JPH11322868A - Resin composition, resin composition for lens and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition suitable as a resin composition for lens whose cured products have a high refractive index and has excellent memory, marring resistance and adhesiveness. SOLUTION: This composition comprises a urethane (meth)acrylate (A), i.e. a reaction product of a diol compound having a molecular weight of >=3,000 (a), a diol compound having a molecular weight of <=500 (b), an organic diisocyanate (c) and a hydroxyl-containing mono(meth)acrylate (d), a reactive monomer (B) and a photopolymerization initiator (C).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an ultraviolet-curable resin composition. More specifically, Fresnel lens sheet for TFT, Fresnel lens for projection TV,
The present invention relates to a resin composition particularly suitable for a sheet-like lens such as a lenticular lens and a cured product thereof.

[0002]

2. Description of the Related Art Heretofore, this type of lens has been formed by a method such as a pressing method or a casting method. The former press method has poor productivity because it is manufactured by a cycle of heating, pressing and cooling. Also, the latter casting method requires a long production time because a monomer is poured into a mold and is polymerized, and requires a large number of molds. Recently, a lens mold and a transparent resin base material (for example, polycarbonate resin, polyester resin , An acrylic resin, a styrene resin, or a mixed base material of these resins and rubber, etc.) to interpose an ultraviolet-curable resin liquid for forming a lens portion. 61-177215, JP-A-61-1987.
-248707, JP-A-61-248708, JP-A-6-248708
3-163330, JP-A-63-167301, JP-A-63-199302, JP-A-64-6935, etc.).

[0003]

The performance required for a Fresnel lens for a projection television is that it has a high refractive index, excellent restorability, and excellent scratch resistance, and also has good adhesion to the transparent resin substrate. However, there are many requirements such as good, but none of them satisfy all of them, and it is desired to provide a more satisfactory resin composition.

[0004]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have made intensive studies and found that curing by ultraviolet rays is fast, excellent in adhesion to a resin substrate, and the cured product is removed. The present inventors have found a resin composition having excellent moldability, resilience, and scratch resistance and a high refractive index, and completed the present invention. That is, the present invention relates to (1) a reaction product of a diol compound (a) having a molecular weight of 3000 or more, a diol compound (b) having a molecular weight of 500 or less, an organic diisocyanate (c), and a hydroxyl group-containing mono (meth) acrylate (d). A resin composition comprising a certain urethane (meth) acrylate (A), a reactive monomer (B) and a photopolymerization initiator (C);
(2) The resin composition according to (1), wherein the diol compound (a) is an aliphatic polyester diol, (3) the urethane (meth) acrylate (A) according to (1), a bisphenol-type epoxy (meth) acrylate (D ), A resin composition comprising a reactive monomer (B) and a photopolymerization initiator (C), (4) any one of (1) to (3) for a lens. (5) (1)
(5) a cured product of the resin composition according to any one of (4) to (4), (6) a cured product having a refractive index (25 ° C.) of 1.545 or more, and (7) a lens. ) Or the cured product according to (6), and (7) the cured product according to (7), wherein the lens is a sheet-like lens.

In the present invention, urethane (meth) acrylate (A) is used. Urethane (meth) acrylate (A) is a diol compound (a) having a molecular weight of 3000 or more.
And a diol compound (b) having a molecular weight of 500 or less, an organic diisocyanate (c), and a hydroxyl group-containing mono (meth) acrylate (d). As a typical reaction method, the components (a) and (b) are reacted with the component (c) (urethane-forming reaction), and then the component (d) is reacted ((meth) acrylate-forming reaction). I can give you a way.

[0006] In the urethanization reaction of the components (a) and (b) with the component (c), it is necessary to use a mixture of the components (a) and (b) to obtain a releasability, resilience, It is preferable in that a urethane (meth) acrylate (A) having excellent scratch resistance and adhesion can be obtained. The mixing ratio (molar ratio) of the component (a) and the component (b) is as follows when (a) + (b) is 1 mole.
(B) / (a) = 80/20 to 20/80 is preferred,
Particularly preferably, (b) / (a) = 70/30 to 30/7
0. The amount of the component (c) used is such that 1.1 to 2.0 equivalents of the isocyanate group of the component (c) are reacted with 1 equivalent of the hydroxyl group of the mixture of the component (a) and the component (b). preferable. Particularly preferably, it is 1.5 to 2.0 equivalents. This urethanation reaction can be performed by a procedure known to those skilled in the art. This urethanization reaction temperature is
Usually, it is normal temperature to 100 ° C, preferably 50 to 85 ° C.

