TW201319093A - Novel (meth)acrylic resin and resin composition utilizing same - Google Patents

Abstract

The present invention proposes: a (meth)acrylic resin represented by formula (1); and a resin composition prepared using the (meth)acrylic resin. In the formula, the benzene ring Ar may be present or absent; a bond a represents a single bond or a double bond when the benzene ring Ar is absent; n represents an integer of 1 to 5; and R1 represents a hydrogen atom or a methyl group. The (meth)acrylic resin can be applied suitably for adhesive agents, is easy to handle, and can achieve flexibility in designing of adhesive agents and high adhesion strength of adhesive agents.

Description

Novel (meth)acrylic resin and resin composition using the novel (meth)acrylic resin

This invention relates to a novel (meth)acrylic resin. More specifically, it relates to a (meth)acrylic resin having a hydroquinone, a catechol, or a resorcinol skeleton, and having a carboxyl group in its molecule, and further The present invention proposes a resin composition suitable for use in an adhesive, which is obtained by using the (meth)acrylic resin.

Conventionally, a (meth)acrylic resin having a carboxyl group in a molecule is widely used in a resist ink composition which is a photoresist pattern for forming a printed wiring substrate (Patent Document 1 and Patent Literature) 2, etc.). This resist ink composition is used to form a desired wiring pattern by development. Specifically, the (meth)acrylic resin composition under the mask of the cut pattern (wiring) is irradiated with an energy ray such as ultraviolet rays to expose the (meth)acrylic resin of the exposed portion (methyl group). The propylene sulfhydryl group is crosslinked. Then, alkali development is carried out by utilizing the alkali solubility of the carboxyl group of the uncured (meth)acrylic resin, thereby forming a fixed pattern.

Moreover, this (meth)acrylic resin is also used as an adhesive. For example, in Patent Document 3, it is used as a photocurable dental adhesive.

However, these (meth)acrylic resins are specifically designed for light hardening. A design in which a water-resistant adhesive such as a chemical or cured product is used as a dental adhesive in the vicinity of normal temperature. Therefore, the use of the (meth)acrylic resin as an adhesive has not been sufficiently established.

[Previous Technical Literature] (Patent Literature)

Patent Document 1: Japanese Patent Laid-Open No. 61-243869

Patent Document 2: Japanese Patent Laid-Open No. 3-143911

Patent Document 3: Japanese Laid-Open Patent Publication No. Hei 5-286822

The present invention has been made in view of the above circumstances, and relates to a novel (meth)acrylic resin having a carboxyl group in a molecule. That is, the present invention proposes a novel (meth)acrylic resin which is suitable for use in an adhesive application, and which can realize the degree of freedom in design of the treatment and the adhesive, and the high adhesion strength of the adhesive.

The inventors of the present invention have intensively conducted a discussion in view of the above-mentioned reasons, and as a result, found that an acid anhydride or the like is a (meth) acrylate of an epoxy resin having a skeleton such as hydroquinone, catechol, or resorcin. Since the compound obtained by the reaction has a small molecular weight, it has a low viscosity, and since the carboxyl group equivalent (the molecular weight corresponding to each carboxyl group) is also small, the polarity can be increased, and when a constituent component as an adhesive is used, it can be obtained. achieve The present invention has been completed by an improvement in adhesion strength and a promoting effect of a heat hardening reaction.

That is, the present invention relates to the following 1) to 12). In the present specification, the term "(meth)acrylic acid" means one or both of "acrylic acid" and "methacrylic acid". In the present specification, the term "(meth)acryloyl group" means one or both of "acryloyl fluorenyl group" and "methacryl fluorenyl group".

1) A (meth)acrylic resin represented by the following formula (1), (wherein, the benzene ring Ar may or may not be present, and when the benzene ring Ar is absent, the bond a represents a single bond or a double bond; further, n represents an integer of 1 to 5, and R ¹ represents a hydrogen atom or a methyl group) .

2) The (meth)acrylic resin according to the above 1), wherein the benzene ring Ar is not present in the above formula (1).

3) The acrylic resin according to the above 1), wherein R ¹ in the above formula (1) is a hydrogen atom.

4) A resin composition containing the (meth)acrylic resin according to any one of the above 1) to 3).

5) The resin composition according to the above 4), which further contains a photopolymerization initiator.

