JPH11292945A - Resin composition, resin composition for lens and its cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition that given cured products of high refractive index, excellent restorability, excoriation resistance and adhesion, and obtain its cured products. SOLUTION: This resin composition comprises (A) a urethane (meth)acrylate operated by reaction between (a) a diol, (b) an organic diisocyanate and (c) a hydroxyl group-bearing mono(meth)acrylate of the formula: (X, Y and Z are each a hydrogen atom, a bromine atom, a 1-5C alkyl group, a 1-5C alkxy group or phenyl group; W is a hydrogen atom or a methyl group), (B) a reactive monomer and (C) s photopolymerization initiator.

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 lens resin composition particularly suitable for a sheet 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 and a large number of dies because a monomer is poured into a die and polymerized, so recently a lens die and a transparent resin substrate (for example, polycarbonate, polyester, Various methods have been proposed in which an ultraviolet-curable resin liquid for forming a lens portion is interposed between acryl, styrene, or a mixed base material of these resins and rubber (for example, JP-A-61-177215). JP-A-61-2487
07, JP-A-61-248708, JP-A-63-163
330, JP-A-63-167301, JP-A-63-19
9302, 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 resilience and abrasion resistance, and close contact with the transparent resin substrate. There are many required items such as good properties, but not all of them can be satisfied at present, and it is desired to provide more satisfactory resin compositions.

[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 have completed the present invention. That is, the present invention provides (1) a diol compound (a), an organic diisocyanate (b) and a compound represented by the general formula (1):

[0005]

Embedded image

Wherein X, Y and Z are each a hydrogen atom,
It is a bromine atom, a C1-C5 alkyl group, a C1-C5 alkoxy group or a phenyl group, and W is a hydrogen atom or a methyl group. ), A urethane (meth) acrylate (A) which is a reaction product of a hydroxyl group-containing mono (meth) acrylate (c), a reactive monomer (B) and a photopolymerization initiator (C). Characteristic resin composition, (2)
(4) The resin composition according to (1), wherein the diol compound (a) is an aromatic polyester diol; (3) the resin composition according to (1), wherein the diol compound (a) is an aromatic polyether diol; Resin composition (1)
(5) The resin composition according to any one of (1) to (3),
(6) a cured product of the resin composition according to any one of (1) to (4);
The cured product according to (5), wherein the cured product has a refractive index (25 ° C.) of 1.545 or more. (7) On the substrate (5) or (6)
(8) The sheet according to (7), wherein the cured product layer is a lens layer.

In the present invention, urethane (meth) acrylate (A) is used. The acrylate (A) can be obtained by reacting the diol compound (a), the organic diisocyanate (b), and the hydroxyl-containing mono (meth) acrylate (c) represented by the general formula (I).
Typical reaction methods include, for example, a method of reacting the component (a) with the component (b), and then reacting the component (c).

The components (a) and (b) are preferably subjected to a urethanization reaction of 1.1 to 2.0 equivalents of the isocyanate group of the component (b) with respect to 1 equivalent of the hydroxyl group of the component (a). 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 from room temperature to
The temperature is 100 ° C, preferably 50 to 85 ° C. Then, in the (meth) acrylate reaction, 0.9 to 1.5 of the hydroxyl group of the component (c) is added to 1 equivalent of the isocyanate group of the compound having a terminal isocyanate group obtained in the urethane reaction. It is preferable to react the equivalent amount,
Particularly preferably, it is 1.0 to 1.1 equivalent. In this reaction, usually 50 to 2000 ppm of hydroquinone is added to the reaction mixture to prevent gelation due to radical polymerization during the reaction.
It is preferable to add a polymerization inhibitor such as hydroquinone monomethyl ether, p-methoxyphenol and p-benzoquinone. The acrylate reaction temperature is usually from room temperature to 100 ° C, preferably from 50 to 85 ° C. The reaction between the isocyanate group and the hydroxyl group proceeds without a catalyst. For example, it is preferable to use a catalyst such as triethylamine, dibutyltin dilaurate, or dibutyltin diacetate.

