JP2000063447A - Resin composition and its cured substance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition which undergoes fast curing on exposure to an ultraviolet ray, is excellent in adherence to a resin substrate, memory properties and resistance to marring, and exhibits a high refractive index by compounding a urethane acrylate, specific imido (meth)acrylate, a reactive monomer other than aforementioned monomers and a photopolymerization initiator. SOLUTION: A urethane (meth)acrylate is obtained by reacting 1 equivalent of a hydroxyl group of a diol compound with 1.1-2.0 equivalents of an isocyanate group of an organic diisocyanate to prepare a compound having an isocyanate group at an end, and reacting 1 equivalent of the isocyanate group of the resultant compound with 0.9-1.5 equivalents of a hydroxyl group of mono (meth) acrylate containing a hydroxyl group. A resin composition is obtained by mixing 10-60 wt.% of the urethane (meth)acrylate, 5-50 wt.% of an imido (meth)acrylate represented by the formula (wherein R is H or methyl), 25-80 wt.% of a reactive monomer other than aforementioned monomers, 0-15 wt.% of a photopolymeriation initiator and 0-40 wt.% of a bisphenol type epoxy (meth) acrylate.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition. More specifically, the present invention relates to a resin composition particularly suitable for a sheet-shaped lens such as a Fresnel lens sheet for TFT, a Fresnel lens for projection television, and a lenticular lens, and a cured product thereof.

Conventionally, this type of lens has been molded by a method such as a pressing method or a casting method. The former pressing method had poor productivity because it was manufactured by a cycle of heating, pressurizing and cooling. Further, the latter casting method requires a long manufacturing time because a monomer is poured into a mold to polymerize, and a large number of molds are required. Therefore, recently, a lens-type transparent resin substrate (for example, polycarbonate resin, polyester resin) is used. , An acrylic resin, a styrene resin, or a mixed base material of these resins and rubber, and the like, various methods of interposing an ultraviolet-curable resin liquid for forming a lens portion have been proposed (see, for example, Japanese Patent Application Laid-Open Publication No. Sho. 61-177215, JP-A-61-
248707, JP 61-248708, JP 63
-163330, JP-A-63-167301, JP-A-6-
3-199302, 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 scratch resistance, and that it adheres well to a transparent resin substrate. There are many requirements such as good things, but at present it is not possible to satisfy all requirements, and it is desired to provide a more satisfactory resin composition.

[0004]

In order to solve the above problems, as a result of intensive studies by the present inventors, the inventors have found that curing by ultraviolet rays is fast, the adhesiveness to a resin substrate is excellent, and the cured product is free from depolymerization. The present invention has been completed by finding a resin composition having excellent moldability, restorability, and scratch resistance and having a high refractive index. That is, the present invention includes (1) urethane (meth) acrylate (A) and general formula (1)

[0005]

[Chemical 2]

(In the formula, R is a hydrogen atom or a methyl group.) An imide (meth) acrylate (B),
(2) Bisphenol type epoxy (meth) acrylate (E), a resin composition containing a reactive monomer (C) other than the component (B) and a photopolymerization initiator (D) as an optional component. Containing the resin composition according to (1),
(3) A resin composition according to (1) or (2) for a lens, (4) a cured product of the resin composition according to any one of (1) to (3), and (5) a refractive index ( 25 ° C) is 1.5
The cured product according to (4), which is 45 or more, the cured product according to (4) or (5), which is a lens (6), and the cured product according to (6), wherein the lens is a sheet lens.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, urethane (meth) acrylate (A) is used. Examples of the urethane (meth) acrylate (A) include a diol compound (a), an organic diisocyanate (b), and a hydroxyl group-containing mono (meth).
It can be obtained by reacting with an acrylate (c). As a typical reaction method, there can be mentioned a method of reacting the components (a) and (b) (urethane reaction), and then reacting the component (c) ((meth) acrylate reaction). . For the urethanization reaction between the component (a) and the component (b), one to two equivalents of the isocyanate group of the component (b) is added to 1 equivalent of the hydroxyl group of the component (a).
It is preferred to react 0 equivalents. Particularly preferably,
It is 1.5 to 2.0 equivalents. This urethanization reaction can be performed by a known procedure. The urethanization reaction temperature is usually room temperature to 100 ° C., preferably 50 to
It is 85 ° C.

