TWI568762B - An esterified epoxy resin, a method for producing the same, and a hardening composition containing the same - Google Patents

Description

Esterified epoxy resin, method for producing the same, and curable composition containing the same

The present invention relates to an esterified epoxy resin excellent in liquid stability, a method for producing the same, and a curable composition containing the same.

In the method for producing a liquid crystal display device, the dropping method is a method in which a liquid crystal panel is directly dropped into a loop of a sealant under vacuum to perform lamination and vacuum opening, and a panel can be produced. This dropping method has many advantages such as a decrease in the use amount of the liquid crystal, a shortening of the injection time of the liquid crystal injection panel, and the like, and has become the mainstream of the current manufacturing method of the liquid crystal panel using the large substrate. 4. The method containing the dropping method is to apply a sealant. After the liquid crystal is bonded, the gap and the alignment are performed, and then the sealant is hardened mainly by ultraviolet curing.

An esterified epoxy resin composed of (meth)acrylic acid was used as a raw material for the sealant (Patent Documents 1 to 3). These documents describe a method of converting an epoxy group to a (meth)acryloyl group, for example, a reaction of a compound having an epoxy group with (meth)acrylic acid. The (meth)acrylated epoxy resin described in Patent Document 3 is particularly excellent in liquid crystal resistance.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 05-295087

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-3260

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2012-77202

The present inventors have found that in the method described in Patent Documents 1 to 3, the sealant containing the (meth)acrylic acid esterified epoxy resin has a high viscosity, and it is impossible to add a latent curing agent (solid type), or The amount of addition is limited, and the stability of the liquid when mixed with a latent hardener is low.

Therefore, the problem of the present invention is to maintain the liquid crystallinity of the sealant containing the esterified epoxy resin (meth)acrylic acid, and to improve the liquid stability of the sealant and to lower the viscosity.

As a result of careful examination of the above-mentioned problems, the inventors of the present invention found that the esterified epoxy resin composed of (meth)acrylic acid described in Patent Documents 1 to 3 generates a hydroxyl group by ring opening of the epoxy ring, which causes generation. The problem of unstable stability and high viscosity of the above liquid stability.

Patent Document 3 describes, for example, the following formula: A resin composition of an esterified epoxy resin composed of methacrylic acid, which is excellent in liquid crystal resistance. However, the hydroxyl group present in the esterified epoxy resin composed of (meth)acrylic acid deteriorates the liquid stability of the sealant, and the viscosity of the sealant increases due to intermolecular hydrogen bonding.

The present invention is as follows.

(1) An esterified epoxy resin characterized by the general formula (1): Represents the resin and sometimes consists of its polymer, or in the general formula (2): Represents the resin and sometimes consists of its polymer, or in the general formula (3): The resin is sometimes composed of a polymer thereof, and in each formula, X-type O-, alkylene group having 1 to 4 carbon atoms, or alkylene group having 2 to 4 carbon atoms, Y-system Alkyl group having 1 to 4 carbon atoms - an extended aryl group having 6 to 20 carbon atoms - an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms - 6 to 20 carbon atoms An aryl group or a group: -R ⁷ -(OR ⁷ ) _n - (wherein R ⁷ is an alkylene group having 1 to 4 carbon atoms, n is an integer of 0 or 1 to 6), and each R ²¹ Each of them is independently hydrogen or a methyl group, and each of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ^{16 is} independently hydrogen, glycidyl, methyl glycidyl, (meth)acryl fluorenyl, Alkyl, fluorenyl, silyl, acetal, or a group: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ or a group: -CH ₂ -C(CH ₃ ) (OR')-CH ₂ -OR ⁸ (wherein R' is hydrogen, (meth)propenyl group, alkyl group, fluorenyl group, formyl group, or acetal group, and R ⁸ is (meth) propylene Sulfhydryl, but present in the base: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ in R', the average hydrogen is less than 0.8), present in the general formula (1) and (2) R ^11, R ^12, R ¹⁴ and R ^15, the glycidyl and methyl glycidyl And oleyl _{group: -CH 2 -CH (OR ')} - CH 2 -OR 8 and _{group: -CH 2 -C (CH 3)} (OR') - CH 2 -OR 8 total average of 2 or more, The average number of glycidyl groups and methyl glycidyl groups and the group: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ and the group: -CH ₂ -C(CH ₃ )(OR')-CH The ratio of the average number of ₂ -OR ⁸ is 10:90~90:10, which exists in R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ of general formula (3), glycidyl group and The methyl glycidyl group and the group: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ and the group: -CH ₂ -C(CH ₃ )(OR')-CH ₂ -OR ^{8 have} an average of 2 More than one, the average number of glycidyl groups and methyl glycidyl groups and groups: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ and base: -CH ₂ -C(CH ₃ )(OR') The ratio of the average number of -CH ₂ -OR ⁸ is 10:90~90:10].

(2) An esterified epoxy resin characterized by the general formula (1a): Represents the resin and sometimes consists of its polymer, or in the general formula (2a): Represents the resin and sometimes consists of its polymer, or in the general formula (3a): The resin is sometimes composed of a polymer thereof, and in each formula, X-type O-, alkylene group having 1 to 4 carbon atoms, or alkylene group having 2 to 4 carbon atoms, Y-system Alkyl group having 1 to 4 carbon atoms - an extended aryl group having 6 to 20 carbon atoms - an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms - 6 to 20 carbon atoms An aryl group or a group: -R ⁷ -(OR ⁷ ) _n - (wherein R ⁷ is an alkylene group having 1 to 4 carbon atoms, n is an integer of 0 or 1 to 6), and each R ²¹ Each of them is independently hydrogen or a methyl group, and each of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ^{16 is} independently hydrogen, glycidyl, methyl glycidyl, (meth)acryl fluorenyl, Or a group: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ or a group: -CH ₂ -C(CH ₃ )(OR')-CH ₂ -OR ⁸ (wherein R' is hydrogen or Methyl) propylene fluorenyl group, R ⁸ is a (meth) acryl fluorenyl group, which is present in the group R: in the group: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ , and the hydrogen is on average less than 0.8 In the general formulae (1a) and (2a), R ¹¹ , R ¹² , R ¹⁴ and R ¹⁵ , glycidyl group and methyl glycidyl group and group: -CH ₂ -CH(OR') and -CH ₂ -OR ⁸ _{group: -CH 2 -C (CH 3)} (OR ') - CH 2 -OR 8 of total average 2 And the average number of groups, glycidyl and methyl glycidyl _{group: -CH 2 -CH (OR ')} - CH 2 -OR 8 group, _{and: -CH 2 -C (CH 3)} (OR') - The ratio of the average number of CH ₂ -OR ⁸ is 10:90 to 90:10, which is present in R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ in the general formula (3a), glycidol Base and methyl glycidyl group with: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ and base: -CH ₂ -C(CH ₃ )(OR')-CH ₂ -OR ⁸ The average number of glycidyl groups and methyl glycidyl groups of 2 or more and the base: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ and the group: -CH ₂ -C(CH ₃ )(OR The ratio of the average number of ')-CH ₂ -OR ⁸ is 10:90~90:10].