Next, in the (meth) acrylated reaction in which the component (d) is reacted, one equivalent of the isocyanate group of the compound having a terminal isocyanate group obtained in the urethane-forming reaction is referred to as a hydroxyl group of the component (d). 0.9 ~
Preferably, 1.5 equivalents are reacted, particularly preferably 1.0 to 1.1 equivalents. For this reaction, usually 5 parts of the reaction mixture is added to prevent gelation due to radical polymerization during the reaction.
It is preferable to add 0 to 2000 ppm of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, and p-benzoquinone. The acrylate reaction temperature is usually from room temperature to
The temperature is 100 ° C, preferably 50 to 85 ° C. Although the reaction between the isocyanate group and the hydroxyl group proceeds without a catalyst, it is preferable to use a conventional catalyst such as triethylamine, dibletin dilaurate, dibutyltin diacetate, or the like.

The urethane (meth) acrylate (A)
Examples of the diol compound (a) having a molecular weight of 4,000 or more used for the production of (a) include aliphatic polyether diols (a-1) such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and polybutylene glycol, and bisphenol A. Aromatic polyether diols (a) such as polyethoxydiol, bisphenol A polypropoxydiol, tetrabromobisphenol A polypropoxydiol, polyethoxy compound of 1,4-dimethanolbenzene, and polypropoxy compound of 1,4-dimethanol-benzene -2),
Ethylene glycol, propylene glycol, 1,3-butanediol, nerpentyl glycol, 3-methyl-
Aliphatic diols such as 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 2-ethyl-2-butyl-1,3-propanediol and succinic acid, maleic acid, adipic acid, etc. Aliphatic polyester diol (a-3) which is a reaction product of an aliphatic dibasic acid or an anhydride thereof, and an aromatic dibasic acid such as phthalic acid, isophthalic acid, and terephthalic acid, or an anhydride thereof; Or an aromatic polyester diol (a-) which is a reaction product of an aromatic diol such as 1,4-dimethylolbenzene or the like with the aliphatic dibasic acid or anhydride thereof.
4) and the like.

Particularly preferred diol compounds (a) include aliphatic polyester diols (a-3). The aliphatic polyester diol (a-3) has a characteristic that even if it has a large molecular weight, it has a relatively low viscosity, and it is easy to obtain performance such as adhesion to a substrate. Molecular weight 300
0 or more is preferable, and particularly preferably 5000 to 1000.
0.

The urethane (meth) acrylate (A)
Examples of the diol compound (b) having a molecular weight of 500 or less used for the production of ethylene glycol, propylene glycol, 1,3-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, Aliphatic diols (b-1) such as 6-hexanediol, 1,9-nonanediol, 2-ethyl-2-butyl-1,3-propanediol and cyclohexane-1,4-dimethanol; Aromatic diols (b-2) such as dimethanolbenzene, aliphatic polyether diols (b-3) such as polypropylene glycol, polyethylene glycol, polybutylene glycol and polytetramethylene glycol, bisphenol A polyethoxy diol, bisphenol A poly Propoxydiol, tetrabromobi Aromatic polyether diol (b-4) such as phenol A polypropoxy diol, and the above-mentioned aliphatic diol (b-1) and an aliphatic dibasic acid such as succinic acid, maleic acid, adipic acid or anhydride thereof Aliphatic polyester diol (b-5) as a reactant,
A reaction product of the aromatic diol (b-2) and the aliphatic dibasic acid or anhydride thereof, or the aliphatic diol (b-1) and an aromatic dibasic acid such as phthalic acid, isophthalic acid, and terephthalic acid Or an aromatic polyester diol (b-6) which is a reaction product with an anhydride thereof.

The urethane (meth) acrylate (A)
Organic diisocyanate (c) used for producing
Examples thereof include tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate.