The resin composition according to the above 4), which further contains a thermal radical polymerization initiator.

7) The resin composition according to the above 4), which further contains an inorganic filler.

8) The resin composition according to the above 4), which further contains a hydrazide compound.

9) The resin composition according to the above 4), which further contains a decane coupling agent.

10) An adhesive for electronic parts, which is produced by using the resin composition as described in 4) above.

11) A liquid crystal display cell adhesive obtained by using the resin composition according to the above 4).

12) A liquid crystal display cell which is formed by adhering a liquid crystal display cell as described in the above 11) with an adhesive.

The (meth)acrylic resin of the present invention is very suitable for use in an adhesive. In other words, since the (meth)acrylic resin of the present invention has a carboxyl group in the molecule and further has a small carboxyl group equivalent, it is possible to enhance the adhesion strength of the adhesive and the effect of promoting the thermosetting reaction. Moreover, the (meth)acrylic resin of the present invention also has the following characteristics: since the molecular weight is small, it is also easy to handle, and further, when used as a stickiness When the agent is applied, it is not easily restricted by the viscosity of other components, so that it is easy to design without using a diluent such as an organic solvent.

Hereinafter, the present invention will be described in detail.

The (meth)acrylic resin represented by the above formula (1) of the present invention can be obtained by 0.1 mol% to 30 mol equivalents, preferably 1 in the presence of a reaction catalyst. The anhydride having a molar equivalent of ~10 moles is obtained by reacting with an epoxy acrylate resin represented by the following formulas (2) to (4). The reaction temperature is preferably from 0 ° C to 100 ° C, more preferably from 10 ° C to 40 ° C. Further, n and R ¹ in the formulae (2) to (4) have the same meanings as n and R ¹ in the above formula (1).

The reaction catalyst is not particularly limited, and a substance such as an alkali can be used, but an organic base is preferably used. It is particularly preferred to use a tertiary amine. Further, two or more kinds may be used in combination, and it is one of the particularly preferable aspects to use 4-methylaminopyridine and triethylamine.

Examples of the acid anhydride include maleic anhydride, dihydromaleic anhydride (succinic anhydride), and phthalic anhydride. In addition, when maleic acid, dihydromaleic acid (succinic acid), phthalic acid or the like is used in place of the acid anhydride, the addition amount can be appropriately designed to obtain (methyl) represented by the above formula (1). ) Acrylic resin.

Further, this synthesis can also be carried out using an organic solvent. The organic solvent to be used may, for example, be 2-butanone or dichloromethane, or may be used in combination of two or more.

The (meth)acrylic resin of the present invention is preferably a (meth)acrylic resin having a resorcinol skeleton as compared with the hydroquinone skeleton or the catechol skeleton. The reason is that the symmetry of the resorcinol skeleton is lower than that of the hydroquinone skeleton, and the resorcinol skeleton is easier to obtain and the resin hardening reaction is faster than the catechol skeleton. Further, from the viewpoint of the rapidity of the reaction, an acrylic tree is preferred as compared with the methacrylic resin. fat. Further, in order to lower the carboxyl group equivalent, maleic anhydride is preferably used as the acid anhydride.

The resin composition obtained by using the (meth)acrylic resin of the present invention is suitably used as an adhesive. In this case, when the total amount of the resin composition is 100 parts by mass, the content of the (meth)acrylic resin is preferably from 0.01 part by mass to 95 parts by mass. Further, it is preferably from 0.1 part by mass to 90 parts by mass, particularly preferably from 1 part by mass to 80 parts by mass. As the remainder, there are a photopolymerization initiator, a thermal radical polymerization initiator, an inorganic filler, a thermosetting agent, a decane coupling agent, and the like.

The photopolymerization initiator which can be contained in the resin composition of the present invention is not particularly limited as long as it can generate a radical due to irradiation with an energy ray such as ultraviolet light or visible light, and the chain polymerization reaction starts. For example, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, diethyl thioxanthone, benzophenone, 2-ethyl hydrazine, 2-hydroxy-2 can be mentioned. -methylpropiophenone, 2-methyl-[4-(methylthio)phenyl]-2-(N-morpholinyl)-1-propane, 2,4,6-trimethylbenzylidene Diphenylphosphine oxide and the like. Further, in the case where the adhesive for liquid crystal display cells is used as described below, when a portion directly in contact with the liquid crystal is used, it is preferred to use (meth)acrylic acid in the molecule from the viewpoint of liquid crystal contamination. The compound of the group, for example, 2-methacryloxyethyl isocyanate and 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propene are preferably used. 1-ketone reaction product. This compound can be obtained by the method described in International Publication No. 2006/027982. When the total amount of the resin composition of the present invention is 100 parts by mass, the content of the photopolymerization initiator is usually 0.1. The mass fraction is preferably 10 parts by mass, preferably 0.2 parts by mass to 5 parts by mass.

