TW201323384A - Novel hydrazide compound and resin composition using same - Google Patents

Abstract

Provided are: a novel hydrazide compound which exhibits excellent curing properties and excellent moisture resistance; a resin composition which can yield a cured product that exhibits extremely excellent moisture-resistance reliability and other excellent characteristics; and an adhesive and a liquid-crystal sealing agent and so on, using the resin composition. The novel hydrazide compound is represented by formula (1) [wherein n is an integer of 0 to 6, and m is an integer of 1 to 4].

Description

Novel hydrazine compound and resin composition obtained using the hydrazine compound

This invention relates to a novel hydrazide compound. More specifically, the present invention relates to an anthraquinone compound having a decalin (bicyclo[4.4.0]nonane) skeleton. Further, the present invention proposes a resin composition mainly used for an adhesive application, and a liquid crystal sealing agent, which are obtained by using the ruthenium compound.

Up to now, antimony compounds have been used as useful materials for epoxy resin hardeners, or formaldehyde adsorbents, polymer crosslinkers, polymer modifiers, slime control agents,醯肼 Polymer raw materials, etc. In particular, it is often used as a latent curing agent for thermosetting resins such as epoxy resins or acrylic resins which are widely used in the fields of paints and adhesives, and a crosslinking agent for ketone-based acrylic emulsifiers. The reason is considered to be: (1) a point which can be cured at a low temperature due to high reactivity; (2) a point which is excellent in storage stability and can be stored as a single solution at normal temperature; (3) a hardening temperature can be adjusted by a skeleton , the point of hardening time; (4) the point where the glass transition temperature of the hardened material is high. In addition, the ruthenium compound is not only reacted with an epoxy resin but also reacted with an acrylic resin by a Michael addition reaction, so that it is mixed with an epoxy resin and an acrylic resin. The mixed resin composition is also a very good hardener.

For the above reasons, ruthenium compounds are often used as resin compositions for adhesive applications, and an antimony compound and an adhesive are proposed, which have various skeletons, and the adhesives are obtained by using the ruthenium compound (patent Literature 1~5).

[Previous Technical Literature] (Patent Literature)

Patent Document 1: Japanese Laid-Open Patent Publication No. SHO 58-96074

Patent Document 2: Japanese Laid-Open Patent Publication No. Hei 6-80619

Patent Document 3: Japanese Patent Laid-Open No. Hei 11-43473

Patent Document 4: Japanese Laid-Open Patent Publication No. 2002-371069

Patent Document 5: Japanese Laid-Open Patent Publication No. 2006-316142

The present invention has been made in view of the above circumstances, and proposes a novel anthraquinone compound. In other words, the present invention relates to an anthracene compound having a decahydronaphthalene skeleton (bicyclo[4.4.0]nonane skeleton). Further, the present invention proposes a resin composition mainly used for an adhesive application, which is obtained by using the ruthenium compound.

The present invention has been developed based on the findings of the present inventors that the ruthenium compound described in the present invention having a bicyclic skeleton has excellent curability and moisture resistance. In other words, the present invention relates to the following 1) to 14). Furthermore, in this In the specification, "(meth)acryl" means one or both of "acrylic" and "methacrylic", and similarly, "(meth)acryloyl (meth) "acryloyl)" means one or both of "acryloyl" and "methacryl".

1)

An anthracene compound represented by the following formula (1): (wherein, n represents an integer from 0 to 6, and m represents an integer from 1 to 4).

2)

The oxime compound according to the above 1), wherein m is an integer of 2 to 4 in the above formula (1).

3)

The oxime compound according to the above 1), wherein, in the formula (1), n is 0.

4)

The oxime compound according to the above 1), wherein m is 2 in the above formula (1).

5)

The hydrazine compound according to the above 1), which is represented by the following formula (2): .

6)

A resin composition comprising: (a) the anthracene compound according to any one of the above 1) to 5), and (b) a curable resin.

7)

The resin composition according to the above 6), wherein the component (b) is selected from the group consisting of epoxy resins, (meth)acrylated epoxy resins, and partially (meth)acrylated epoxy resins. Kind or more than two.