Next, in the (meth) acrylate reaction for reacting the component (c), 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 by the urethanization reaction. 0.9 ~
It is preferable to react 1.5 equivalents, particularly preferably 1.0 to 1.1 equivalents. In this reaction, the reaction mixture usually contains 5% 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, p-benzoquinone. The acrylate reaction temperature is usually 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 catalyst such as triethylamine, dibutyltin dilaurylate or dibutyltin diacetate.

The above-mentioned diol compound (a) used for producing the urethane (meth) acrylate (A).
Examples of the aliphatic diol (a1), the aromatic diol (a2), the aliphatic polyether diol (a3),
Examples thereof include aromatic polyether diol (a4), aliphatic polyester diol (a5) and aromatic polyester diol (a6).

Examples of the aliphatic diol (a1) include ethylene glycol, propylene glycol and 1,3-
Butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 2-ethyl-2-butyl-1,3-propanediol, cyclohexane-1 , 4
-Examples include dimethanol. Aromatic diol (a
Examples of 2) include 1,4-dimethanolbenzene and the like. Examples of the aliphatic polyether diol (a3) include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol and the like. Examples of the aromatic polyether diol (a4) include bisphenol A polyethoxydiol, bisphenol A polypropoxydiol, tetrabromobisphenol A polypropoxydiol, 1,4-dimethanolbenzene polyethoxy compound, 1,4-dimethanol- Examples thereof include polypropoxy compounds of benzene. Examples of the aliphatic polyester diol (a5) include a reaction product of the above aliphatic diol (a1) with an aliphatic dibasic acid such as succinic acid, maleic acid and adipic acid, or an anhydride thereof. Examples of the aromatic polyester diol (a6) include the above aliphatic diol (a1) and phthalic acid, isophthalic acid,
Examples thereof include a reaction product of an aromatic dibasic acid such as terephthalic acid or an anhydride thereof, a reaction product of the aromatic diol (a2) and the aliphatic dibasic acid or an anhydride thereof, and the like.

Examples of the organic diisocyanate (b) used for producing the urethane (meth) acrylate (A) include tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and trimethylhexamethylene diisocyanate. I can give you.

Examples of the hydroxyl group-containing mono (meth) acrylate (c) used for producing the urethane (meth) acrylate (A) include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth). Acrylate, 4-hydroxybutyl (meth) acrylate, poly (n = 2 to 10 as an average value)
Ethylene glycol mono (meth) acrylate, poly (n = 2 to 10 as an average value) propylene glycol mono (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 2-hydroxy-3- (o- Examples thereof include phenylphenyloxy) propyl (meth) acrylate.

In the present invention, the imide (meth) acrylate (B) represented by the general formula (1) is used. Examples of the imide (meth) acrylate (B) include those represented by the general formula (1)
In which R is a hydrogen atom (Toagosei Co., Ltd.)
Manufactured by Aronix TO-1429) and compounds in which R is a methyl group.

In the present invention, a reactive monomer (C) other than the component (B) is used. Examples of the reactive monomer (C) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethyloxyethyl (meth) acrylate, and 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 as an average value) ethoxydi (meth) acrylate, acryloylmorpholine, tribromophenyloxyethyl (meth) acrylate, tribromobenzyl (meth) acrylate, styrene , It may be mentioned α- methyl styrene.

As the preferable reactive monomer (C), acrylates having a high refractive index, for example, monoacrylate having a phenyl ether group such as phenyloxyethyl acrylate, o-phenylphenyloxy acrylate, tribromophenyloxyethyl acrylate and the like. Monomers (C1) and acrylates that improve adhesion, such as bisphenol A polyethoxydiacrylate,
A diacrylate monomer (C2) of a dihydric alcohol such as 1,6-hexanediol diacrylate can be used.

In the present invention, a photopolymerization initiator (D) can be used. By using this photopolymerization initiator (D), the resin composition of the present invention can be made into an ultraviolet curable resin composition. As the photopolymerization initiator (D),
For example, 1-hydroxycyclohexyl phenyl ketone,
Phenyl-2-hydroxy-2-propyl ketone, 2,
4,6-Trimethylbenzoyl-diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl)-
2,4,4-trimethylpentylphosphine oxide, methylbenzoyl formate and the like can be mentioned.

In the present invention, a bisphenol type epoxy (meth) acrylate (E) can be used.
By using this bisphenol type epoxy (meth) acrylate (E), a cured product having a higher refractive index can be obtained. Examples of the bisphenol-type epoxy (meth) acrylate (E) include epoxy (meth) acrylate obtained by reacting a bisphenol-type epoxy resin with (meth) acrylic acid. Particularly preferable one is bisphenol A type epoxy acrylate.

