JP2002338946A - Sealant resin composition and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a sealant resin composition which can give a cured product excellent in adhesion and humidity resistance and used for liquid crystal panels and organic electroluminescent (EL) panels and to provide a cured product thereof. SOLUTION: The sealant resin composition comprises (A) a (meth) acrylate oligomer, (B) a maleimide derivative, and (C) a polymerizable compound, as an optional component, other than components (A) and (B).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition for a sealing material such as a liquid crystal display panel and an organic EL display panel, and a cured product thereof.

[0002]

2. Description of the Related Art In a liquid crystal cell, a liquid crystal is usually injected between a pair of electrode substrates whose periphery is surrounded by a sealing material layer through an injection hole through a cut in the sealing material layer, and then the injection hole is sealed with a sealing material. It is manufactured by sealing.

[0003] Conventionally, organic materials, particularly two-pack type epoxy resin compositions and one-pack type epoxy resin compositions, have been mainly used as seal materials.

[0004] However, the two-pack type epoxy resin composition has a problem that the pot life is short and the viscosity tends to increase, so that it has to be prepared for each lot and the production efficiency is poor. On the other hand, the one-pack type epoxy resin composition is 150 to 200.
Since it is necessary to heat at a high temperature of ° C. for several tens of minutes, the production efficiency is still insufficient.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and is intended to be carried out in a short time at room temperature.
An object of the present invention is to provide a resin composition for a sealing material, which has a characteristic of being cured by ultraviolet irradiation and forms a cured layer having excellent adhesion, moisture resistance, stain resistance, and flexibility, and a cured product thereof. I do.

[0006]

Means for Solving the Problems As a result of diligent studies, the present inventors have found that the above object can be achieved by using (meth) acrylate oligomer (A) and maleimide derivative (B) as main components. , Arrived at the departure.

That is, the present invention provides (1) a (meth) acrylate oligomer (A) and a maleimide derivative (B)
And (2) a resin composition for a sealing material characterized by containing a polymerizable compound (C) other than the components (A) and (B) as an optional component; (3) The polymerizable compound (C) is selected from the group consisting of (meth) acrylate monomers, vinyl ether compounds and N-vinyl compounds, wherein the resin composition for a sealing material according to (1) is (meth) acrylate. It relates to at least one kind of the resin composition for a sealing material according to (1), and (4) a cured product of the resin composition for a sealing material according to any one of (1) to (3).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition for a sealing material of the present invention comprises a (meth) acrylate oligomer (A), a maleimide derivative (B), and optionally a polymerizable compound (A) other than the components (A) and (B). C).

In the present invention, a (meth) acrylate oligomer (A) is used. Specific examples of the (meth) acrylate oligomer (A) include polyester (meth) acrylate (A-1), urethane (meth) acrylate (A-2), and epoxy (meth) acrylate (A-
3) can be cited as a typical example.

Polyester (meth) acrylate (A-
1) is a general term for (meth) acrylates having one or more ester bonds in the main chain, and urethane (meth) acrylate (A-2) is a (meth) acrylate having one or more urethane bonds in the main chain. Epoxy (meth) acrylate (A-3) is used as a generic term for (meth) acrylate obtained by reacting a bifunctional or more functional epoxy compound with (meth) acrylic acid.

Polyester (meth) acrylate (A-
Examples of 1) include, for example, caprolactone-modified 2-hydroxyethyl (meth) acrylate, ethylene oxide and / or propylene oxide-modified phthalic acid (meth)
Monofunctional (poly) ester (meth) acrylates such as acrylate, ethylene oxide-modified succinic acid (meth) acrylate, and caprolactone-modified tetrahydrofurfuryl (meth) acrylate; hydroxypivalic acid ester neopentyl glycol di (meth) acrylate, and caprolactone-modified Hydroxypivalic acid ester neopentyl glycol di (meth) acrylate, epichlorohydrin-modified phthalic acid di (meth) acrylate;
1 mol or more of ε-caprolactone, γ-butyrolactone, δ- in 1 mol of trimethylolpropane or glycerin
Mono-, di- or tri (meth) acrylate of triol obtained by adding a cyclic lactone compound such as valerolactone;