The component (a) includes, for example, an aliphatic diol compound (a-1) and an aromatic diol compound (a-
2), aliphatic polyether diol (a-3), aromatic polyether diol (a-4), aliphatic polyester diol (a-5), aromatic polyester diol (a
-6) and the like. Particularly preferred diol compounds (a) include, for example, aromatic polyether diol (a-4) and aromatic polyester diol (a-
And diol compounds having a high refractive index such as 6).

Examples of the aliphatic diol compound (a-1) include ethylene glycol, propylene glycol, 1,3-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-
Hexanediol, 1,9-nonanediol, 2-ethyl-2-butyl-1,3-propanediol and the like can be mentioned. As the aromatic diol compound (a-2), for example, 1,4-dimethylol Examples of the aliphatic polyether diol (a-3) include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

As the aromatic polyether diol (a-4), for example, bisphenol A diethoxydiol,
Bisphenol A tetraethoxydiol, bisphenol A polyethoxydiol, tetrabuberom bisphenol A polyethoxydiol, bisphenol A dipropoxydiol, bisphenol A tetrapropoxydiol, bisphenol A polypropoxydiol,
Examples thereof include tetrabromobisphenol A polypropoxydiol, 1,4-dimethylolbenzenediethoxydiol, 1,4-dimethylolbenzenepolyethoxydiol, and 1,4-dimethylolbenzenepropoxydiol.

The aliphatic polyester diol (a-5) includes, for example, the aliphatic diol compound (a-1)
And a reaction product thereof with an aliphatic dibasic acid such as succinic acid, maleic acid and adipic acid, or an anhydride thereof.

The aromatic polyester diol (a-6) includes, for example, the aromatic diol compound (a-2)
And a reaction product (a) of the above with an aliphatic dibasic acid or an anhydride thereof
-6-1), a reaction product (a-6-2) of the aliphatic diol compound (a-1) with an aromatic dibasic acid such as phthalic acid, isophthalic acid, and terephthalic acid, or an anhydride thereof; And a reaction product of an aromatic diol compound (a-2) and the aromatic dibasic acid or anhydride thereof (a-6-3).
And the like.

The organic diisocyanate (b) includes, for example, tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate and the like.

In the above general formula (1), X, Y and Z
Is a hydrogen atom, a bromine atom, a C1-C5 alkyl group, a C1-C5 alkoxy group or a phenyl group,
R4 is a hydrogen atom or a methyl group. Examples of the C1-C5 alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and the like.
Examples of the C1-C5 alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group,
and an n-pentoxy group. As a preferable combination of X, Y and Z, for example, X is an alkyl group or an alkoxy group at the 4-position, Y and Z are hydrogen atoms, and X is 2
A phenyl group, Y and Z are hydrogen atoms, X is a bromine atom at position 3, Y is a bromine atom at position 5, and Z is a hydrogen atom;
X is a bromine atom at position 2, Y is a bromine atom at position 4, and Z is
Is a bromine atom at the 6-position.

As the hydroxyl group-containing mono (meth) acrylate (c) represented by the general formula (1), for example, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 2-hydroxy-3- (2,4 , 6-Tribromophenyloxy) propyl (meth) acrylate, 2-
Hydroxy-3- (p-methylphenyloxy) propyl (meth) acrylate, 2-hydroxy-3- (p-
Methoxyphenyloxy) propyl (meth) acrylate, 2-hydroxy-3- (3,5-dibromophenyloxy) propyl (meth) acrylate, 2-hydroxy-3- (o-phenylphenyloxy) propyl (meth) acrylate And the like.

As the reactive monomer (B) used in the present invention, 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 (degree of polymerization: n = 2 to 15 on average) ethoxydi (meth) acrylate, acryloylmorpholine, tribromophenyloxyethyl (meth) acrylate, tribromobenzyl (meth) Acrylate, styrene, α-methylstyrene and the like can be mentioned.