The urethane (meth) acrylate (A)
Examples of the hydroxyl group-containing mono (meth) acrylate (d) used for the production of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, poly ( N = 2 to 10 as average value) Ethylene glycol mono (meth) acrylate, poly (n = 2 to 10 as average value) propylene glycol mono (meth)
Acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 2-hydroxy-3-
(O-phenylphenylooxy) propyl (meth) acrylate and the like.

In the present invention, the reactive monomer (B) is used. As the reactive monomer (B), for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethyloxyethyl (meth) acrylate, 2-hydroxy- 3-phenyloxypropyl (meth) acrylate, o-phenylphenyloxyethyl (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A Poly (n = 2 to 15 on average) ethoxydi (meth) acrylate, acryloylmorpholine, tribromophenyloxyethyl (meth) acrylate, tribromobenzyl (meth) acrylate, styrene , It may be mentioned α- methyl styrene. Preferred reactive monomers include acrylate monomers, for example, acrylates having a high refractive index, particularly having a phenyl ether group such as phenyloxyethyl acrylate, o-phenylphenyloxyethyl acrylate, and tribromophenyloxyethyl acrylate. Monoacrylate monomers (B1) and acrylates that improve adhesion, especially diacrylate monomers (B2) of dihydric alcohols such as polyethylene glycol diacrylate, bisphenol A polyethoxy diacrylate, and 1,6-hexanediol diacrylate. Can be mentioned.

In the present invention, a photopolymerization initiator (C) is used. Examples of the photopolymerization initiator (C) include 1-hydroxycyclohexylphenyl ketone, phenyl-2-hydroxy-2-propyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and bis (2,6-dimethoxybenzoyl) ) -2,4,4-trimethylpentylphosphine oxide, methylbenzoyl formate and the like.

In the present invention, bisphenol type epoxy (meth) acrylate (D) can be used.
When this bisphenol-type epoxy (meth) acrylate (D) is used, a cured product having a higher refractive index can be obtained. Examples of the bisphenol type epoxy (meth) acrylate (D) include, for example, bisphenol A type epoxy resin (for example, manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 1001, 1002, 1004, 1010, etc., having an average molecular weight of 900 to 6000, Epoxy equivalent 400
~ 5000. ), Bisphenol F type epoxy resin (for example, YDF-200 manufactured by Toto Kasei Co., Ltd.)
1, 2004, 170, etc., epoxy equivalent 160
There are ~ 1000. ) Or an epoxy (meth) acrylate obtained by reacting an epoxy resin such as diglycidyl ether of bisphenol A polyalkylene glycol with (meth) acrylic acid. Particularly preferred examples include bisphenol A type epoxy acrylate.

In the resin composition of the present invention, (A), (B),
The proportions of the components (C) and (D) used are (A) to
When the total amount of the component (D) is 100 parts by weight, the content of the component (A) is preferably 10 to 60% by weight, and particularly preferably 20 to 60% by weight.
５０50% by weight. (B) The component is 30 to 85% by weight.
And particularly preferably 40 to 75% by weight.
The component (C) is preferably from 0.5 to 15% by weight, particularly preferably from 1 to 5% by weight. (D) The component is 0-55.
% By weight, particularly preferably 5 to 40% by weight.

In the resin composition of the present invention, urethane (meth) acrylate other than the component (A) may be used in addition to the above components. Furthermore, antifoaming agents, leveling agents, antioxidants, plasticizers, release agents, polymerization inhibitors, light stabilizers, non-reactive polymer resins (eg, polyester elastomers, polyurethane elastomers, acrylic polymers, etc.) are also used in combination. can do.

The resin composition of the present invention comprises the above (A)
The components (B) and (C) are contacted and mixed, and if necessary, urethane (meth) other than the components (D) and (A)
Add acrylate, defoamer, leveling agent, antioxidant, plasticizer, release agent, polymerization inhibitor, light stabilizer, non-reactive polymer resin, etc. As a transparent liquid composition. The viscosity of the liquid composition is 500 to 10000 cps
(25 ° C.) is preferred.

The cured product of the present invention can be obtained by irradiating the above-mentioned resin composition of the present invention with ultraviolet rays according to a conventional method. This cured product has good transparency and a high refractive index. The refractive index is preferably, for example, 1.545 or more at 25 ° C.