1 mol or more of ε-caprolactone per 1 mol of pentaerythritol or ditrimethylolpropane,
Mono, di, tri or tetra (meth) acrylate of triol obtained by adding a cyclic lactone compound such as γ-butyrolactone or δ-valerolactone; 1 mol or more of ε-caprolactone or γ-butyrolactone per 1 mol of dipentaerythritol , Mono-triol obtained by adding a cyclic lactone compound such as δ-valerolactone, or mono- (meth) acrylate or poly-polyhydric alcohol such as triol, tetraol, pentaol or hexaol of poly (meth) acrylate (Meth) acrylate;

(Poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) butylene glycol, 3-methyl-1,5
Diol components such as pentanediol and hexanediol and maleic acid, fumaric acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebacic acid, azelaic acid, 5-sodium (Meth) acrylates of polyester polyols which are reactants with polybasic acids such as sulfoisophthalic acid and anhydrides thereof; the diol components and polybasic acids and anhydrides thereof and ε-caprolactone, γ-
Examples include, but are not limited to, polyfunctional (poly) ester (meth) acrylates such as (meth) acrylate of a cyclic lactone-modified polyester diol composed of butyrolactone, δ-valerolactone, and the like.

Urethane (meth) acrylate (A-2)
Is a general term for (meth) acrylates obtained by reacting a hydroxy compound (A-2-) having at least one (meth) acryloyloxy group with an isocyanate compound (A-2-).

Examples of the hydroxy compound (A-2-) having at least one (meth) acryloyloxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
-Hydroxybutyl (meth) acrylate, 4-hydroxyethyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, Examples include (meth) acrylate compounds having various hydroxyl groups such as 2-hydroxy-3-phenoxypropyl (meth) acrylate, and ring-opening products of the above-mentioned (meth) acrylate compounds having a hydroxyl group and ε-caprolactone.

As the isocyanate compound (A-2-), for example, P-phenylenediisocyanate, m-
Phenylene diisocyanate, P-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate,
Aromatic diisocyanates such as naphthalene diisocyanate; diisocyanates having an aliphatic or alicyclic structure such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, lysine diisocyanate; Polyisocyanates such as one or more burettes of monomers or isocyanates obtained by trimerizing the diisocyanate compound; polyisocyanates obtained by a urethanization reaction between the isocyanate compound and the polyol compound.

Epoxy (meth) acrylate (A-3)
Is a generic term for (meth) acrylates obtained by reacting an epoxy resin (A-3-) having a bifunctional or higher epoxy group with (meth) acrylic acid (A-3-).

Specific examples of epoxy resin (A-3-) include bisphenol-type polyepoxides obtained by reacting epichlorohydrin with bisphenol A, bisphenol F, etc .; novolak-type polyepoxides obtained by reacting epichlorohydrin with novolak resins; Representative examples include, but are not limited to, cycloaliphatic polyepoxides obtained by epoxidizing the reaction product of butanediene and crotonaldehyde with peracetic acid.

The epoxy (meth) acrylate (A
For -3), a partially esterified epoxy (meth) acrylate containing an epoxy group can also be preferably used. Further, a liquid at room temperature is preferred, but any solid can be used as long as it is soluble in the polymerizable compound (C) described below.

Among the (meth) acrylate oligomers (A), particularly preferred are the epoxy (meth) acrylates (A-3) and the like.

In the present invention, the maleimide derivative (B) is used. Specific examples of the maleimide derivative (B) include a 1-3-functional maleimide compound described in JP-A-58-40374, a maleimide group-containing urethane oligomer described in JP-A-3-12414, and the like. Can be.