The bisphenol type epoxy resin used to obtain the bisphenol type epoxy (meth) acrylate (E) is, for example, a bisphenol A type epoxy resin (eg, Epicoat 1001, 1002, 1004 manufactured by Yuka Shell Epoxy Co., Ltd.). , 1010, etc., average molecular weight 900-6000, epoxy equivalent 400
~ 5,000 are available. ), Bisphenol F type epoxy resin (for example, YDF-200 manufactured by Tohto Kasei Co., Ltd.)
Epoxy equivalent 160 with product names such as 1, 2004, 170
There are ~ 1000 things. ), Or diglycidyl ether of bisphenol A polyalkylene glycol.

(A), (B) in the resin composition of the present invention,
As the usage ratio of the components (C), (D) and (E),
When the total amount of the components (A) to (E) is 100 parts by weight,
The component (A) is preferably 10 to 60% by weight, particularly preferably 20 to 40% by weight. The component (B) is 5 to
It is preferably 50% by weight, particularly preferably 10 to 40% by weight. The component (C) is preferably 25 to 80% by weight,
It is particularly preferably 30 to 65% by weight. The component (D) is preferably 0 to 15% by weight, more preferably 0.5.
-15% by weight, particularly preferably 1-5% by weight.
The component (E) is preferably 0 to 40% by weight, particularly preferably 5 to 30% by weight.

In addition to the above components, the resin composition of the present invention may further contain additives such as defoaming agents, leveling agents, antioxidants, plasticizers, release agents, polymerization inhibitors and light stabilizers. , A non-reactive polymer resin (for example, polyester elastomer,
Polyurethane elastomer, acrylic polymer, etc.) can also be used together.

The resin composition of the present invention comprises the above (A),
The components (B) and (C) are dissolved and mixed, and if necessary, the components (D) and (E), the above-mentioned additives, the non-reactive polymer resin, etc. are added and mixed uniformly. By dissolving, it can be usually obtained as a transparent liquid composition at room temperature. The viscosity of the liquid composition is 500 to 10,000
About cps (25 ° C.) is preferable.

The resin composition of the present invention can be preferably used for lenses, but can also be used for screen printing inks, paint coatings, adhesives and the like in addition to lenses.

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

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 layer. Is adhered, and then in that state, an energy ray such as ultraviolet rays is irradiated from the side of the resin substrate by a high pressure mercury lamp or the like to cure the resin composition, and then the mold is released from the mold. In this way, the normal refractive index (25 ° C) is 1.54.
A Fresnel lens having 5 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. Examples of the material of the transparent resin substrate include polycarbonate resin, polystyrene resin, polyester resin, polyacrylic resin, and mixed resins thereof.

[0025]

EXAMPLES The present invention will be described in more detail with reference to Examples below, 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 Polyester diol (polyester diol of neopentyl glycol and adipic acid, molecular weight 2000, OH
Value 56.1) 120 parts, ethylene glycol 2.48
Part, 34.8 parts of tolylene diisocyanate were charged and reacted at 80 ° C. for 10 hours after heating, then 24.4 parts of 2-hydroxyethyl acrylate and 0.1 part of methquinone were charged and reacted at 80 ° C. for 10 hours. Urethane acrylate (A-1) was obtained.

Synthesis Example 2 Polytetramethylene glycol (molecular weight 650, OH
Value, 172.6) 130 parts, ethylene glycol 49.
After charging 6 parts and 348 parts of tolylene diisocyanate, the temperature was raised and reacted at 80 ° C. for 10 hours, then 243.6 parts of 2-hydroxyethyl acrylate and 0.4 parts of methoquinone were charged and reacted at 80 ° C. for 10 hours to carry out urethane acrylate. (A-2) was obtained.

Examples 1 to 3 Each component was mixed and dissolved in a formulation as shown in Table 1 (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 substrate is adhered on it, and the resin is irradiated with ultraviolet rays to cure and released from the mold to obtain a Fresnel lens. I went. Various evaluations were performed by the following methods.

(1) Releasability: Difficulty in releasing a cured resin from a mold. Good: Good releasability from the mold △: Releasing is somewhat difficult x: Releasing is difficult or there is a lump. (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. ◎ ・ ・ ・ ・ It disappeared instantly. ○: Disappeared within 60 seconds. B: disappeared within 1 to 60 minutes. × ... It took 60 minutes or more to disappear.