8)

The resin composition according to the above 6), further comprising (c) an inorganic filler.

9)

The resin composition according to the above 6), which further contains (d) a decane coupling agent.

10)

An adhesive for electronic parts which uses the resin composition as described in 6) above.

11)

An adhesive for a liquid crystal display unit which uses the resin composition as described in 6) above.

12)

A liquid crystal sealing agent which uses the resin composition as described in the above 6).

13)

A liquid crystal display unit which is adhered by using an adhesive for a liquid crystal display unit as described in the above 11).

14)

A liquid crystal display unit which is adhered using a liquid crystal sealing agent as described in the above 12).

Since the novel hydrazine compound of the present invention is excellent in curability and high in hydrophobicity, it can realize a cured product excellent in moisture resistance reliability when used in an adhesive application. Further, in the liquid crystal display unit obtained by the liquid crystal dropping method, a sealant obtained by using a linear alkyl skeleton such as hydrazine (ADH) or hydrazine (SDH) or the like is used. Light leakage often occurs in the vicinity of the cured product, but the novel bismuth compound of the present invention does not exhibit such a phenomenon, and exhibits excellent display characteristics.

[Preferred form of implementing the invention]

Hereinafter, the present invention will be described in detail.

The hydrazine compound represented by the above formula (1) of the present invention can be obtained by reacting a corresponding carboxylic acid compound with an alcohol. After the alkyl ester is formed, it is reacted with hydrazine hydrate; or, the corresponding alkyl carboxylate is reacted with hydrazine hydrate.

Specifically, first, in the presence of an acid catalyst such as sulfuric acid, the corresponding carboxylic acid and the alcohol are stirred at a temperature of about 50 to 100 ° C for 5 to 10 hours to obtain an alkyl ester of the corresponding carboxylic acid compound. .

The carboxylic acid compound corresponding to the carboxylic acid compound is a compound having a carboxyl group bonded to the bicyclic skeleton of the present invention, and specifically, a compound represented by the following formula (3).

(wherein, n represents an integer from 0 to 6, and m represents an integer from 1 to 4).

The alcohol to be used is not particularly limited as long as it is a linear or branched aliphatic alcohol having 1 to 4 carbon atoms. If the reactivity in the next step, that is, the reactivity in the next step, is considered, methanol is used. optimal. When the carboxylic acid compound is used as 1 mol, the amount of the alcohol to be used is preferably from 10 to 100 mol, more preferably from 20 to 50 mol.

The acid catalyst is particularly excellent in sulfuric acid. When the carboxylic acid compound is used as 1 mol, the amount of the acid catalyst used is preferably 0.01 to 1 mol, more preferably 0.05 to 0.5 mol.

The reaction temperature is preferably from 50 to 100 ° C, and the reaction time is preferably from about 3 to 10 hours. The reaction can be traced by thin layer chromatography (TLC) or the like. The reaction solution containing the target ester can be directly used in the next reaction, that is, with hydrazine hydrate. The reaction can also be used in the next reaction after isolation and purification from the reaction liquid by a separation operation such as extraction, concentration, or crystallization.

After the step of synthesizing the alkyl ester of the above carboxylic acid compound, water and hydrazine are mixed in the alkyl ester of the carboxylic acid compound at 0 to 30 ° C, and then reacted at 50 to 100 ° C for 1 to 10 hours.

Although this step does not necessarily require a solvent, it is preferably carried out using water or a water-soluble organic solvent. Examples of the water-soluble organic solvent include alcohols and N-methylpyrrolidone, and alcohols are preferred, and isopropanol is particularly preferred.

This step is carried out by, for example, dissolving an alkyl ester of the above carboxylic acid compound in the above organic solvent, and dropping hydrazine hydrate at 0 to 30 °C. After the dropwise addition, the mixture is heated to 50 to 100 ° C and allowed to react for 1 to 10 hours to obtain the target ruthenium compound.

