin composition having a viscosity of 30,000 mPa · s.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Satoshi Futami             2-11-21 Tsukiji, Chuo-ku, Tokyo J             Within SRL Co., Ltd. (72) Inventor Shingo Itai             2-11-21 Tsukiji, Chuo-ku, Tokyo J             Within SRL Co., Ltd. (72) Inventor Takaki Tanabe             2-11-21 Tsukiji, Chuo-ku, Tokyo J             Within SRL Co., Ltd. F-term (reference) 4J027 AC03 AC04 AC06 AC09 AC09 AG04                       AG09 AG12 AG13 AG22 AG23                       AG24 AG32 BA04 BA07 BA08                       BA10 BA11 BA13 BA14 BA15                       BA16 BA23 BA24 BA26 BA27                       BA28 BA29 CA25 CB03 CB09                       CB10 CC04 CC05 CC06 CC08                       CD04

Claims (6)

[Claims] 1. The following components (A), (B) and (C): (A) (a) a hydroxyl group-containing (meth) acrylate and (b).
After reacting the organic polyisocyanate, then (c)
Urethane (meth) acrylate obtained by reacting a diol represented by the formula (1); (In the formula, R ¹ is a hydrogen atom, a methyl group, or an ethyl group, and these may be mixed in R ¹ in one molecule, provided that 50 mol% or more of R ^{1 s} are all R ^{1 s.} Other than a hydrogen atom, R ² represents a hydrogen atom or a methyl group.
m and n each represent a number of 1 to 20) (B) an ethylenically unsaturated group-containing compound other than the component (A); (C) a photocurable resin containing a photopolymerization initiator. Composition. 2. The light according to claim 1, which contains 5 to 70% by weight of component (A), 10 to 70% by weight of component (B), and 0.01 to 10% by weight of component (C). Curable resin composition. 3. The refractive index at 25 ° C. after curing is 1.5.
The photocurable resin composition according to claim 1, which is 3 or more. 4. The component (B) has the formula (2): (In the formula, R ³ is a hydrogen atom or a methyl group, and R ⁴ is-(OCH ₂ CH
₂ ) _p -,-(OCH ₂ CH (CH ₃ )) _q- , or OCH ₂ CH (OH) CH _2-
R ⁵ each independently represents a hydrogen atom or a halogen atom except fluorine, and R ⁶ represents a hydrogen atom, a halogen atom other than fluorine, or Ph-C (CH ₃ ) _2- , Ph-, or a carbon number of 1 to 20. Is an alkyl group, and p and q each represent a number of 1 to 10).
The photocurable resin composition according to any one of 3 above. 5. The photocurable resin composition according to claim 1, which is used for forming an optical member. 6. An optical member comprising a cured product of the photocurable resin composition according to any one of claims 1 to 5.