(3) A method for producing an esterified epoxy resin, comprising the following steps (1A) to (1C): (1A) a polyfunctional epoxy compound having 2 or more epoxy groups in a molecule, in a metal In the presence of a catalyst, a step of reacting with a polyhydroxy compound having 2 or more hydroxyl groups in the molecule to obtain a ring-opened form of a polyfunctional epoxy compound, (1B) obtaining the step (1A) The step of epoxidizing the hydroxyl group of the epoxy ring-opening compound of the polyfunctional epoxy compound to obtain an epoxy resin, and (1C) the step of reacting the epoxy resin obtained in the step (1B) with (meth)acrylic anhydride.

(4) A method for producing an esterified epoxy resin according to the above item (2), which is characterized by containing the general formula (4): a resin represented by an epoxy resin sometimes composed of a polymer thereof, or a general formula (5): a resin represented by an epoxy resin sometimes composed of a polymer thereof, or a general formula (6): The resin represented by the resin and the epoxy resin sometimes composed of the polymer thereof (wherein X is -O-, an alkylene group having 1 to 4 carbon atoms, or an alkylene group having 2 to 4 carbon atoms) , Y is an alkyl group having 1 to 4 carbon atoms - an exoaryl group having 6 to 20 carbon atoms - an alkyl group having 1 to 4 carbon atoms, and an alkyl group having 1 to 4 carbon atoms 6 to 20 of an extended aryl group, or a group: -R ⁷ -(OR ⁷ ) _n - (wherein, R ⁷ is an alkylene group having 1 to 4 carbon atoms, and n is an integer of 0 or 1 to 6), Each of R ^{21 is} independently hydrogen or methyl, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently hydrogen, glycidyl, or methyl glycidyl, but are present in general. At least two of R ¹ , R ² , R ⁴ and R ^{5 in} the formulae (4) and (5) are glycidyl groups or methyl glycidyl groups, and R ¹ and R ² are present in the general formula (6). And at least two of R ³ , R ⁴ , R ⁵ and R ⁶ are glycidyl or methyl glycidyl groups are reacted with (meth)acrylic anhydride.

(5) The method for producing an esterified epoxy resin according to the above item (4), which comprises the method of the following steps (2A) to (2B), wherein the general formula (4) of the above item (4) is produced. The resin represented by any one of the general formula (6) and the epoxy resin sometimes composed of the polymer thereof, (2A) are given by the general formula (7a): Or general formula (8a): Or general formula (9a): [In each formula, X and R ²¹ are the epoxy compounds represented by the above-mentioned item (4)], in the presence of a metal catalyst, and the following general formula (10): HO-Y-OH (10) (wherein, Y is as defined in the above item (4)), and the dihydroxy compound is reacted to obtain a general formula (7b): a resin represented by an epoxy ring ring sometimes composed of a polymer thereof, or a general formula (8b): a resin represented by an epoxy ring ring sometimes composed of a polymer thereof, or a general formula (9b): a step of forming a resin and an epoxy ring-opening material which is sometimes composed of a polymer (wherein X, Y and R ²¹ are as defined above), (2B) a general result obtained in the step (2A) The step of epoxidizing the resin represented by any one of the formula (7b) to the general formula (9b) and the hydroxyl group of the epoxy ring-opening material composed of the polymer.

(6) A method for producing an esterified epoxy resin, which comprises the following steps (1A), (1B), (1C') and (1D), wherein (1A) has an epoxy group having 2 or more in the molecule; a polyfunctional epoxy compound, which is reacted with a polyhydroxy compound having 2 or more hydroxyl groups in the molecule in the presence of a metal catalyst to obtain an epoxy ring-opening of a polyfunctional epoxy compound, and (1B) a step ( 1A) a step of epoxidizing a hydroxyl group of the epoxy ring-opening compound of the obtained polyfunctional epoxy compound to obtain an epoxy resin, and (1C') reacting the epoxy resin obtained in the step (1B) with (meth)acrylic acid to obtain a step of partially esterifying the epoxy resin, (1D) partially esterifying the epoxy resin obtained in the step (1C') with a (meth) propylene sulfhydrylating agent, an alkylating agent, a thiolating agent, a germyl group The step of reacting the agent or the acetalizing agent.

(7) A method for producing an esterified epoxy resin according to the above item (1), which is characterized by containing the general formula (1'): a resin and a partially esterified epoxy resin sometimes composed of a polymer thereof, or in the general formula (2'): a resin and a partially esterified epoxy resin sometimes composed of a polymer thereof, or in the general formula (3'): a resin represented by a resin and a partially esterified epoxy resin sometimes composed of a polymer thereof (in the formula, X-O-, an alkyl group having 1 to 4 carbon atoms, or a carbon number of 2 to 4) An alkylene group, Y is an alkylene group having 1 to 4 carbon atoms, an extended aryl group having 6 to 20 carbon atoms, an alkylene group having 1 to 4 carbon atoms, and an alkylene group having 1 to 4 carbon atoms. An extended aryl group having 6 to 20 carbon atoms or a group: -R ⁷ -(OR ⁷ ) _n - (wherein R ⁷ is an alkylene group having 1 to 4 carbon atoms, and n is 0 or 1 to 6 Integer), each R ^{21 is} each independently hydrogen or methyl, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently hydrogen, glycidyl, methyl glycidyl, or :-CH ₂ -CH(OH)-CH ₂ -OR ⁸ (wherein R ⁸ is a propylene fluorenyl group or a methacryl fluorenyl group), and R ^{11 is} present in the general formulae (1') and (2') And at least two of R ¹² , R ¹⁴ and R ¹⁵ are glycidyl, methyl glycidyl, or a group: -CH ₂ -CH(OH)-CH ₂ -OR ⁸ or a group: -CH ₂ -C ( CH ₃ )(OH)-CH ₂ -OR ⁸ , the average number of glycidyl groups and methyl glycidyl groups and the group: -CH ₂ -CH(OH)-CH ₂ -OR ⁸ and the group: -CH ₂ - the average ratio of the number of -CH _{C (CH 3) (OH)} 2 -OR 8 of 10: 90 ~ 90: 10, present in the general formula ^{(3 ') R 11, R} 12, R 13, R 14, R 15 and R ¹⁶ is at least two glycidyl groups, glycidyl methyl, Or an average of -CH ₂ -CH(OH)-CH ₂ -OR ⁸ or a group: -CH ₂ -C(CH ₃ )(OH)-CH ₂ -OR ⁸ , glycidyl and methyl glycidyl The ratio of the number to the base: -CH ₂ -CH(OH)-CH ₂ -OR ⁸ and the base: -CH ₂ -C(CH ₃ )(OH)-CH ₂ -OR ⁸ is 10:90 ~90:10] Reacts with a (meth) propylene sulfhydrylating agent, an alkylating agent, a thiolating agent, a formylating agent, or an acetalizing agent.