The lens of the present invention is obtained by applying the resin composition of the present invention to a mold, for example, a mold having a Fresnel lens shape, providing a transparent layer of the resin composition, and forming a transparent resin substrate on the transparent layer. Then, in this state, the resin composition is cured by irradiating ultraviolet rays from the resin substrate side with a high-pressure mercury lamp or the like, and then released from the mold. In this way, a Fresnel lens having a normal refractive index (25 ° C.) of 1.545 or more is obtained. The thickness of the cured product layer of the resin composition of the present invention is preferably about 10 to 300 μm. As the material of the transparent resin substrate, for example, polycarbonate resin,
Polystyrene resin, polyester resin, polyacrylic resin, or a mixed resin thereof can be used.

[0021]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but it goes without saying that the present invention is not limited to the following Examples. (Synthesis example of urethane (meth) acrylate (A)) Synthesis example 1 1870 g of polyester diol (3-methyl-1,5-pentanediol adipate, average molecular weight 5500)
(0.34 mol), neopentyl glycol 174.7
g (1.68 mol), tolylene diisocyanate 522
g, and reacted at 85 ° C. for about 15 hours until the concentration of isocyanate groups became about 3.27%. Then, 243.6 g of 2-hydroxyethyl acrylate and 1.4 g of methoquinone were charged and the reaction was carried out at 85 ° C. for about 10 hours. The reaction was performed until the concentration of the isocyanate group became 0.3% or less, to obtain urethane acrylate (A-1). The obtained product had a refractive index (25 ° C.) of 1.521.

Synthesis Example 2 1100 g of polyester diol (3-methyl-1,5-pentanediol adipate, average molecular weight 5500)
(0.2 mol), bisphenol A poly (average n = 4) propoxydiol (average molecular weight 460) 82
8 g (1.8 mol), tolylene diisocyanate 522
g, and reacted at 85 ° C. for about 15 hours until the isocyanate group concentration became about 3.43%. Then, 243.6 g of 2-hydroxyethyl acrylate and 1.3 g of methquinone were charged, and the reaction was carried out at 85 ° C. for about 10 hours. The reaction was continued until the concentration of the isocyanate group became 0.3% or less to obtain urethane acrylate (A-2). The obtained product had a refractive index (25 ° C.) of 1.531.

(Synthesis example of urethane acrylate for comparative example) Synthesis example 3 Polyester diol (3-methyl-1,5-pentanediol adipate, average molecular weight 5500) 5500
g, 348 g of tolylene diisocyanate, 85
C. for about 15 hours at a concentration of about 1.44 isocyanate groups.
%, And then 243.6 g of 2-hydroxyethyl acrylate and 3.0 g of methoquinone were charged.
85 ° C. for about 10 hours, when the concentration of the isocyanate group is 0.3
% To obtain urethane acrylate.
The refractive index (25 ° C.) of the obtained product was 1.475.

Synthesis Example 4 920 g of bisphenol A tetrapropoxydiol (average molecular weight: 460), tolylene diisocyanate 522
g, and reacted at 85 ° C. for about 15 hours until the concentration of isocyanate groups became about 5.8%, and then 243.6 g of 2-hydroxyethyl acrylate and 0.1 g of methoquinone were added.
8 g was charged and reacted at 85 ° C. for about 10 hours until the concentration of isocyanate groups became 0.3% or less to obtain urethane acrylate. The refractive index (25 ° C.) of the obtained product was 1.563.

Examples 1 and 2 Comparative Examples 1 and 2 Each component was mixed and dissolved according to the formulation shown in Table 1 (the numerical values indicate parts by weight) to obtain a resin composition (transparent liquid) of the present invention. . This resin composition is applied on a Fresnel lens mold, a transparent methacrylic resin-based substrate is adhered thereon, cured by irradiating ultraviolet rays, and released from the mold to obtain a Fresnel lens. Was done. Various evaluations were performed by the following methods.

(1) Releasability: difficulty in releasing the cured resin from the mold.・ ・ ・: Good releasability from the mold △: Slightly difficult to release ×: Difficult to release or mold remaining. (2) Restorability: A metal round bar having a diameter of 10 mm was pressed against the surface of the cured resin layer released from the mold, and the time until the trace completely disappeared was measured.・: Disappeared instantaneously.・ ・ ・: Disappeared within 60 seconds. Δ: Disappeared in 1 to 60 minutes. ×: It took 60 minutes or more to disappear.