Preferred reactive monomers include, for example, acrylates having a high refractive index such as phenyloxyethyl acrylate, o-phenylphenyloxyethyl acrylate, and tribromophenyloxyethyl acrylate; polyethylene glycol diacrylate; Acrylates having improved adhesion such as ethoxydiacrylate and 1,6-hexanediol diacrylate can be given.

As the photopolymerization initiator (C), for example, 1-
Hydroxycyclohexyl phenyl ketone, phenyl-
2-hydroxy-2-propyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4
Examples thereof include 4-trimethylpentylphosphine oxide and methylbenzoyl formate.

The proportions of the components (A), (B) and (C) in the resin composition of the present invention are as follows: when the total amount of the components (A) to (C) is 100 parts by weight, Is 10-6
It is preferably 0% by weight, particularly preferably 20 to 50% by weight. The component (B) is preferably from 30 to 85% by weight, particularly preferably from 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.

The resin composition of the present invention comprises, in addition to the above components, a urethane (meth) acrylate other than the component (A),
Bisphenol A type epoxy (meth) acrylate can also be used. Furthermore, defoaming agents, leveling agents, antioxidants, plasticizers, release agents, polymerization inhibitors, light stabilizers, non-reactive polymer resins (for example, polyester elastomers,
Polyurethane elastomer, acrylic polymer, etc.) can also be used in combination.

The resin composition of the present invention comprises the above (A)
The components (B) and (C) may be added with other components as necessary, and then contacted and mixed to obtain a liquid composition. The viscosity of the liquid composition is 500 to 10000c
Ps (25 ° C.) is preferable.

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 sheet of the present invention has a cured resin layer of the above-mentioned resin composition of the present invention provided on a transparent resin substrate.
The thickness of the cured product layer is preferably about 10 to 300 μm.
Examples of the material of the transparent resin plate include a polycarbonate resin, a polystyrene resin, a polyester resin, a polyacryl resin, and a mixed resin thereof.

In the sheet of the present invention, when the cured product layer is formed into a lens shape, a sheet lens is obtained. The method for producing this sheet-shaped lens is, for example, to apply a resin composition to a mold having a Fresnel lens shape, provide a layer of the resin composition, adhere a transparent resin substrate on the layer, and then apply After the resin composition is cured by irradiating ultraviolet rays from the transparent resin substrate side with a high-pressure mercury lamp or the like, the mold is released from the mold. In this way, the ordinary refractive index (25
C.) of 1.545 or more to obtain a Fresnel lens.

[0026]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but it is needless to say that the present invention is not limited to the following Examples. Synthesis Example 1 (Synthesis example of urethane (meth) acrylate (A)) Polyester diol of 3-methyl-1,5-pentanediol and isophthalic acid (OH value (mgKOH / g) 5
6, 2000 g of average molecular weight 2000 g and 348 g of tolylene diisocyanate are charged and reacted at 85 ° C. for about 15 hours until the concentration of isocyanate groups becomes about 3.58%, and then 468 g of 2-hydroxy-3-phenyloxypropyl acrylate And methoquinone (1.4 g) were charged at 85 ° C. for about 10 hours, and the isocyanate group concentration was 0.3
% Of the urethane acrylate (A-
1) was obtained. The refractive index of the obtained product (25 ° C.)
1.536.

Synthesis Example 2 Bisphenol A polypropoxy (degree of polymerization: n = 10 on average) Diol (average molecular weight 808) 1616
g, and 522 g of tolylene diisocyanate.
C. for about 15 hours at a concentration of about 3.93
%, And then 468.3 g of 2-hydroxy-3-phenyloxypropyl acrylate and 1.3 g of methoquinone were charged and reacted at 85 ° C. for about 10 hours until the concentration of isocyanate groups became 0.3% or less. And urethane acrylate (A-2). The obtained product had a refractive index (25 ° C.) of 1.556.