(8) The method for producing an esterified epoxy resin according to the above item (7), which comprises the general formula (1' of the above item (7) by the following steps (2A) to (2C); a resin represented by any of the general formulas (3') and a partially esterified epoxy resin sometimes composed of a polymer thereof, (2A) is given by the general formula (7a): General formula (8a): Or general formula (9a): [In each formula, X and R ²¹ are an epoxy compound represented by the above-mentioned item (7), in the presence of a metal catalyst, and the following general formula (10): HO-Y-OH (10) (in the formula, Y is as defined in the above item (7)), the dihydroxy compound is reacted to obtain the general formula (7b): An epoxy ring or a general formula (8b) which is represented by a resin and sometimes a polymer thereof: An epoxy ring or a general formula (9b) which is represented by a resin and sometimes a polymer thereof: a resin represented by the epoxy ring-opening compound (wherein, X, Y and R ²¹ are as defined above), and (2B) a general formula obtained by the step (2A) 7b)~ The resin represented by any one of the general formula (9b) and the hydroxyl group of the epoxy ring-opening material which is sometimes composed of the polymer are epoxidized to obtain the general formula (4): The resin represented by the resin and sometimes the polymer thereof, or the general formula (5): Resin represented by epoxy resin and sometimes composed of its polymer, or general formula (6): The resin represented by the resin and the epoxy resin sometimes composed of the polymer thereof (wherein X is -O-, an alkylene group having 1 to 4 carbon atoms, or an alkylene group having 2 to 4 carbon atoms) , Y is an alkyl group having 1 to 4 carbon atoms - an exoaryl group having 6 to 20 carbon atoms - an alkyl group having 1 to 4 carbon atoms, and an alkyl group having 1 to 4 carbon atoms 6 to 20 of an extended aryl group, or a group: -R ⁷ -(OR ⁷ ) _n - (wherein, R ⁷ is an alkylene group having 1 to 4 carbon atoms, and n is an integer of 0 or 1 to 6), Each of R ^{21 is} independently hydrogen or methyl, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently hydrogen, glycidyl, or methyl glycidyl, but are present in general. At least two of R ¹ , R ² , R ⁴ and R ^{5 in} the formulae (4) and (5) are glycidyl groups or methyl glycidyl groups, and R ¹ and R ² are present in the general formula (6). And at least two of R ³ , R ⁴ , R ⁵ and R ⁶ are glycidyl or methyl glycidyl groups, and (2C) any one of general formulas (4) to (6) obtained in the step (2B). The resin represented by the resin and the epoxy resin sometimes composed of the polymer thereof are reacted with (meth)acrylic acid.

(9) A curable composition characterized by containing the esterified epoxy resin according to the above item (1) or (2).

(10) A curable composition comprising the esterified epoxy resin obtained by the production method according to any one of the items (3) to (8) above.

According to the present invention, the solubility to the liquid crystal can be suppressed, the contamination of the liquid crystal can be prevented, the viscosity of the sealant can be lowered, and the liquid stability of the sealant can be improved.

[Best Mode for Carrying Out the Invention]

Preferred embodiments of the present invention are described below.

The present invention is a general formula (1) to (3) [in each formula, X-form O-, an alkylene group having 1 to 4 carbon atoms, or an alkylene group having 2 to 4 carbon atoms, and Y is a carbon atom. Number of 1-4 alkyl groups - 6 to 20 carbon atoms of the extended aryl group - an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms - a carbon number of 6 to 20 An aryl group or a group: -R ⁷ -(OR ⁷ ) _n - (wherein, R ⁷ is an alkylene group having 1 to 4 carbon atoms, and n is an integer of 0 or 1 to 6), and each of R ^{21 is} each other Independently hydrogen or methyl, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently hydrogen, glycidyl, methyl glycidyl, (meth)acrylonitrile, alkyl , a mercaptoalkyl group, an acetal group, or a group: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ or a group: -CH ₂ -C(CH ₃ )(OR')-CH ₂ -OR ⁸ ( Wherein R' is hydrogen, (meth)propenyl, alkyl, fluorenyl, germyl, or acetal, and R ⁸ is (meth)acryl fluorenyl, but is present at the group: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ in R', the average hydrogen is less than 0.8), and R ¹¹ , R ¹² , R ¹⁴ and R present in the general formulae (1) and (2) ^15, with the glycidyl and methyl glycidyl _{group: -CH 2 -CH (OR ')} - CH 2 -OR 8 _{Group: -CH 2 -C (CH 3)} (OR ') - CH 2 -OR 8 total average of 2 or more, glycidyl and methyl glycidyl groups with the average number of glycidyl: -CH ₂ -CH (OR')-CH ₂ -OR ⁸ and the base: -CH ₂ -C(CH ₃ )(OR')-CH ₂ -OR ⁸ The average number of the ratio is 10:90~90:10, which exists in general In R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ in the formula (3), a glycidyl group and a methyl glycidyl group are bonded to a group: -CH ₂ -CH(OR')-CH ₂ - OR ⁸ and base: -CH ₂ -C(CH ₃ )(OR')-CH ₂ -OR ⁸ totals 2 or more on average, the average number of glycidyl groups and methyl glycidyl groups and base: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ and the ratio of the base: -CH ₂ -C(CH ₃ )(OR')-CH ₂ -OR ⁸ is 10:90~90:10] A resin represented by an ester and an epoxy resin sometimes composed of a polymer thereof.

In the present invention, the polymer contained may be a dimer, a trimer, a tetramer, a pentamer or the like. The general formula (1) is a polymer Said. The polymers of the general formulae (2) and (3) can also be represented by the same general formula (1). The amount of the polymer can vary.