The thermal radical polymerization initiator which can be contained in the resin composition of the present invention is not particularly limited as long as it can generate a radical by heating and initiates a chain polymerization reaction, and is not particularly limited, and examples thereof include, for example, : organic peroxide, azo compound, benzoin compound, benzoin ether compound, acetophenone compound, tetraphenyl-1,2-ethylene glycol (benzopinacol), etc., more suitable to use tetraphenyl-1,2- Ethylene glycol. For example, as an organic peroxide, the following commercial products can be obtained: Kayamek A, Kayamek M, Kayamek R, Kayamek L, Kayamek LH, Kayamek SP-30C, Perkadox CH-50L, Perkadox BC-FF, Cadox B-40ES Perkadox 14, Trigonox 22-70E, Trigonox 23-C70, Trigonox 121, Trigonox 121-50E, Trigonox 121-LS50E, Trigonox 21-LS50E, Trigonox 42, Trigonox 42LS, Kayaester P-70, Kayaester TMPO-70, Kayaester CND -C70, Kayaester O, Kayaester O-50E, Kayaester AN, Kayabutyl B, Perkadox 16, Kayacarbon BIC-75, Kayacarbon AIC-75 (Kayaku Akzo Co., Ltd.); Permek N, Permek H, Permek S, Permek F, Permek D, Permek G, Perhexa H, Perhexa HC, Perhexa TMH, Perhexa C, Perhexa V, Perhexa 22, Perhexa MC, Percure AH, Percure AL, Percure HB, Perbutyl H, Perbutyl C, Perbutyl ND, Perbutyl L, Percumyl H , Percumyl D, Peroyl IB, Peroyl IPP, Perocta ND (manufactured by Nippon Oil Co., Ltd.), and the like. Further, as an azo compound, the following commercial products can be obtained: VA-044, V-070, VPE-0201, VSP-1001 (Wako Pure Chemical Industries Co., Ltd. System) and so on. When the total amount of the resin composition of the present invention is 100 parts by mass, the content of the thermal radical polymerization initiator is preferably 0.0001 part by mass to 10 parts by mass, more preferably 0.0005 part by mass to 7 parts by mass. It is particularly preferably 0.001 parts by mass to 3 parts by mass.

Examples of the inorganic filler which may be contained in the resin composition of the present invention include molten cerium oxide, crystalline cerium oxide, cerium carbide, cerium nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, and calcium sulfate. , mica, talc, clay, alumina, magnesia, zirconia, aluminum hydroxide, magnesium hydroxide, calcium citrate, aluminum silicate, lithium aluminum niobate, zirconium silicate, barium titanate, glass fiber, carbon fiber, Molybdenum disulfide, asbestos, etc., preferably molten cerium oxide, crystalline cerium oxide, cerium nitride, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, Calcium citrate and aluminum citrate are more preferably molten cerium oxide, crystalline cerium oxide, aluminum oxide or talc. These inorganic fillers can be used in combination of two or more kinds. In particular, when the above-mentioned liquid crystal display cell adhesive is used, if the average particle diameter is too large, when a liquid crystal display cell having a narrow gap is produced, a problem such as a gap cannot be formed smoothly when the upper and lower glass substrates are bonded together. The reason is therefore suitably 3 μm or less, preferably 2 μm or less. The particle diameter can be measured by a laser diffraction/scattering particle size distribution analyzer (dry type) (manufactured by SEISHIN Co., Ltd.; LMS-30).