The hydrazine hydrate used in this step is preferably from 1 to 20 mol, more preferably from 5 to 15 mol, based on 1 mol of the alkyl ester of the carboxylic acid compound.

The end point of the reaction can be confirmed by thin layer chromatography (TLC) or the like. However, when isopropanol is used as the organic solvent, the ruthenium compound formed is gradually precipitated as white crystals because of low solubility. . Therefore, the ruthenium compound of the present invention can be easily obtained by filtration and drying.

The ruthenium compound of the present invention is exemplified by the compounds listed in Tables 1 to 3, but is not particularly limited as long as the structure of the formula (1) is sufficiently satisfied.

A resin composition obtained by using the hydrazine compound of the present invention contains Sub- (b) hardening resin. Examples of the curable resin include an epoxy resin, a (meth)acrylated epoxy resin, a (meth)acrylate monomer, a (meth)acrylate oligomer, and a partial (meth)acrylate. Epoxy resin, etc. Further, when used for an adhesive, in the above, one or two selected from the group consisting of epoxy resins, (meth)acrylated epoxy resins, and partially (meth)acrylated epoxy resins The case of the curable resin composed above is particularly preferable. For example, an epoxy resin, a mixture of an epoxy resin and a (meth)acrylated epoxy resin, a (meth)acrylated epoxy resin, a partially (meth)acrylated epoxy resin, or the like can be given.

In particular, when it is used as an adhesive for a liquid crystal display unit, when it is used in a portion in direct contact with the liquid crystal, it is preferable that the liquid crystal is contaminated and the solubility is low. Examples of preferred epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, and cresol novolak type ring. Oxygen resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester epoxy resin, propylene oxide Amine type epoxy resin, ethyl carbendazole type epoxy resin, isocyanurate type epoxy resin, phenol novolac type epoxy resin having a trisphenol methane skeleton; difunctional phenolic diepoxypropyl group An ether compound or a di-epoxypropyl ether compound of a difunctional alcohol; and such a halide, a hydride, etc., but are not limited thereto.

A (meth)acrylonitrile-based epoxy resin or a partial (meth)acryl-based epoxy resin can be obtained by subjecting an epoxy resin to a conventional reaction with (meth)acrylic acid. It can be obtained by, for example, adding a predetermined equivalent ratio of (meth)acrylic acid, a catalyst (for example, benzyldimethylamine, triethylamine, benzylmethyltrimethyl chloride) to an epoxy resin. Alkyl ammonium, triphenylphosphine, triphenylstibine, etc., and polymerization inhibitors (eg, p-methoxyphenol, hydroquinone, methylhydroquinone, thiophene (phenothiazine), dibutylhydroxytoluene, etc., and the esterification reaction is carried out, for example, at 80 to 110 °C.

The epoxy resin as the raw material is not particularly limited, and a bifunctional or higher epoxy resin is preferable, and examples thereof include a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, and a phenol novolac. Varnish type epoxy resin, 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 type epoxy resin, epoxy propylamine type epoxy resin, ethyl uret urea type epoxy resin, isocyanurate type epoxy resin, phenol novolak type epoxy having trisphenol methane skeleton a resin; a di-epoxypropyl ether compound of a difunctional phenol; a diepoxypropyl etherate of a difunctional alcohol; and such a halide, a hydride, and the like. Among these, from the viewpoint of liquid crystal contamination, a bisphenol type epoxy resin or a novolak type epoxy resin is more preferable. Further, the ratio of the epoxy group to the (meth) acrylonitrile group is not particularly limited, and is appropriately selected from the viewpoints of step suitability and liquid crystal contamination.

In the resin composition of the present invention, a monomer and/or oligomer of a (meth) acrylate may be further used as needed. Examples of such a monomer or oligomer include a reaction product obtained by reacting dipentaerythritol with (meth)acrylic acid, and a reaction obtained by reacting dipentaerythritol-caprolactone with (meth)acrylic acid. There are no special restrictions on things.