(3) Scratch resistance: A methacrylic resin substrate (width 100 mm, on the surface of the cured resin layer separated from the mold)
A length of 100 mm and a thickness of 2.5 mm) was strongly pressed vertically, and was reciprocated 10 times at an interval of about 100 mm at a speed of about 1 second for 1 reciprocation, and then scratches were observed on the surface. ◎ ・ ・ ・ ・ No scratches are observed. ○ ... Several streaky scratches are observed. △ ・ ・ ・ ・ Strip-shaped scratches are partially observed. × ・ ・ ・ ・ Strip-shaped scratches are observed on the entire surface.

(4) Adhesion: A resin composition is formed on a transparent methacrylic resin substrate to a film thickness of 200 μm, a width of 20 mm, and a length of 1
50mm, then high pressure mercury lamp (80w / cm,
A test piece was prepared by irradiating at 500 mj / cm ² without ozone and curing the test piece, and the peel strength of the cured resin film on the methacrylic resin substrate at 90 ° C. was measured by a tensile tester (peel speed 100 mm / min). . ◎ ・ ・ ・ 2 kg / cm or more ○ ・ ・ ・ ・ 1-2 kg / cm △ ・ ・ ・ ・ 0.5-1 kg / cm × ・ ・ ・ ・ 0.5 kg / cm or less (5) Refractive index: cured The refractive index (25 ° C.) of the resin was measured.

[0032]

[Table 1]                                   Table 1                                             Example Comparative Example                                       1 2 3 1 Urethane acrylate (A-1) 30 20 30 Urethane acrylate (A-2) 30 Bisphenol A Epoxy Acryl Rate * 1 10 Imido acrylate * 2 15 15 15 o-phenylphenyloxyethyl Acrylate 10 10 10 25 Bisphenol A poly (as an average value n is about 4) ethoxydiacrylate 45 45 45 45 45 Phenyl-2-hydroxy-2- Propyl ketone 3 3 3 3 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Releasability ○ ○ ○ ○ Restorability ◎ ○ ○ ○ Scratch resistance ◎ ◎ ○ ○ Adhesion ◎ ◎ ◎ × Refractive index 1.551 1.555 1.561 1.562

Note) * 1 Bisphenol A-type epoxy acrylate: Bisphenol A-type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 1004, epoxy equivalent 925, average molecular weight 1850) is equivalent to 0 acrylic acid per 1 equivalent of epoxy group. .98 mol reacted and diluted with phenoxyethyl acrylate (bisphenol A
Type epoxy acrylate 60% by weight). * 2 Imido acrylate: Aronix TO-142
9 (a compound manufactured by Toa Gosei Chemical Industry Co., Ltd., wherein R is a hydrogen atom in the above formula (1)).

From the evaluation results shown in Table 1, it is understood that the cured product of the resin composition of the present invention has a high refractive index and is excellent in restoration properties, scratch resistance, adhesiveness, releasability and the like. Further, it is understood from the comparison between Example 3 and Examples 1 and 2 that the combined use of the bisphenol type epoxy acrylate (E) further increases the refractive index.

[0035]

EFFECTS OF THE INVENTION The cured product of the resin composition of the present invention has a high refractive index and is excellent in restoration properties, scratch resistance, adhesiveness and releasability.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J027 AE02 AG01 AG03 AG04 AG09                       AG12 AG13 AG14 AG23 AG24                       AJ08 BA02 BA03 BA07 BA08                       BA11 BA13 BA19 CB10 CC05                       CD04

Claims (7)

[Claims] 1. A urethane acrylate (A), represented by the general formula (1): (In the formula, R is a hydrogen atom or a methyl group.), An imide (meth) acrylate (B), a reactive monomer (C) other than the component (B), and a photopolymerization initiator as an optional component. A resin composition comprising (D). 2. The resin composition according to claim 1, which contains a bisphenol type epoxy (meth) acrylate (E). 3. The resin composition according to claim 1, which is used for lenses. 4. A cured product of the resin composition according to claim 1. 5. The cured product according to claim 4, which has a refractive index (25 ° C.) of 1.545 or more. 6. The cured product according to claim 4, which is a lens. 7. The cured product according to claim 6, wherein the lens is a sheet lens.