When the total amount of the resin composition of the present invention is 100 parts by mass, the content of the inorganic filler in the resin composition is usually from 1 part by mass to 60 parts by mass, preferably from 5 parts by mass to 60 parts by mass, more preferably Preferably, it is 10 parts by mass to 50 parts by mass. When the content of the inorganic filler is too small, the adhesion strength is lowered, Moreover, the reliability of moisture resistance is also deteriorated, so the decrease in the adhesive strength after moisture absorption sometimes increases. On the other hand, when the content of the inorganic filler is too large, there may be a case where a gap of the liquid crystal display unit cell cannot be formed.

The thermosetting agent which can be contained in the resin composition of the present invention is not particularly limited (the above-mentioned thermal radical polymerization initiator is not included), and examples thereof include polyamines, polyhydric phenols, and hydrazine compounds. The ruthenium compound is particularly suitable for use. For example, the following aromatic hydrazines: salicylate, diterpene terephthalate, diammonium isophthalate, diammonium 2,6-naphthoate, 2,6-pyridine dioxime, 1,2,4-Benzenetriazine, tetrakisperylene 1,4,5,8-naphthoic acid, tetraterpene tetrabenzoic acid, and the like. Further, in the case of an aliphatic hydrazine, for example, formazan, acetamidine, cesium propionate, bismuth oxalate, diammonium malonate, diterpene succinate, diammonium glutarate may be mentioned. , diammonium adipate, dinonyl pimelate, 1,4-cyclohexane dioxime, diterpenic tartrate, diterpene malate, diimide diacetate, N, N' - N,N'-hexamethylenebis (semicarbazide), triterpene citrate, triammonium oxyacetate, triterpene Cyclohexanetricarboxylate, 1,3-double ( 1,3-bis(hydrazinocarboethyl-5-isopropylhydantoin), etc. having a carbendazim skeleton and preferably having a valeric acid a diterpene compound of a skeleton (a skeleton in which a carbon atom of an intraurethone ring is substituted with an isopropyl group), a ginseng (1-mercaptocarbonylmethyl)isocyanate, and a bis(nonylcarbonyl) group Ethyl)isomeric cyanurate, ginseng (2-mercaptocarbonylethyl)isocyanate, ginseng (3-mercaptocarbonylpropyl)isocyanate, bis(2-indenyl) Carbonyl ethyl) isomeric cyanurate or the like. From the hardening reactivity and potential level In terms of balance, it is preferred that: diammonium isophthalate, diammonium malonate, diammonium adipate, ginseng (1-mercaptocarbonylmethyl)isocyanate, ginseng ( 2-mercaptocarbonylethyl)isocyanate, ginseng (2-mercaptocarbonylethyl)isocyanate, ginseng (3-mercaptocarbonylpropyl)isocyanate, special Preferably, it is ginseng (2-mercaptocarbonylethyl)isocyanate. When the total amount of the resin composition of the present invention is 100 parts by mass, the amount of the heat curing agent used is preferably 0.1 part by mass to 20 parts by mass, more preferably It is 1 part by mass to 10 parts by mass, and may be used in combination of two or more kinds.

Examples of the decane coupling agent which may be contained in the resin composition of the present invention include 3-glycidoxypropyltrimethoxydecane and 3-glycidoxypropylmethyldimethoxydecane. 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, N-phenyl-γ-aminopropyltrimethoxy Baseline, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyltrimethoxy Decane, 3-aminopropyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, vinyltrimethoxydecane, N-(2-(vinylbenzylamino)ethyl)-3 -Aminopropyltrimethoxydecane hydrochloride, 3-methacryloxypropyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane Wait. When the total amount of the resin composition of the present invention is 100 parts by mass, the content of the decane coupling agent in the resin composition is preferably 0.05 parts by mass to 3 parts by mass.