The resin composition of the present invention is preferably used for an adhesive. At this time, the phase The content of the component (a) cerium compound is preferably from 1 to 20 parts by mass, more preferably from 1 to 10 parts by mass, per 100 parts by mass of the component (b) curable resin. The remainder is: an inorganic filler, a decane coupling agent, a photopolymerization initiator, a thermal radical polymerization initiator, a thermosetting accelerator, and the like.

The inorganic filler (component (c)) which the resin composition of the present invention may contain may, for example, be fused cerium oxide, cerium oxide cerium, cerium carbide, cerium nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, sulfuric acid. Calcium, 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., with molten cerium oxide, crystalline cerium oxide, tantalum nitride, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium citrate Aluminum citrate is preferred, and molten cerium oxide, crystalline cerium oxide, aluminum oxide, and talc are more preferable. These inorganic fillers can be used in combination of two or more kinds. In particular, when it is used as an adhesive for a liquid crystal display unit, if the average particle diameter of the inorganic filler is too large, the gap between the upper and lower glass substrates may not be formed when the liquid crystal display unit having a narrow gap is formed. The reason is mainly 3 μm or less, preferably 2 μm or less. The particle size 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 to 60 parts by mass, preferably from 5 to 50 parts by mass. When the content of the inorganic filler is too small, the adhesion strength is lowered and the moisture resistance reliability is also poor, so sometimes moisture absorption The adhesion strength will also be greatly reduced. On the other hand, when the content of the inorganic filler is too large, when used as an adhesive for a liquid crystal display unit, a gap of the liquid crystal cell may not be formed.

The decane coupling agent (component (d)) which the resin composition of the present invention may contain may, for example, be 3-glycidoxypropyltrimethoxydecane or 3-glycidoxypropylmethyldimethoxy Baseline, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, N-phenyl-γ-aminopropyl Trimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyltrimethyl Oxydecane, 3-aminopropyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, vinyltrimethoxydecane, N-(2-(vinylbenzylamino)ethyl) 3-aminopropyltrimethoxydecane hydrochloride, 3-methylpropenyloxypropyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxy Base decane and the like. 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 0.01 to 3 parts by mass.

The photopolymerization initiator which can be contained in the resin composition of the present invention is not particularly limited as long as it is a compound capable of generating a radical by irradiation of an energy ray such as ultraviolet rays or visible light, and the chain polymerization reaction is carried out, and examples thereof include, for example: Benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, diethylthioxanthone, benzophenone, 2-ethyl hydrazine, 2-hydroxy-2-methylpropiophenone , 2-methyl-[4-(methylthio)phenyl]-2-(N-morpholinyl)-1-propane, 2,4,6-trimethylbenzhydryldiphenylphosphine oxide Things and so on. In addition, when used as an adhesive for the liquid crystal display unit described below, when used in the liquid When the crystal is directly contacted, it is preferred to use a compound having a (meth)acryloyl group in the molecule from the viewpoint of liquid crystal contamination, and it is preferred to use, for example, a 2-methylpropenyloxy group. A reaction product obtained by reacting ethyl isocyanate with 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one. 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 to 20 parts by mass, preferably 1 to 15 parts by mass.

The thermal radical polymerization initiator which may be contained in the resin composition of the present invention is not particularly limited as long as it is a compound capable of generating a radical by heating to initiate a chain polymerization reaction, and examples thereof include an organic peroxide. An azo compound, a benzoin compound, a benzoin ether compound, an acetophenone compound, a benzopinacol or the like is preferably used as the benzopinacol. The organic peroxide can be obtained in the form of a commercially available product, for example: Kayamek A, Kayamek M, Kayamek R, Kayamek L, Kayamek LH, Kayamek SP-30C, Perdox CH-50L, Perdox BC-FF, Cadox B-40ES, Perdox 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, Kayaeste O-50E, Kayaester AN, Kayabutyl B, Perdox 16, Kayacarbon BIC-75, Kayacarbon AIC-75 (made by 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 (made by Nippon Oil Co., Ltd.), etc. Further, the azo compound can be obtained, for example, in the form of a commercially available product: VA-044, V-070, VPE-0201, VSP-1001, etc. (made by Wako Pure Chemical Industries, Ltd.). 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 to 10 parts by mass, more preferably 0.0005 to 7 parts by mass, and 0.001 to 3 parts by mass. Excellent quality.