Further, typical examples include N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, N-allylmaleimide, Nn-butylmaleimide, N-2 -Methyl-propylmaleimide, N-cyclohexylmaleimide, N-2-ethylhexylmaleimide, N- (2-
Dimethylaminoethyl) maleimide, N- (1-methoxymethylpropyl) maleimide, N, N'-1,6-hexanebismaleimide, bis (3-N-maleimidopropyl) polytetramethylene glycol, bis (2-N-
Maleimidopropyl) polypropylene glycol, bis (2-N-maleimidoethyl) polyethylene glycol, 1,2 (1,3 or 1,4) -bis (N-maleimidomethyl) cyclohexane,

[0023]

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[0024]

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[0025]

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And maleimide compounds in which a hydrogen atom bonded to an unsaturated carbon atom in the maleimide group of these maleimide compounds is substituted with a chlorine atom, a bromine atom, a methyl group, an ethyl group, a methoxy group, or the like. be able to. Particularly preferred imide compounds are N- (1-
Methoxymethylpropyl) maleimide, N-cyclohexylmaleimide, bis (3-N-maleimidopropyl)
Polytetramethylene glycol, bis (2-N-maleimidopropyl) polypropylene glycol, bis (2-
N-maleimidoethyl) polyethylene glycol, 1,
2 (1,3 or 1,4) -bis (N-maleimidomethyl) cyclohexane and the like can be mentioned.

In the present invention, the polymerizable compound (C) is used. Specific examples of the polymerizable compound (C) include (meth) acrylate monomers (C-1), vinyl ether compounds (C-2), and N-vinyl compounds (C-3).

(Meth) acrylate monomers (C-
Specific examples of 1) include 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, carbitol (meth) acrylate, 2-hydroxy -3-phenyloxypropyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, 1,4-butanediol di (meth) acrylate,
1,9-nonanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta, and Hexa (meth) acrylate and the like can be mentioned.

Specific examples of the vinyl ether compounds (C-2) include hydroxymethyl vinyl ether, chloromethyl vinyl ether, hydroxyethyl vinyl ether, 1,4-butanediol divinyl ether, 1,6
-Hexanediol divinyl ether, 4-hydroxybutyl vinyl ether, trimethylolpropane trivinyl ether, cyclohexane dimethanol mono or divinyl ether, cyclohexane mono or divinyl ether, triethylene glycol divinyl ether, polytetramethylene glycol divinyl ether, polyurethane polyvinyl ether, polyester Polyvinyl ether and the like can be mentioned.

Specific examples of the N-vinyl compounds (C-3) include N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinylacetamide and the like.

The polymerizable compound (C) is not limited to the above-mentioned compounds. As long as the compound has a copolymerizability with the component (A) and the component (B), one or more of the compounds can be used in combination without particular limitation.

In the resin composition for a sealing material of the present invention,
As the usage ratio of the components (A) to (C), the component (A) is preferably 20 to 80% by weight, particularly preferably 3 to 80% by weight.
0 to 70% by weight, component (B) is preferably 3 to 50% by weight, particularly preferably 10 to 30% by weight, and component (C) is preferably 0 to 77% by weight, particularly preferably 20 to 70% by weight.
６０60% by weight.

The resin composition for a sealing material of the present invention comprises
By using the components (A) to (C), the composition is cured by irradiation with ultraviolet rays, and the cured product has sufficient performance. However, in order to further improve the performance, a photopolymerization initiator, an epoxy resin, Thermosetting agent, silane coupling agent, filler,
Other additives and the like can be used.

Specific examples of the photopolymerization initiator include radical-type photopolymerization initiators such as α-diketones such as benzyl and diacetyl; acyloins such as benzoin; benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Benzophenones such as thioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, benzophenone, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone; acetophenone , P-dimethylaminoacetophenone, α, α'-dimethoxyacetoxybenzophenone, 2,2'-dimethoxy-2-phenylacetophenone, P-methoxyacetophenone,
Acetophenones such as -methyl- {4- (methylthio) phenyl} -2-morpholino-1-propanone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; anthraquinone ,
Quinones such as 1,4-naphthoquinone; halogen compounds such as phenacyl chloride, tribromomethylphenylsulfone and tris (trichloromethyl) -S-triazine; acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide And the like. As the cationic photopolymerization initiator,
Triallylsulfonium salts, diallyliodonium salts and the like can be used. Commercially available products include, for example, Adeka Optomer SP-150 and Adeka Optomer SP-1
70 (above, Asahi Denka Kogyo Co., Ltd., trade name), Syracure UVI-6990 (Union Carbide Co., Ltd., trade name) and the like.