The resin composition of the present invention may contain, as another resin component, one or two selected from the group consisting of epoxy resins, (meth)acrylated epoxy resins, and partially (meth)acrylated epoxy resins. A curable resin composed of the above. For example, an epoxy resin, a mixture of an epoxy resin and a (meth)acrylated epoxy resin, a (meth)acrylated epoxy resin, a partial (meth)acrylated epoxy resin, etc. are mentioned. In particular, in the case of using an adhesive for a liquid crystal display cell, when a portion directly in contact with the liquid crystal is used, a resin having low contamination and solubility to liquid crystal is preferable. Examples of suitable epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, and cresol novolak type. Epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester epoxy resin, glycidylamine Epoxy resin, intramethylene urea resin, iso-cyanate epoxy resin, phenol novolak epoxy resin with trisphenol methane skeleton, and other difunctional phenolic diglycidyl The ether compound, the diglycidyl ether compound of the difunctional alcohol, and the halide or hydride of these materials are not limited thereto. A (meth) propylene oxime epoxy resin or a partial (meth) propylene oxime epoxy resin can be obtained by a conventional reaction of an epoxy resin and (meth)acrylic acid. For example, a predetermined equivalent ratio of (meth)acrylic acid to a catalyst (for example, benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenyl) may be added to the epoxy resin. Phosphine, triphenylstibine, etc., polymerization inhibitors (for example, hydroquinone monomethoxide, hydroquinone, methyl hydroquinone, phenothiazine) (phenothiazine), dibutylhydroxytoluene, etc., obtained by, for example, an esterification reaction at 80 ° C to 110 ° C. The epoxy resin as a raw material is not particularly limited, and is preferably a bifunctional or higher epoxy resin such as bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, or phenol. Novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin , glycidyl ester type epoxy resin, glycidylamine type epoxy resin, ethyl uret urea type epoxy resin, iso-cyanate type epoxy resin, phenol novolak type epoxy resin having a trisphenol methane skeleton And other difunctional phenolic diglycidyl ether compounds, difunctional alcohol diglycidyl ether compounds, and halides, hydrides and the like of these materials. Among these, from the viewpoint of liquid crystal contamination, a bisphenol epoxy resin or a novolac epoxy resin is preferred. Further, the ratio of the epoxy group to the (meth) acrylonitrile group is not limited, and can be appropriately selected from the viewpoints of step suitability and liquid crystal contamination.

In the resin composition of the present invention, a monomer or oligomer of a (meth) acrylate may be further optionally added. Examples of such a monomer or oligomer include a reaction product of dipentaerythritol and (meth)acrylic acid, a reaction product of dipentaerythritol caprolactone and (meth)acrylic acid, and the like, but are not particularly limited.

In the resin composition of the present invention, an organic filler, an additive such as a pigment, a leveling agent, an antifoaming agent, or a solvent may be further optionally added.

As an example of a method of obtaining the resin composition of the present invention, there are the methods described below. First, as the (meth)acrylic resin of the present invention, a photopolymerization initiator and other (meth)acrylic resins, Epoxy resin or the like is dissolved by heating, and after cooling to room temperature, an inorganic filler, a decane coupling agent, a thermal radical polymerization initiator, a thermal curing agent, or the like is mixed, followed by, for example, a three-roll mill, a sand mill, a ball mill, or the like. A known mixing device is uniformly mixed and filtered with a metal mesh to thereby produce the resin composition of the present invention.

The resin composition of the present invention is very useful as an adhesive for electronic parts. Examples of the adhesive for electronic components include an adhesive for a flexible printed wiring board, an adhesive for TAB (Tape automated bonding), an adhesive for a semiconductor, and various adhesives for displays. Limited to this.

Further, the resin composition of the present invention is useful as an adhesive for liquid crystal display cells, and is particularly useful as a liquid crystal sealing agent. The liquid crystal display cell when the resin composition of the present invention is used as a liquid crystal sealing agent is exemplified below.

In the liquid crystal display cell produced by the liquid crystal display cell adhesive of the present invention, a pair of substrates on which a predetermined electrode has been formed are disposed oppositely at a predetermined interval, and the liquid crystal sealing agent of the present invention seals the periphery. And the liquid crystal is sealed in the gap. The type of liquid crystal to be enclosed is not particularly limited. Here, the substrate is composed of a substrate which is composed of glass, quartz, plastic, tantalum, or the like, and at least one of which has light transmissivity. In the liquid crystal sealing agent of the present invention, a spacer such as a glass fiber (gap control material) is added, and then a substrate of the pair of substrates is coated using a dispenser, a screen printing device, or the like. After the liquid crystal sealing agent is applied, it is temporarily hardened at 80 ° C to 120 ° C as needed. Then, liquid crystal was dropped on the inside of the crucible of the liquid crystal sealing agent, and superposed on the other glass substrate in a vacuum to perform gap forming. After the gap is formed, the liquid crystal sealing agent portion is irradiated with ultraviolet rays by an ultraviolet ray irradiator to cure the light. The ultraviolet irradiation amount is preferably 500 mJ/cm ² to 6000 mJ/cm ² , more preferably 1000 mJ/cm ² to 4000 mJ/cm ² . Then, if necessary, it is cured at 90 ° C to 130 ° C for 1 to 2 hours, whereby the liquid crystal display unit cell of the present invention can be obtained. The liquid crystal display cell of the present invention obtained in this manner has no display failure due to liquid crystal contamination, and is a liquid crystal display cell excellent in adhesion and moisture resistance. Examples of the spacer include glass fibers, cerium oxide particles, and polymer particles. The diameter varies depending on the purpose, and is usually 2 μm to 8 μm, preferably 4 μm to 7 μm. The amount of the spacer used is usually 0.1 parts by mass to 4 parts by mass, preferably 0.5 parts by mass to 2 parts by mass, more preferably 0.9 parts by mass to 1.5 parts by mass, per 100 parts by mass of the liquid crystal sealing agent of the present invention.