The alkylene group having 1 to 4 carbon atoms is, for example, a methylene group, an ethyl group, a trimethyl group, and a tetramethylene group, preferably a methylene group and an ethyl group.

The Alkylidene group having 2 to 4 carbon atoms, for example, an ethylene group, a propylene group, an isopropylidene group, a methylpropylene group and a butylene group, preferably an ethylene group and an isopropylidene group. .

The arylene group having 6 to 20 carbon atoms is a monocyclic or polycyclic aromatic group, and examples thereof include a stretching phenyl group, a stretching naphthyl group and a stretching group, and preferably a stretching phenyl group.

Examples of the alkylene group having 1 to 4 carbon atoms and 6 to 20 carbon atoms in the exoaryl group having 1 to 4 carbon atoms and 6 to 20 carbon atoms in the extended aryl group are as described above. definition. The alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 20 carbon atoms are preferably, for example, a methylene-phenylene group. In the present invention, the order of bonding of each group in the exoaryl group having from 6 to 20 carbon atoms having 1 to 4 carbon atoms is not limited. For example, an oxygen atom bonded to R ¹ to R ⁶ may be bonded to an alkyl group having 1 to 4 carbon atoms in an alkyl group having 1 to 4 carbon atoms and 6 to 20 carbon atoms. It is also possible to bond an extended aryl group having 6 to 20 carbon atoms.

The alkyl group having 1 to 4 carbon atoms - the aryl group having 6 to 20 carbon atoms - the number of carbon atoms having 1 to 4 carbon atoms in the alkyl group having 1 to 4 carbon atoms and the number of carbon atoms 6~ An illustration of the exoaryl group of 20 is as defined above. The alkyl group having 1 to 4 carbon atoms - the aryl group having 6 to 20 carbon atoms - the alkyl group having 1 to 4 carbon atoms is preferably a phenylene bis(methylene group).

Alkyl groups are, for example, methyl, ethyl, propyl, allyl, benzyl Base, p-methoxybenzyl, trityl group, and the like.

The mercapto group is, for example, an ethenyl group, a trimethylethenyl group, a benzamidine group, a t-butoxycarbonyl group or the like.

The mercapto group is, for example, trimethylmethanealkyl, triethylmethane, t-butyldimethylformamidin, triisopropylcarbenyl, t-butyldiphenylcarbenyl or the like.

The acetal group (Acetal) may, for example, be a methoxymethyl group, an ethoxyethyl group, a tetrahydropyranyl group, a benzyloxymethyl group, a methoxyethoxymethyl group, a methylthiomethyl group or the like.

In the present invention, among R ¹¹ to R ¹⁶ , hydrogen is preferably as small as possible. Among R ¹¹ to R ¹⁶ , the average hydrogen is preferably 1 or less, more preferably 0.5 or less, still more preferably 0.1 or less, and most preferably 0.

In the present invention, among R ¹¹ to R ¹⁶ , a glycidyl group and a methyl glycidyl group are bonded to a group: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ and a group: -CH ₂ -C (CH ₃ The total of (OR')-CH ₂ -OR ⁸ is preferably 3 or more on average, more preferably 3.8 or more in the case of the formulas (1) and (2), and 5.8 or more in the case of the formula (3). When it is the best formula (1) and (2), it is four or more, and when it is formula (3), it is six or more.

The average number of glycidyl groups and methyl glycidyl groups and groups: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ and groups: -CH ₂ -C(CH ₃ )(OR')-CH ₂ The ratio of the average number of -OR ⁸ is 10:90~90:10.

The hydrogen present in the group: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ is preferably 0.7 or less, more preferably 0.5 or less, still more preferably 0.3 or less, most preferably Good for 0.

In the esterified epoxy resin, the number of glycidyl groups and methyl glycidyl groups, and the number of (meth)acrylonitrile groups can be calculated by HPLC. Specifically, peaks corresponding to the number of each epoxy group and the number of each (meth)acryl fluorenyl group can be obtained by HPLC, and the ratio of the respective numbers can be calculated from the respective peak areas. In the esterified epoxy resin, a glycidyl group, a methyl glycidyl group, a (meth)acryloyl group-containing group: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ and a group:- The number of CH ₂ -C(CH ₃ )(OR')-CH ₂ -OR ⁸ . Further, when the esterified epoxy resin is a mixture, the number of glycidyl groups and methyl glycidyl groups and the number of (meth)acrylonitrile groups are calculated as the average value of the mixture. For example, when expressed by the general formula (1) and the general formula (2), the mixture of the esterified epoxy resins is a mixture of the epoxy resins represented by the general formula (4) and the general formula (5) described later and their epoxy resins. a part of the base is a (meth)acrylonitrile-based resin, and a partially esterified epoxy resin represented by the general formula (3) sometimes contains a mixture of the epoxy resin represented by the general formula (6) described later and The case where a part of the epoxy group is a (meth)acrylonitrile-based resin.

The bonding position of X in the general formula (1) is preferably 4, 4'-position, that is, a bisphenol type epoxy resin skeleton. Further, the bonding position of the naphthalene ring in the compound represented by the general formula (2) is preferably 1,6-bonded.

In the esterified epoxy resin, the ratio of the glycidyl group and the methyl glycidyl group to the acrylonitrile group and the methacrylic acid group can be determined by HPLC and epoxy equivalent. Specifically, the amount of esterification of the epoxy equivalent of the epoxy resin which only increases the raw material can be calculated to be esterified to some extent by measuring the epoxy equivalent of the esterified epoxy resin. Moreover, by mass spectrometry (LC-MS) of each peak of HPLC, the molecular weight and the ratio of each component can be obtained. The ratio of epoxy groups to acryl groups.

The number average molecular weight of the esterified epoxy resin of the present invention is preferably from 500 to 10,000, more preferably from 800 to 5,000. Moreover, the viscosity of the esterified epoxy resin at 25 ° C is preferably from 1,000 to 600,000 mPa. s, more preferably 1,000 to 100,000 mPa. s, the best is 1,000~50,000mPa. s. When it is within this range, it can be filled with more hardener or powder than ever before. Further, in the present invention, the viscosity is a value measured by an E-type viscometer.

The esterified epoxy resin of the present invention represented by the general formula (1) is preferably, for example, (wherein R is (meth)acryloyl group, Me or Et, etc.) And/or Further, a polymer such as a hexamethacrylate, an octa methacrylate or a dimer or a trimer may be contained.