In the resin composition of the present invention, it can be further formulated as needed: an organic filler; and an additive such as a pigment, a leveling agent, an antifoaming agent, or a solvent.

An example of a method of obtaining the resin composition of the present invention is as follows. First, the curable resin (ingredient (b)) is heated to dissolve the photopolymerization initiator, and after cooling to room temperature, the cerium compound (ingredient (a)) and inorganic filler (ingredient (c)) of the present invention are mixed. a decane coupling agent (ingredient (d)), a thermal radical polymerization initiator, and the like, and then uniformly mixed by using a conventional mixing device such as a three-roll mill, a sand mill, a ball mill, or the like, and then filtered by a metal mesh. That is, the resin composition of the present invention can be produced.

The resin composition of the present invention is very useful as an adhesive for electronic parts. Examples of the adhesive for an electronic component 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 a display. It is not limited to this.

Further, the resin composition of the present invention is very useful as an adhesive for liquid crystal display units, and is particularly useful as a liquid crystal sealing agent. The following is an example of a liquid crystal display unit when the resin composition of the present invention is used as a liquid crystal sealing agent.

A liquid crystal display unit manufactured by using an adhesive for a liquid crystal display unit of the present invention is disposed such that one of the predetermined electrodes is formed facing the substrate at a predetermined interval, and the liquid crystal sealing agent of the present invention is used to seal the periphery. A liquid crystal is enclosed in the gap. The type of the liquid crystal to be enclosed is not particularly limited. Here, the substrate is composed of a combination substrate having at least one side that is translucent, and the combination substrate is made of glass, quartz, plastic, tantalum or the like. In the liquid crystal display unit of the present invention, after a spacer such as a glass fiber (gap control material) is added to the liquid crystal sealing agent of the present invention, a dispenser or a screen printing device or the like is used, and one of the pair of substrates is used. After the liquid crystal sealing agent is applied, it is pre-cured at 80 to 120 ° C as needed. Then, after the liquid crystal is dropped on the inner side of the bank of the liquid crystal sealing agent, another substrate (for example, a glass substrate) is laminated in a vacuum to form a gap. After the gap is formed, the liquid crystal sealing agent portion is irradiated with ultraviolet rays using an ultraviolet ray irradiator to perform photocuring. The ultraviolet irradiation amount is preferably 500 to 6000 mJ/cm ² , more preferably 1000 to 4000 mJ/cm ² . Then, if necessary, it is cured at 90 to 130 ° C for 1 to 2 hours, whereby the liquid crystal display unit of the present invention can be obtained. The liquid crystal display unit of the present invention thus obtained does not cause display failure due to liquid crystal contamination, and is excellent in adhesion and moisture resistance reliability. The spacer may, for example, be glass fiber, cerium oxide beads, polymer beads or the like. The diameter of the spacer varies depending on the purpose, and is usually 2 to 8 μm, preferably 4 to 7 μm. The amount of the spacer used is usually about 0.1 to 4 parts by mass, preferably about 0.5 to 2 parts by mass, more preferably about 0.9 to 1.5 parts by mass, per 100 parts by mass of the liquid crystal sealing agent of the present invention.

The novel hydrazine compound of the present invention is very suitable for use in adhesives. In other words, since not only the reactivity is good, but also the storage stability is good, and the hydrophobicity is high, the moisture resistance reliability of the cured product is also remarkable. Further, the resin composition obtained by using the ruthenium compound of the present invention is very useful as an adhesive for electronic parts and an adhesive for liquid crystal display units.

[Examples]

The invention is illustrated in more detail below by way of examples, but the invention is not limited by the examples. In addition, as long as it is not specifically described, in this article, "parts" and "%" are the quality standards.