The novel (meth)acrylic resin of the present invention is very suitable for use in an adhesive. In other words, since the molecule has a carboxyl group and the carboxyl group equivalent is small, the adhesion strength can be improved and the thermosetting reaction can be promoted. Further, the (meth)acrylic resin of the present invention is also characterized in that it is easy to handle because of its small molecular weight, and is also less susceptible to the viscosity of other components when used as an adhesive, and thus is easy to design. In addition, the resin composition obtained by using the (meth)acrylic resin of the present invention is very useful as an adhesive for electronic components and an adhesive for liquid crystal display cells.

[Examples]

Hereinafter, the present invention will be described in more detail by way of Synthesis Examples and Examples, but the present invention is not limited thereto. In addition, as long as there is no special record, the "parts" and "%" in this article are based on quality.

[Synthesis Example 1: Synthesis of acrylated resorcinol diglycidyl ether]

181.2 g of resorcinol diglycidyl ether (Nagase ChemteX Co., Ltd.) was dissolved in 266.8 g of toluene, and 0.8 g of dibutylhydroxytoluene was added thereto as a polymerization inhibitor, and the temperature was raised to 60 °C. Then, 117.5 g of 100% equivalent of acrylic acid of epoxy group was added, and the temperature was further raised to 80 ° C, and thereto was added trimethylammonium chloride, that is, 0.6 g of a reaction catalyst, and stirred at 98 ° C for about 30 hours to obtain a reaction liquid. . This reaction liquid was washed with water, and toluene was distilled off, whereby 253 g of an epoxy acrylate (acrylated resorcinol diglycidyl ether) of the intended resorcinol diglycidyl ether was obtained.

[Synthesis Example 2: Synthesis of maleic anhydride adduct of acrylated resorcinol diglycidyl ether]

Adding 3.66 g of epoxy acrylate of resorcinol diglycidyl ether obtained in Synthesis Example 1, 0.049 g of 4-dimethylaminopyridine, 6.07 g of triethylamine, and 1000 ml of dichloromethane at room temperature After stirring to dissolve, 11.8 g of maleic anhydride was added, and the mixture was stirred at room temperature overnight. The obtained reaction solution was washed three times with dilute hydrochloric acid and three times with water, and then dichloromethane was distilled off, whereby 5 g of acrylated resorcinol diglycidyl ether having a carboxyl group in the molecule was obtained. LC MS (m / z) = 561 (MH), IR 1705cm -1 (COOH).

(Modulation of sealant for liquid crystal dropping method) [Example 1]

The acrylic resin of the present invention synthesized in Synthesis Example 2 was dissolved by heating at 90 ° C in the ratio shown in the following Table 1, and the photopolymerization initiator was heated and dissolved therein, and then cooled to room temperature to add a decane coupling agent. After the cerium oxide and the thermal curing agent were stirred, the mixture was dispersed in a three-roll mill and filtered through a metal mesh (635 mesh) to prepare a sealing agent for a liquid crystal dropping method of Example 1.

[Comparative Examples 1 to 2]

In the same manner, the acrylic resin synthesized in Synthesis Example 1 was heated at 90 ° C in the same manner, and the photopolymerization initiator was heated and dissolved therein, and then cooled to room temperature to add a decane coupling agent. After the cerium oxide, the thermal curing agent, and the hardening accelerator were stirred, the mixture was dispersed in a three-roll mill and filtered through a metal mesh (635 mesh) to prepare a liquid crystal dropping method seal of Comparative Examples 1 and 2. Agent.