In the present invention, the general formulae (1a) to (3a) are used, wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently hydrogen, glycidyl, methyl glycidyl, (Meth)acryloyl group, or a group: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ or a group: -CH ₂ -C(CH ₃ )(OR')-CH ₂ -OR ⁸ (formula In the case where R' is a hydrogen or a (meth) acrylonitrile group, and R ⁸ is a (meth) acryl fluorenyl group, the resin represented by the same formula as in the general formulae (1) to (3) and sometimes An esterified epoxy resin composed of a polymer.

The method for producing an esterified epoxy resin according to the present invention comprises the following steps (1A) to (1C): (1A) a polyfunctional epoxy compound having 2 or more epoxy groups in a molecule, in a metal catalyst In the presence of a polyhydroxy compound having 2 or more hydroxyl groups in the molecule, a step of obtaining an epoxy ring-opening of the polyfunctional epoxy compound, and (1B) a ring of the polyfunctional epoxy compound obtained in the step (1A) The step of epoxidizing the hydroxyl group of the oxygen ring-opening to obtain an epoxy resin, and (1C) the step of reacting the epoxy resin obtained in the step (1B) with (meth)acrylic anhydride.

<Step (1A)>

In the step (1A), the starting compound, that is, the polyfunctional epoxy compound having 2 or more epoxy groups in the molecule, forms a hydroxyl group by ring opening of an epoxy group. At the same time, a hydroxyl group derived from a polyhydroxy compound is formed. The ring-opening of the polyfunctional epoxy compound means a compound in which the epoxy groups of the polyfunctional epoxy compound are all ring-opened.

The polyfunctional epoxy compound is not particularly limited as long as it is an epoxy compound having 2 or more epoxy groups in one molecule. The polyfunctional epoxy compound is, for example, the following compound.

The polyfunctional epoxy compound is, for example, a polyalkylene glycol such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or tripropylene glycol, dimethylolpropane, trimethylolpropane or a spiro ring. An aliphatic polyvalent glycidyl ether compound obtained by reacting a polyhydric alcohol such as spiroglycol or glycerin with epichlorohydrin.

Examples of the polyfunctional epoxy compound include aromatic diols such as bisphenol A, bisphenol S, bisphenol F, and bisphenol AD, and glycols modified with ethylene glycol, propylene glycol, and alkanediol. An aromatic polyvalent glycidyl ether compound obtained by the reaction of epichlorohydrin.

The polyfunctional epoxy compound is, for example, an aliphatic polyvalent glycidyl ester compound obtained by reacting an aromatic dicarboxylic acid such as adipic acid or isaconic acid with epichlorohydrin, isophthalic acid, terephthalic acid or benzene. An aromatic polyvalent glycidyl ester compound obtained by reacting an aromatic dicarboxylic acid such as tetraacid with epichlorohydrin.

The polyfunctional epoxy compound is, for example, an aromatic polyvalent glycidylamine compound obtained by reacting an aromatic amine such as diaminodiphenylmethane, aniline or m-xylylenediamine with epichlorohydrin.

Polyfunctional epoxy compounds such as Hydantoin And an indole-type polyvalent glycidyl compound obtained by reacting the derivative with epichlorohydrin.

The polyfunctional epoxy compound is, for example, a phenol resin derived from phenol or cresol and formaldehyde, a phenol obtained by reacting a phenol resin with epichlorohydrin, and a phenol type polyvalent glycidyl ether compound.

In the present invention, the polyfunctional epoxy compound is, for example, the following general formula (7a): General formula (8a): And general formula (9a): The epoxy compound represented by the formula (wherein X and R ²¹ are as described above) is preferred.

The preferred polyfunctional epoxy compound of the present invention, that is, the epoxy compound represented by the general formula (7a) to the general formula (9a), for example, a commercially available product such as EPICLON 850 (manufactured by Dainippon Ink Co., Ltd.), epikote 828EL, Bisphenol A type epoxy resin such as epikote 1004 (all of which is manufactured by Japan Epoxy Resin Co., Ltd.), epicote 806, and epikote 4004 (all of which are manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON HP4032, EPICLON EXA A tetrafunctional epoxy resin such as a naphthalene type epoxy resin such as -4700 (all of which is manufactured by Dainippon Ink Co., Ltd.) or VG-3101 (manufactured by Mitsui Petrochemical Co., Ltd.).

In the present invention, the polyhydroxy compound having two or more hydroxyl groups in the molecule is not particularly limited as long as it is a compound having two or more hydroxyl groups in the molecule. Specific examples of the polyhydroxy compound include, for example, the following compounds.

a compound having two hydroxyl groups in the molecule, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, and 1,6-hexane Monoalkanediols such as alcohols and polyalkylene glycols; catechol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,2-dihydroxypurine (anthraquinone) and 2,3- a divalent aromatic hydroxy compound such as dihydroxyquinoxaline; an aromatic alcohol such as benzene-1,4-dimethanol, benzene-1,3-dimethanol or benzene-1,4-diethanol; 4-hydroxymethyl A hydroxyalkylphenol such as a phenol, a 3-hydroxymethylphenol, a 4-hydroxymethylphenol or a 3-hydroxyethylphenol.

a compound having three hydroxyl groups in the molecule, such as glycerin, trimethylolpropane, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane , 1,2,6-hexanetriol and 1,1,1-tris(hydroxymethyl)propane, etc.; 3-pyrrolol; pyrogallol, 3,4,5-trihydroxytoluene, 1,2 a trivalent aromatic polyhydroxy compound such as a 4-trihydroxyindole, a gallic acid, or a gallic acid ester compound such as methyl gallate, propyl gallate or octyl gallate.

Examples of the compound having four or more hydroxyl groups in the molecule include pentaerythritol, diglycerin, tetramethylolethane, and alkylglycoside (methyl glycoside, ethyl glycoside, etc.). Further, 2,3,4,4'-tetrahydroxybenzophenone, ellagic acid, hexahydroxybenzene, tannic acid, and calixarene compounds such as catechol or benzenetriol An aromatic polyhydroxy compound having a tetravalent or higher value.

In the present invention, the polyhydroxy compound is preferably one having 2 to 6 hydroxyl groups in the molecule, more preferably having 2 to 4 hydroxyl groups in the molecule, and particularly preferably the following general formula (10): HO-Y-OH (10) (wherein Y is as described above) is a dihydroxy compound.

The dihydroxy compound represented by the general formula (10) is preferably a monoalkylene glycol such as ethylene glycol, propylene glycol, butane-1,4-diol diethylene glycol or triethylene glycol, or a polyalkylene glycol; An aromatic alcohol such as benzene-1,4-dimethanol, benzene-1,3-dimethanol or benzene-1,4-diethanol; (2-hydroxyphenyl)methanol, (2-hydroxyphenyl)-2 - a hydroxyalkylphenol such as ethanol.