One or more of these photopolymerization initiators are used. The mixing ratio is from 0 to 1 in the resin composition.
It is preferably 0% by weight.

Specific examples of the epoxy resin include bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin;
Novolak-type epoxy resins, such as novolak-type epoxy resins and cresol-novolak-type epoxy resins, cycloaliphatic epoxy resins, and heterocyclic epoxy resins are exemplified. The compounding ratio is preferably 0 to 30% by weight in the resin composition.

Specific examples of the thermosetting agent include 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl as the thermosetting agent for reacting the epoxy group in the epoxy resin or the component (A). -4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenylimidazolium-trimellitate, 2,4-diamino-6
-[2-Methylimidazole- (1)]-ethyl-S-
Imidazoles such as triazine; organic acid hydrazides such as succinic dihydrazide, adipic hydrazide, salicylic acid dihydrazide; acid anhydrides; amines; Lewis acids; dicyandiamide. As a thermosetting agent for reacting the (meth) acryloyl group of the component (A), 1,1-bis (t-butylperoxy) -3,3,3 is used.
Organic and peroxides such as 5-trimethylcyclohexane, cumene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, lauroyl peroxide and benzoyl peroxide Things.

One or more of these thermosetting agents are used. The compounding ratio is preferably 0 to 15% by weight in the resin composition.

Specific examples of the silane coupling agent include:
Vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane and vinyltrimethoxysilane, acrylicsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy Silanes, epoxysilanes such as γ-glycidoxypropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyl Examples include aminosilanes such as trimethoxysilane and the like, and γ-mercaptopropyltrimethoxysilane and γ-chloropropyltrimethoxysilane. The mixing ratio is preferably 0 to 20% by weight in the resin composition of the present invention.

Specific examples of the filler include spacers such as transparent glass beads, talc, kaolin, clay, barium sulfate, quartz, magnesium carbonate, calcium carbonate, silica, fine silica, titanium oxide, aluminum oxide, aluminum hydroxide, and the like. Examples include inorganic fillers such as aluminum silicate, spacers such as plastic beads, and organic fillers such as fine acrylic polymer and fine butyl nitrile rubber. When the particle size of these fillers is 1.5 μm or less, it is preferable since thixotropic properties can be improved. The mixing ratio is 0 in the resin composition of the present invention.
Preferably it is 〜50% by weight.

Other additives include, for example, colorants,
Examples include a leveling agent, an antifoaming agent, and a polymerization inhibitor.

The resin composition for a sealing material of the present invention comprises the above components (A) to (C), a photopolymerization initiator, an epoxy resin, a thermosetting agent, a silane coupling agent,
It can be obtained by mixing and dissolving a filler and other additives, and then kneading with a three-roll or the like.

The resin composition for a sealing material of the present invention can be cured by irradiating ultraviolet rays. As the curing conditions, a high-pressure mercury lamp is usually used for ultraviolet curing, and irradiation conditions vary depending on the type of lamp used, the composition and amount of the sealing material, the distance from the lamp, and the like, and may be adjusted according to these conditions. Although not particularly limited, for example, an energy amount of 600 mJ / cm ² to 50
Irradiation conditions of about 00 mJ / cm ² are employed.

When the thermosetting is used in combination, it differs depending on the kind of the used thermosetting agent, the kind of the other material, the mixing ratio and the like, and is not particularly limited.
Conditions of about 1 hour or more at 50 ° C. are usually adopted.

[0045]

EXAMPLES Hereinafter, the present invention will be further described with reference to specific examples and comparative examples, but the present invention is not limited to those described in the examples. Example 1 As a component (A), a 50% esterified epoxy acrylate in which 50% of the equivalent of the epoxy group of a bisphenol A type epoxy resin (Yuika Shell Epoxy Co., Ltd., Epicoat 828) was acrylated with acrylic acid. With respect to 100 parts, 30 parts of cyclohexylmaleimide as the maleimide derivative of the component (B), 10 parts of pentaerythritol triacrylate as the polymerizable compound of the component (C), and 2-phenyl-
4 parts of 4,5-dihydroxymethylimidazole, 4 parts of dihydrazine adipate, 50 parts of talc and 10 parts of fine silica as an inorganic filler, and γ-glycidoxypropyltrimethoxysilane 5 as a coupling agent
After kneading the parts with a three-roll mill, 5 parts of a spacer was mixed with 100 parts of the resin composition for a sealing material further prepared to prepare a sealing material for a liquid crystal display panel.