The test evaluation was carried out in the following manner.

(moisture resistance test)

To 100 g of the obtained liquid crystal sealing agent, 1 g of 5 μm glass fiber was added as a spacer and stirred and mixed. The liquid crystal sealing agent was applied onto a glass substrate of 50 mm×50 mm, and a glass piece of 1.5 mm×1.5 mm was attached to the liquid crystal sealing agent, and after irradiating ultraviolet rays of 3000 mJ/cm ² by a UV irradiation machine. It was put into an oven and hardened at 120 ° C for 1 hour. The test piece was placed in a pressure cooker tester (TPC-411: manufactured by Tabai Espec Co., Ltd.) at 121 ° C, 2 atm, and humidity of 100% for 12 hours, and a bond tester was used. (SS-30WD: manufactured by Sejin Trading Co., Ltd.) to measure the shear adhesion strength of the glass piece. The results are shown in Table 1.

(hardening speed test)

With respect to the obtained liquid crystal sealing agent, a complex viscosity was measured by a dynamic viscoelasticity measuring apparatus (Rheosol-G5000, manufactured by UBM Co., Ltd.). The setting of the dynamic viscoelasticity measuring device is as follows. Cone: parallel cone with a diameter of 20 mm, frequency: 1 Hz, bending angle: 3 deg., measured temperature was raised from 30 ° C to 120 ° C at a rate of 18 ° C / min, and then maintained at 120 ° C. Viscosity reaches 10,000 Pa. The time at s is shown in Table 1.

1 synthesized by Synthesis Example 2. 2 Synthesized by Synthesis Example 1. 3HCIC (made by Japan FINECHEM Co., Ltd.). * HCIC is finely pulverized by a jet mill to an average particle size of 1.5 μm and a maximum particle size of 5 μm. 4Sila-Ace S-510 (manufactured by CHISSO Co., Ltd.) 5Admafine SEZ (manufactured by ADMATECHS Co., Ltd.) 6 was synthesized by the method described in International Publication WO2006/027982. 7CIC acid (manufactured by Shikoku Chemicals Co., Ltd.). * CIC acid is finely pulverized by a jet mill to an average particle size of 1.5 μm and a maximum particle size of 5 μm.

From the results of Table 1, it is known that Comparative Example 1 has a CIC acid, so it reaches 10,000 Pa. The time is very fast, but the wet adhesion resistance is poor. Further, in Comparative Example 2, since the CIC acid was not contained, the moisture-resistant adhesive strength was high, but the curing rate was slow. On the other hand, in Example 1, without using CIC acid, it reached 10,000 Pa. The time in s can be fast and the moisture-resistant adhesive strength is high. Therefore, the (meth)acrylic resin of the present invention can simultaneously improve both wet adhesion resistance and hardenability.

[Industrial availability]

The novel (meth)acrylic resin of the present invention and the resin composition using the novel (meth)acrylic resin are very useful as an adhesive for electronic components, particularly a liquid crystal sealing agent.

Claims (12)

A (meth)acrylic resin, which is represented by the following formula (1). (wherein, the benzene ring Ar may or may not be present, and when the benzene ring Ar is absent, the bond a represents a single bond or a double bond; further, n represents an integer of 1 to 5, and R ¹ represents a hydrogen atom or a methyl group) . The (meth)acrylic resin according to claim 1, wherein the benzene ring Ar is not present in the above formula (1). The acrylic resin according to claim 1, wherein, in the above formula (1), R ¹ is a hydrogen atom. A resin composition containing the (meth)acrylic resin according to any one of claims 1 to 3. The resin composition according to claim 4, which further contains a photopolymerization initiator. The resin composition according to claim 4, which further contains a thermal radical polymerization initiator. The resin composition according to claim 4, which further contains an inorganic filler. The resin composition according to claim 4, which further contains a ruthenium compound. The resin composition according to claim 4, which further contains a decane coupling agent. An adhesive for electronic parts, which is produced by using the resin composition as described in claim 4. An adhesive for liquid crystal display cells, which is obtained by using the resin composition as described in claim 4. A liquid crystal display unit cell which is formed by adhering a liquid crystal display cell as described in claim 11 with an adhesive.