The metal catalyst can be used as long as it is a catalyst for ring-opening reaction of an epoxy group, and for example, a metal such as copper, zinc, iron, magnesium, silver, calcium, tin, or the like, and BF ₄ ^- , SiF ₆ ^{2 -} a metal catalyst composed of an anion such as PF ₆ ^- or CF ₃ SO ₂ ^- . Preferred is tin borofluoride (Sn(BF ₄ ) ₂ ).

In the present invention, the polyhydroxy compound is used in an amount of from 1 equivalent to 10 equivalents, preferably from 4 equivalents to 8 equivalents, per equivalent of the epoxy group in the polyfunctional epoxy compound. In the present invention, by high-speed liquid chromatography (HPLC), it is confirmed that all of the epoxy groups react with the polyhydroxy compound to form an epoxy ring-opening by the disappearance of the peak of the polyfunctional epoxy compound and the single-end reactant of the starting material. Things. Wherein, the single-end reactant means that one part of the epoxy group of the polyfunctional epoxy compound is an unopened reactant, for example, the compound represented by the general formulas (7a) and (8a) is opened by only one epoxy group. The compound of the ring, in addition, the compound represented by the general formula (9a) is a compound which is opened by only one or two epoxy groups.

In the present invention, the amount of metal catalyst used is relative to the total The weight of the mixture should be from 10 to 1,000 ppm, preferably from 20 to 200 ppm.

The reaction temperature in the step (1A) is not particularly limited and may be from 50 ° C to 130 ° C, preferably from 70 ° C to 120 ° C. The reaction in the step (1A) can be carried out in the presence or absence of an organic solvent. The organic solvent which can be used, for example, an aromatic hydrocarbon such as benzene or toluene: a cycloaliphatic ketone such as cyclohexanone; and a dihydroxy compound of a starting material.

<Step (1B)>

The hydroxyl group of the epoxy ring-opening of the polyfunctional epoxy compound obtained in the step (1A) is epoxidized by the step (1B). In the step (1B), part or all of the hydroxyl group in the epoxy ring-opening of the polyfunctional epoxy compound is epoxidized. In the present invention, 50% to 100% of the hydroxyl group of the epoxy ring-opening material of the polyfunctional epoxy compound is preferably epoxidized, more preferably 75% to 100% by epoxidation.

The epoxy ring-opening compound of the polyfunctional epoxy compound is a raw material compound in the step (1B), for example, a compound in which all of the epoxy groups of the above polyfunctional epoxy compound are ring-opened. It is preferably an epoxy ring-opening compound of an epoxy compound represented by the general formula (7a) to the general formula (9a), and the following general formula (7b): An epoxy ring or a general formula (8b) which is represented by a resin and sometimes a polymer thereof: a resin represented by an epoxy ring ring sometimes composed of a polymer thereof, or a general formula (9b): The resin represented by the epoxy ring-opening compound which is sometimes composed of a polymer thereof (wherein, X, Y and R ²¹ are as defined above).

In the step (1B), a reaction in which a known hydroxyl group is epoxidized may be used for the epoxidation, for example, an epichlorohydrin method and an oxidation method, preferably an epichlorohydrin method.

The epichlorohydrin method is an epoxy ring-opening of the polyfunctional epoxy compound obtained in the step (1A), which is reacted with epichlorohydrin or methyl epichlorohydrin in the presence of a phase-shifting catalyst. A method of epoxidizing a hydroxyl group of an epoxy ring-opening of a polyfunctional epoxy compound.

Epichlorohydrin method can be used to produce epichlorohydrin or methyl epoxide Propane is reacted in a molar number which is the desired number of epoxy groups. The amount of epichlorohydrin or methyl epichlorohydrin relative to the hydroxyl group of the epoxy ring-opening of the polyfunctional epoxy compound is from 0.5 moles to 20 moles, preferably from 0.5 to 10 moles.

Phase-shifting catalysts such as methyltrioctylammonium chloride, methyltriammonium chloride and tetramethylammonium chloride tetramethylammonium chloride and chlorinated aryl chloride such as benzyltrimethylammonium chloride The fourth ammonium salt of an alkyltrialkylammonium or the like is preferably benzyltrimethylammonium chloride. The amount of the phase shifting catalyst used is preferably from 0.1 to 5% by weight, more preferably from 0.5 to 3.0% by weight, based on the total weight of the reactant.

The reaction may be carried out in the presence of a solvent such as a hydrocarbon such as hexane or pentane; an ether such as diethyl ether, t-butyl methyl ether or diisopropyl ether; or a ketone such as acetone or methyl ethyl ketone, or may be used in excess. Epichlorohydrin and methyl epichlorohydrin are used as solvents. The reaction is carried out at a temperature of from 30 to 90 ° C, preferably from 40 to 65 ° C, preferably from about 50 to about 55 ° C.

The aqueous alkali solution is, for example, calcium hydroxide, potassium hydroxide or sodium hydroxide. The amount of the alkali metal to be used is 1 equivalent to the hydroxyl group of the epoxy ring-opening material of the polyfunctional epoxy compound, preferably 0.5 to 2.0 equivalents.

The oxidation method comprises a step of allylation of a hydroxyl group of an epoxy ring-opening compound of the polyfunctional epoxy compound obtained in the step (1A) to obtain a polyallyl ether compound; and an allylic group of the polyallyl ether compound A method of the step of oxidizing a base or a 2-methyl-2-propenyl group. In the present invention, allylation of a hydroxyl group includes making a hydroxyl group an allyloxy group or a 2-methyl-2-propenyloxy group. The situation.

In the present invention, the step of obtaining a polyallyl compound is carried out by reacting an epoxy ring-opening compound of a polyfunctional epoxy compound with an allyl halide or a 2-methyl-2-propenyl halide. The step of converting the hydroxyl group of the epoxy ring-opening of the functional epoxy compound to an allyloxy group or a 2-methyl-2-propenyloxy group. Specifically, after the epoxy ring-opening compound and the allyl halide of the polyfunctional epoxy compound are dissolved in dimethyl hydrazine, a fourth-order ammonium salt is added to maintain the reaction temperature at 40 ° C or lower, and the aqueous alkali solution is added. After the dropwise addition, the reaction was carried out at 30 to 40 ° C for about 6 hours.

Halides in allyl halides and 2-methyl-2-propenyl halides, for example, chlorine and bromine. The allyl halide and the 2-methyl-2-propenyl halide are added in an amount of 1 to 30 moles per hydroxy group of the epoxy ring-opening of the polyfunctional epoxy compound.