(3) Scratch resistance: A methacrylic resin-based substrate (100 mm wide,
(100 mm in length, 2.5 mm in thickness) was pressed firmly vertically and reciprocated 10 times at an interval of about 100 mm at a speed of 1 reciprocation of about 1 second, and then a scratch on the surface was observed.・: No scratches are observed.・ ・ ・: Several streak-like scratches are observed. Δ: A band-like scratch is partially observed. ×: Band-like scratches are observed over the entire surface. (4) Adhesion: A resin composition is applied on a transparent methacrylic resin-based substrate to a thickness of 200 μm, a width of 20 mm, and a length of 150 mm, and then a high-pressure mercury lamp (80 w / cm, ozoneless).
Then, a test piece was prepared by irradiating with 500 mj / cm 2 at a temperature of 100 ° C., and the peel strength at 90 ° C. of the cured resin film on the methacrylic resin-based substrate was measured by a tensile tester (peeling speed: 100 mm / min). ◎ ・ ・ ・ ・ 2kg / cm or more ○ ・ ・ ・ ・ ・ ・ 1 to 2kg / cm △ ・ ・ ・ ・ 0.5 to 1kg / cm × ・ ・ ・ ・ 0.5kg / cm or less (5) Refractive index: cured The refractive index (25 ° C.) of the resin was measured.

[0028]

Table 1 Example Comparative Example 1 2 3 12 1 Urethane acrylate (A-1) obtained in Synthesis Example 1 40 20 Urethane acrylate (A-2) obtained in Synthesis Example 2 35 Obtained in Synthesis Example 3 Urethane acrylate 35 Urethane acrylate obtained in Synthesis Example 4 35 Phenoxyethyl acrylate 15 18 11.7 15 30 o-phenylphenyl poly (average value n = 1.5) Ethoxy acrylate 15 o-phenylphenyloxyethyl acrylate 15 15 Bisphenol A poly (average Ethoxy acrylate 25 26 20 30 30 polyethylene glycol diacrylate 10 1,6-hexanediol diacrylate 5 65 5 phenyl-2-hydroxy-2-propyl ketone 33 33 33 Bisphenol A type epoxy acrylate Rate * 1 33.3 releasability ○ ○ ○ ○ × resilient ◎ ◎ ◎ △ × scratch resistance ◎ ◎ ◎ △ × adhesion ◎ ◎ ◎ ◎ △ refractive index 1.550 1.552 1.555 1.535 1.555

Note) * 1 Bisphenol A type epoxy acrylate: Acrylic acid is equivalent to 1 equivalent of epoxy group of bisphenol A type epoxy resin (Epicoat 1004, manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent 925, average molecular weight 1850). .98 mol, diluted with 40% by weight of phenoxyethyl acrylate.

From the evaluation results shown in Table 1, it can be seen that the cured product of the resin composition of the present invention has a high refractive index and is excellent in restorability, abrasion resistance, adhesion, mold release, and the like. Also, a comparison between Example 3 and Examples 1 and 2 reveals that the use of bisphenol-type epoxy acrylate (D) further increases the refractive index.

[0031]

The cured product of the resin composition of the present invention has a high refractive index and is excellent in resilience, scratch resistance, adhesion, and releasability.

Claims (8)

[Claims] An urethane (meth) which is a reaction product of a diol compound (a) having a molecular weight of 3000 or more, a diol compound (b) having a molecular weight of 500 or less, an organic diisocyanate (c), and a hydroxyl group-containing mono (meth) acrylate (d). A) A resin composition comprising an acrylate (A), a reactive monomer (B) and a photopolymerization initiator (C). 2. The resin composition according to claim 1, wherein the diol compound (a) is an aliphatic polyester diol. 3. It contains the urethane (meth) acrylate (A) according to claim 1, a bisphenol type epoxy (meth) acrylate (D), a reactive monomer (B) and a photopolymerization initiator (C). The resin composition characterized by the above-mentioned. 4. The resin composition according to claim 1, which is used for a lens. 5. A cured product of the resin composition according to claim 1. 6. The cured product according to claim 5, having a refractive index (25 ° C.) of 1.545 or more. 7. The cured product according to claim 5, which is a lens. 8. The cured product according to claim 7, wherein the lens is a sheet lens.