Synthesis Example 3 (Synthesis Example of Urethane Acrylate for Comparative Example) Bisphenol A polypropoxy (degree of polymerization: n = 10 on average) Diol (average molecular weight 80 g) 1616
g, and 522 g of tolylene diisocyanate.
C. for about 15 hours at a concentration of about 3.93
%, Then poly (degree of polymerization: n = 6 on average) ethylene glycol monoacrylate 70
5.6 g and 0.8 g of methoquinone were charged at 85 ° C. to about 10 g.
The reaction was continued for a period of time until the concentration of the isocyanate group became 0.3% or less to obtain urethane acrylate. The obtained product had a refractive index (25 ° C.) of 1.533.

Examples 1 and 2 and Comparative Example 1 A resin composition having the composition shown in Table 1 (the numerical values indicate parts by weight) was applied on a Fresnel lens mold, and a transparent methacrylic resin was applied thereon. The system substrate was adhered, cured by irradiating ultraviolet rays, released from the mold to obtain a Fresnel lens, and various evaluations were made. The evaluation was performed by the following method.

(1) Releasability: difficulty in releasing the cured resin from the mold.・ ・ ・: Good mold release from the mold △: Slightly difficult to release ×: Difficult to release or mold residue (2) Restorability: Gold of cured resin layer The time required for the trace of the metal round bar having a diameter of 10 mm to completely disappear on the surface released from the mold 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 m in width) is provided on the surface of the cured resin layer which has been released from the mold.
(m, length: 100 mm, thickness: 2.5 mm) vertically and strongly, and reciprocated 10 times at an interval of about 100 mm, at a speed of about 1 second, and observed scratches on the surface.・: 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: The resin composition was coated on a transparent methacrylic resin substrate to a thickness of 200 μm, a width of 20 mm and a length of 15
The test piece was applied to a thickness of 0 mm and then irradiated with a high pressure mercury lamp (80 w / cm, ozoneless) at 500 mj / cm 2 to prepare a cured test piece, and the peel strength was measured.
(Measurement method of peel strength: Peel strength at 90 ° C. of the cured resin film on the methacrylic resin-based substrate was measured by a tensile tester (peel speed: 100 mm / min). ··· Peel strength 1-2 kg / cm △ ··· Peel strength 0.5-1 kg / cm × ··· Peel strength 0.5 kg / cm or less (5) Refractive index: Refractive index of cured resin (25 ° C.).

[0033]

Table 1 Example 1 Comparative Example 12 1 Urethane acrylate (A-1) obtained in Synthesis Example 1 35 Urethane acrylate (A-2) obtained in Synthesis Example 2 36.5 Urethane acrylate obtained in Synthesis Example 3 36.5 Phenoxyethyl acrylate 20.6 30.0 30.0 o-phenylphenyloxyethyl acrylate 10.0 7.0 7.0 1,6-hexanediol diacrylate 3.5 6.5 6.5 Bisphenol A poly (n = 10) ethoxydiacrylate 31 20 20 1-hydroxycyclophenyl ketone 33 33離 Releasability ○ ○ ○ Restorability ◎ ◎ ◎ Scratch resistance ◎ ◎ ○ Adhesion ○ ○ × Refractive index 1.550 1.552 1.541

From the evaluation results shown in Table 1, 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.

[0035]

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] 1. A diol compound (a), an organic diisocyanate (b) and a compound represented by the general formula (1): ## STR1 ## (Wherein, X, Y and Z are each a hydrogen atom, a bromine atom,
It is a C1-C5 alkyl group, a C1-C5 alkoxy group or a phenyl group, and W is a hydrogen atom or a methyl group. ) Containing urethane (meth) acrylate (A), a reactive monomer (B), and a photopolymerization initiator (C), which are reactants of a hydroxyl group-containing mono (meth) acrylate (c) represented by Characteristic resin composition. 2. The resin composition according to claim 1, wherein the diol compound (a) is an aromatic polyester diol. 3. The resin composition according to claim 1, wherein the diol compound (a) is an aromatic polyether diol. 4. The resin composition according to claim 1, which is a resin composition for lenses. 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. A sheet having a cured product layer according to claim 5 on a substrate. 8. The sheet according to claim 7, wherein the cured layer is a lens layer.