The fourth-order ammonium salt is, for example, a tetraalkylammonium halide such as tetrabutylammonium bromide or a tetraarylammonium halide such as tetraphenylammonium chloride. The fourth-stage ammonium salt is added in an amount of from 1 mol to 0.1 mol per mol of the epoxy ring-opening of the polyfunctional epoxy compound.

The aqueous alkali solution is, for example, calcium hydroxide, potassium hydroxide or sodium hydroxide. The amount of the alkali metal to be used is 1 equivalent to the hydroxyl group of the epoxy ring-opening material of the polyfunctional epoxy compound, preferably 2 to 8 equivalents.

The step of oxidizing the allyl or 2-methyl-2-propenyl group of the polyallyl etherate is a step of reacting the polyallyl ether compound with hydrogen peroxide in the presence of potassium carbonate. Specifically, the allylation of the hydroxyl group of the epoxy ring-opening compound of the polyfunctional epoxy compound is carried out by polyallyl etherification The compound is added with a solvent such as methanol or ethanol or a solvent such as nitrile such as acetonitrile or benzonitrile and potassium carbonate, and 5 to 40%, preferably 30 to 35%, of hydrogen peroxide is dropped under stirring. After the completion of the dropping, the oxidation reaction is carried out for 0.5 to 10 hours, preferably for 1 to 6 hours.

The amount of hydrogen peroxide added is 1 to 15 moles per mole of the polyallyl ether compound obtained by allylation of the hydroxyl group of the epoxy ring-opening compound of the polyfunctional epoxy compound. The reaction temperature is, for example, 45 ° C or lower, preferably 20 to 40 ° C.

The epoxy resin obtained in the step (1B) is preferably a compound represented by the general formula (7), the general formula (5) and the general formula (6) of the general formulae (7b) to (9b).

The composition of the epoxy resin represented by the general formula (4), for example Further, a polymer of a dimer, a trimer or the like may be sometimes included.

In the general formulae (4) to (6), at least two of R ¹ to R ⁶ are a glycidyl group or a methyl glycidyl group. In the present invention, the epoxy group means both a glycidyl group and a methyl glycidyl group. Among them, the glycidyl group is 2,3-epoxypropyl group, and the methyl glycidyl group is 2,3-epoxy-2-methylpropyl group. In the present invention, among R ¹ to R ⁶ , three or more are glycidyl groups or methyl glycidyl groups, and among R ¹ to R ⁶ , all of them are glycidyl groups or methyl glycidyl groups.

In the present invention, the number of the glycidyl group and the methyl glycidyl group in the general formula (4) to the general formula (6) can be calculated by high-speed liquid chromatography (HPLC). Specifically, a peak corresponding to the number of glycidyl groups and methyl glycidyl groups can be obtained by HPLC, and the ratio of the number of glycidyl groups and methyl glycidyl groups can be calculated from the respective peak areas. Thereby, the number of glycidyl groups and methyl glycidyl groups contained in the compound can be calculated. Further, in the general formulae (4) to (6), when the epoxy resin is a mixture, the number of glycidyl groups and methyl glycidyl groups is calculated as the average value of the mixture. In other words, the number of epoxy groups is determined by mass analysis (LC-MS) in each peak of HPLC, and the average number of epoxy groups in the mixture is calculated from the ratio of the components in the mixture. For example, a mixture of epoxy resins represented by the general formula (4) and the general formula (5) may contain a compound having 3 or 4 epoxy groups and a polymer thereof, and is represented by the general formula (6). The epoxy resin sometimes contains a compound having 3, 4, 5, and 6 epoxy groups and a polymer thereof.

The bonding position of X of the compound represented by the general formula (4) is preferably a 4, 4'-position, that is, a bisphenol type epoxy resin skeleton. Further, the bonding position of the naphthalene ring in the compound represented by the general formula (5) is preferably 1,6-bonded.

In the present invention, the number average molecular weight of the epoxy resin is preferably from 200 to 5,000. In the present invention, the number average molecular weight is a number average molecular weight obtained by gel permeation chromatography (GPC) in terms of polystyrene.

In the present invention, the epoxy equivalent of the epoxy resin is preferably 100 to 3,000 g/eq., more preferably 150 to 1,000 g/eq. In the present invention, the epoxy equivalent is obtained by averaging the mixture when the epoxy resin is a mixture. In the present invention, the epoxy equivalent can be obtained in accordance with JIS K7236:2001 (corresponding to ISO3001:1999).

<Step (1C)>

In the step (1C), the glycidyl group, the methyl glycidyl group and the hydroxyl group of the epoxy resin obtained by the production method of the above steps (1A) to (1B) are (meth)acrylic anhydride (methyl) ) propylene thiolation. The epoxy resin obtained by the production method comprising the steps (1A) to (1B) is preferably a resin represented by the general formula (4) to the general formula (6) and an epoxy compound sometimes composed of the polymer thereof. Resin.

The (meth)acrylic anhydride is not particularly limited, and for example, a commercially available acid anhydride of acrylic acid or methacrylic acid can be used.

In the present invention, when the epoxy resin obtained by the production method comprising the steps (1A) to (1B) is reacted with (meth)acrylic anhydride, the epoxy obtained by the production method comprising the steps (1A) to (1B) is used. When the epoxy group of the resin is 1 equivalent, the amount of the (meth)acrylic anhydride to be reacted is preferably 10 to 90 equivalent %, more preferably 20 to 80 equivalent %, particularly preferably 25 to 75 equivalent %.

In the method for producing an esterified epoxy resin, the reaction between the glycidyl group and the methyl glycidyl group and the (meth)acrylic anhydride is carried out quantitatively, so that the esterification ratio of the obtained esterified epoxy resin can also be obtained by a ring. Oxygen equivalent is estimated.

The (meth)acrylic anhydride is in the above-mentioned range with respect to the epoxy group of the epoxy resin obtained by the manufacturing method of the steps (1A) to (1B). In the inner reaction, an esterified epoxy resin having low viscosity and high liquid stability can be obtained.

The above reaction can be carried out in the presence of a phase shifting catalyst or a basic catalyst.

The phase shifting catalyst can be selected from the foregoing catalysts, preferably benzyltrimethylammonium chloride. The amount of the phase-shifting catalyst used is preferably 0.001 to 5% by weight, and more preferably 0.001 to 2.0% by weight based on the total weight of the reactant.

The basic catalyst is preferably a trivalent organic phosphorus compound and/or an amine compound. The basic atom of the basic catalyst is phosphorus and/or nitrogen.