(Preparation of Liquid Crystal Display Panel) The above prepared sealing material is screen-printed on a glass substrate with a transparent electrode (periphery) while leaving a liquid crystal injection hole, and a second glass substrate with a transparent electrode is formed on the glass substrate. Were bonded and pressed, and then irradiated with ultraviolet rays using a high-pressure mercury lamp (2 KW) for 30 seconds, and then heated at 150 ° C. for 30 minutes to cure the sealing material.

After filling the obtained empty cell with the fluorine-based liquid crystal composition through the injection hole, the injection hole is sealed with the sealing material, and the sealing material in the sealed portion is cured in the same manner. A liquid crystal display panel was obtained. The obtained liquid crystal display panel was evaluated for adhesion and moisture resistance. Table 1 shows the results.

Evaluation method. Adhesion: Liquid crystal cell was placed in an environment of 80 ° C. × 95% RH for 20 minutes.
Leave for 0 hours, indoor natural leaving 10 hours as one cycle,
After a 10-cycle test, the cell was peeled off using a knife. ○ ・ ・ ・ ・ ・ ・ ・ No peeling △ ・ ・ ・ ・ ・ ・ ・ Slightly difficult to peel × ・ ・ ・ ・ ・ ・ ・ Slightly easy to peel

Moisture resistance: After leaving the liquid crystal cell in an environment of 80 ° C. × 95% RH for 1000 hours, 5 V, 50 Hz is applied between terminals.
And the reliability was determined from the current value by the change rate. ○ ・ ・ ・ ・ ・ ・ ・ Small fluctuation (current value is less than twice the initial value) and good reliability △ ・ ・ ・ ・ ・ ・ ・ Slight fluctuation (current value is 2-3 of initial value)
×), slightly poor reliability × ····· Large fluctuation (current value exceeds 3 times the initial value), poor reliability

Comparative Example 1 In Example 1, the component (B) cyclohexylmaleimide 3
A liquid crystal display panel was prepared in the same manner as in Example 1 except that 0 part was changed to 0 part, and evaluated similarly. The results are shown in Table 1.

[0051]

Note * 1: Since it was not cured by irradiation with ultraviolet rays, it did not cure sufficiently even after thermal curing.

As is clear from the evaluation results in Table 1, the resin composition for a sealing material of the present invention is sufficiently cured by irradiation with ultraviolet rays and heat, and the cured product is excellent in adhesion and moisture resistance.

[0054]

The resin composition for a sealing material of the present invention is an ultraviolet-curing type, so it cures in a short time, and has already been cured by irradiation with ultraviolet light during heat treatment. No slippage of the upper and lower substrates caused by the difference in thermal expansion between different substrates
Since it is excellent in adhesion, moisture resistance, and the like, a highly reliable liquid crystal cell and organic EL cell can be obtained.

Continued on front page F term (reference) 2H089 JA11 LA41 QA07 TA01 4H017 AA04 AB01 AC16 4J027 AB03 AB05 AB10 AB15 AB16 AB19 AB23 AB25 AE01 AE02 AE03 AE04 AG04 AG09 AG15 AG23 AG24 AG27 AG33 BA03 BA07 BA08 BA13 BA15 BA17 CA11 CA18 CC02 CC05 CD06

Claims (4)

[Claims] 1. A sealing material comprising a (meth) acrylate oligomer (A), a maleimide derivative (B), and optionally a polymerizable compound (C) other than the components (A) and (B). Resin composition. 2. The resin composition for a sealing material according to claim 1, wherein the (meth) acrylate oligomer (A) is an epoxy (meth) acrylate. 3. The resin composition for a sealing material according to claim 1, wherein the polymerizable compound (C) is at least one selected from the group consisting of (meth) acrylate monomers, vinyl ether compounds and N-vinyl compounds. . 4. A cured product of the resin composition for a sealing material according to any one of claims 1 to 3.