[Example 1] Synthesis of dioxane 2,6-decahydronaphthalene dicarboxylate (dimethyl 3,8-bicyclo[4.4.0]decanedicarboxylate) (Compound No. 6 in Table 2) (step 1)

2,6-decahydronaphthalene dicarboxylic acid (3,8-bicyclo[4.4.0]decanedicarboxylic acid: synthesized by the method described in Example 1 of JP-A-2004-331645) 30.0 g dissolved In 127 g of methanol, 1.3 g of sulfuric acid was added. After stirring for 8 hours under reflux, an evaporator was used to remove methanol. Toluene was added to the obtained liquid, and further, a 7% aqueous sodium hydrogencarbonate solution was added thereto and stirred, and then liquid separation was carried out. Then, a 7% aqueous solution of sodium hydrogencarbonate was added to the organic layer and After stirring, liquid separation was carried out. This operation was repeated using pH test paper until the water layer became neutral. Then, ion-exchanged water was added to the organic layer and stirred, and then liquid separation was carried out. Repeat this operation twice. An evaporator was used to remove toluene, and dimethyl 2,6-decahydronaphthalate (dimethyl 3,8-bicyclo[4.4.0]decanedicarboxylate) 32 g was obtained. Further, this compound is also available from the market as H-NDCM (manufactured by Mitsubishi Gas Corporation).

(Step 2)

20.0 g of 2,6-decahydronaphthalene dicarboxylate (dimethyl 3,8-bicyclo[4.4.0]decanedicarboxylate) synthesized in the step 1 was dissolved in 74 mL of isopropyl alcohol, and 44.4 g of hydrazine monohydrate was added dropwise over 30 minutes using a dropping funnel. Then, the temperature was raised to 80 ° C and stirred for 3 hours. The precipitated crystals were collected by filtration and dried, whereby 2.8 g of the desired 2,6-decahydronaphthalene dicarboxylate (3,8-bicyclo[4.4.0]decanedicarboxylic acid dioxime) was obtained. ( ¹ H-NMR data: 8.9 (2H), 4.1 (4H), 2.0 to 2.1 (2H), 1.6 to 1.7 (4H), 1.4 to 1.5 (8H), 1.2 (2H)

[Reference Synthesis Example 1] Synthesis of epoxy acrylate of bisphenol A epoxy resin

282.5 g of bisphenol A type epoxy resin (product name: YD-8125, manufactured by Nippon Steel Chemical Co., Ltd.) was dissolved in 266.8 g of toluene, and dibutylhydroxytoluene as a polymerization inhibitor was added thereto to 0.8 g. After that, the temperature was raised to 60 °C. Then, 117.5 g of 100% equivalent of acrylic acid of epoxy group was added, and further heated to 80 ° C, and then a reaction catalyst, that is, 0.6 g of trimethylammonium chloride was added thereto, and stirred at 98 ° C for about 30 hours. The reaction solution was obtained. After the reaction liquid was washed with water, toluene was distilled off, whereby 395 g (KAYARAD ^RTM R-93100) of the desired bisphenol A type epoxy acrylate was obtained.

(Modulation of liquid crystal sealant) [Embodiment 2]

The curable resin component (component (b)) was mixed and stirred at a ratio shown in the following Table 4, and then a photopolymerization initiator was added thereto, and the mixture was heated and dissolved at 90 °C. After cooling to room temperature, an inorganic filler (ingredient (c)), a decane coupling agent (ingredient (d)), and a hardening agent (ingredient (a)) synthesized in Example 1 were added and stirred, and a three-roll mill was used. The liquid crystal sealant was prepared by dispersing it and filtering it with a metal mesh (635 mesh).

[Comparative Example 1]

A liquid crystal sealing agent was prepared in the same manner as in Example 2 except that the compound synthesized in Example 1 was used instead of 0.65 g of hexamethylene hydride (manufactured by Otsuka Chemical Co., Ltd.).

[Comparative Example 2]

The same procedure as in Example 2 except that 0.96 g of ginseng (2-mercaptocarbonylethyl)isocyanurate (manufactured by Nippon FINECHEM Co., Ltd.) was used instead of the compound synthesized in Example 1 as a curing agent. It is carried out to modulate the liquid crystal sealant.

The evaluation test was carried out in the following manner.

(Measurement of adhesion strength)

1 g of 5 μm glass fiber as a spacer was added to 100 g of each liquid crystal sealing agent prepared, and the mixture was stirred and mixed. After applying the liquid crystal sealing agent to a glass substrate of 50 mm × 50 mm, a glass piece of 1.5 mm × 1.5 mm was attached to the liquid crystal sealing agent, and irradiated with a UV irradiation machine at 3000 mJ/cm ² . After the ultraviolet rays, they were placed in an oven at 120 ° C to be thermally hardened for 1 hour. The shear strength of the glass piece was measured using a bond tester (SS-30WD, manufactured by Sejin Corporation). Will be shown in Table 4.

(Determination of wet adhesion strength)

A measurement sample identical to the above-described adhesion strength measurement was prepared. The measurement sample was placed in a pressure cooker tester (TPC-411, manufactured by ESPEC Co., Ltd.) under the conditions of 121 ° C, 2 atm, and 100% humidity for 12 hours, and then the sample was measured using the above-mentioned bond strength tester. The results are shown in Table 4.

(panel display characteristic test)

After the prepared liquid crystal sealing agent was filled in a syringe and defoamed, a liquid crystal sealing agent was applied to a glass substrate using a dispenser (SHOTMASTER 300, manufactured by Musashi Engineering Co., Ltd.) (orientation film: SE-made by Nissan Chemical Co., Ltd.) After 6414 was applied and rubbed, a suitable amount of liquid crystal was dropped in the sealing frame. The substrate was placed in a vacuum bonding apparatus, and after laminating another substrate in a vacuum, it was allowed to harden at 120 ° C for 1 hour. After the obtained analog panel was energized, it was observed on the polarizing film. Further, after a plurality of vibrations or pressures were applied in the vicinity of the contact between the liquid crystal and the liquid crystal sealing agent, they were observed with a microscope. The observation results were judged in the following manner.

○: Unorientation was not confirmed, and no light leakage was observed near the seal.

×: It was confirmed that there was a poor orientation, and light leakage was observed in the vicinity of the seal portion.

The results are shown in Table 4.

From the results of Table 4, it was confirmed that the ruthenium compound of the present invention has excellent curability and is excellent in moisture resistance, and as a liquid crystal sealant. When used with a hardener, it exhibits good panel display characteristics.

[Industrial availability]

The novel hydrazine compound of the present invention and a resin composition obtained by using the hydrazine compound are very useful as an adhesive for electronic parts, and are particularly useful as a liquid crystal sealing agent.

Claims (14)

An anthracene compound represented by the following formula (1): (wherein, n represents an integer from 0 to 6, and m represents an integer from 1 to 4). The oxime compound according to claim 1, wherein, in the above formula (1), m is an integer of 2 to 4. The oxime compound according to claim 1, wherein, in the above formula (1), n is 0. The oxime compound according to claim 1, wherein m is 2 in the above formula (1). The hydrazine compound according to claim 1, which is represented by the following formula (2): . A resin composition comprising: (a) the hydrazine compound according to any one of claims 1 to 5, and (b) a curable resin. The resin composition according to claim 6, wherein the component (b) is one selected from the group consisting of epoxy resins, (meth)acrylated epoxy resins, and partially (meth)acrylated epoxy resins. Kind or more than two. The resin composition according to claim 6, which further contains (c) no Machine packing. The resin composition according to claim 6, which further contains (d) a decane coupling agent. An adhesive for an electronic component which uses the resin composition as claimed in claim 6. An adhesive for a liquid crystal display unit which uses the resin composition as claimed in claim 6. A liquid crystal sealing agent which uses the resin composition as claimed in claim 6. A liquid crystal display unit which is adhered by using an adhesive for a liquid crystal display unit according to claim 11. A liquid crystal display unit which is adhered using a liquid crystal sealing agent as claimed in claim 12.