Further, it is also possible to use a polymer-supporting alkaline catalyst in which a basic catalyst is supported on a polymer.

a trivalent organic phosphorus compound, for example, an alkylphosphine such as triethylphosphine (PHOSPHINE), tri-n-propylphosphine or tri-n-butylphosphine, or a salt thereof, triphenylphosphine, tri-m-toluene Arylphosphines such as phosphines, tris-(2,6-dimethoxyphenyl)phosphines and salts thereof, phosphite, triethyl phosphite, tris(nonylbenzene) a phosphite triester such as a phosphite or a salt thereof. a salt of a trivalent organic phosphorus compound, for example, triphenylphosphine. Ethyl bromide (Bromide), triphenylphosphine. Butyl bromide, triphenylphosphine. Octyl bromide, triphenylphosphine. Mercapto bromide, triphenylphosphine. Isobutyl bromide, triphenylphosphine. Propyl chloride, triphenylphosphine. Amyl chloride, triphenylphosphine. Hexyl bromide and the like. Among them, triphenylphosphine is preferred.

The amine compound is, for example, a second-stage amine such as diethanolamine, a third-grade amine such as triethanolamine, dimethylbenzylamine, tris(dimethylamino)methylphenol or tris(diethylamino)methylphenol. Amine, 1,5,7-triazabicyclo[4.4.0]癸-5- Alkene (TBD), 7-methyl-1,5,7-triazabicyclo[4.4.0]non-5-ene (Me-TBD), 1,8-diazabicyclo[5.4.0] Undeca-7-ene (DBU), 6-dibutylamino-1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo [4.3.0] Strongly basic amines such as guan-5-ene (DBN), 1,1,3,3-tetramethylguanidine (guanidine) and salts thereof. Among them, preferred is 1,5,7-triazabicyclo[4.4.0]non-5-ene (TBD). The salt of the amine compound is, for example, benzyltrimethylammonium chloride or benzyltriethylammonium chloride.

The polymer carrying the basic catalyst is not particularly limited, and a polymer obtained by crosslinking a polystyrene with divinylbenzene or a polymer obtained by crosslinking an acrylic resin with divinylbenzene can be used. These polymers are insoluble in a solvent (for example, methyl ethyl ketone or methyl isobutyl amide) for the reaction of an epoxy resin obtained by the production method containing the steps (1A) to (1B) with (meth)acrylic anhydride. Base ketone, toluene, etc.) and raw materials and products.

The basic catalyst supported by the polymer can chemically bond the basic catalyst with the insoluble polymer, or introduce the basic catalyst into the monomer, and then polymerize the monomer, and then use divinylbenzene or the like. The cross-linking monomer is subjected to 3-dimensional cross-linking to produce a basic catalyst supported by a polymer which is insoluble in a solvent such as methyl ethyl ketone, methyl isobutyl ketone or toluene.

The basic catalyst supported by the polymer, specifically, for example, diphenylphosphinopolystyrene, 1,5,7-triazabicyclo[4.4.0]non-5-ene polystyrene, N , N-(diisopropyl)aminomethylpolystyrene, N-(methylpolystyrene)-4-(methylamino)pyridine, and the like. The basic catalysts to be supported by these polymers may be used singly or in combination of two or more.

The alkaline catalyst supported by the polymer can be used by a commercially available person. A commercially available polymer-supported alkaline catalyst, for example, PS-PPh ₃ (diphenylphosphinopolystyrene, manufactured by Biotage Co., Ltd.), PS-TBD (1,5,7-triazabicyclo[4.4 .0] 癸-5-ene polystyrene, manufactured by Biotage Co., Ltd.).

When the ratio of the basic catalyst supported by the polymer is 1 equivalent to the epoxy group of the epoxy resin obtained by the production method of the steps (1A) to (1B), the alkaline catalyst supported by the polymer is more Preferably, it is 0.5 to 10.0 milliequivalent, more preferably 1.0 to 5.0 milliequivalent. When the ratio of use of the basic catalyst supported by the polymer is within the above range, it is preferable from the viewpoints of the reaction rate, the reaction time, and the catalyst cost.

In the production method of the present invention, the temperature in the reaction step of the epoxy resin and (meth)acrylic anhydride obtained by the production method comprising the steps (1A) to (1B) is preferably 60 to 130 ° C, more preferably It is 80 to 130 ° C, more preferably 90 to 120 ° C.

In the presence of a catalyst, when the epoxy resin obtained by the production method of the steps (1A) to (1B) is reacted with (meth)acrylic anhydride, in order to prevent gelation, in the reaction system and on the reaction system The oxygen concentration in the gas phase must be properly maintained. For example, when air is actively blown into the reaction system, oxidation of the catalyst may occur, resulting in a decrease in activity, so care must be taken.

Further, a polymerization inhibitor may be added, and examples of the polymerization inhibitor include hydroquinone, p-hexyloxyphenol, and BHT (dibutylhydroxytoluene), and they may be used singly or in combination 2. The amount added is preferably from 50 to 1000 ppm based on the weight of the reaction system.

The esterification ring obtained by reacting the epoxy resin obtained by the production method of the steps (1A) to (1B) with (meth)acrylic anhydride Since the oxygen resin is hardened by an active energy ray such as ultraviolet rays, it is preferred to carry out the reaction in a container that shields ultraviolet rays. Further, by reacting the epoxy resin obtained by the production method of the steps (1A) to (1B) with (meth)acrylic anhydride, in order to prevent gas phase polymerization, a solvent-based reflux solvent can be exhibited for the epoxy resin. In the presence of the solvent, it is necessary to remove the solvent after the end of the reaction, so that it is preferably carried out without a solvent. The reflux solvent is, for example, acetone, methyl ethyl ketone or the like.

In the production method of the present invention, when a basic catalyst supported by a polymer is used, the epoxy resin obtained by the production method comprising the steps (1A) to (1B) is reacted with (meth)acrylic anhydride, and then partially The esterified epoxy resin is obtained by removing the basic catalyst supported by the polymer. The method of removing the polymer-supported alkaline catalyst is preferably carried out using filtration or centrifugation.

A method of filtering a basic catalyst supported by a polymer, for example, a method of filtering a polymer-supported alkaline catalyst using a mesh mesh NY-10HC (manufactured by Sefar, Switzerland) having a mesh size of 10 μm.

A method of centrifugally separating a basic catalyst supported by a polymer, for example, a method of removing a polymer-supported alkaline catalyst by solid-liquid separation using a centrifugal separator.

The method for producing the esterified epoxy resin of the present invention is preferably used for producing a resin represented by the general formula (1) to the general formula (3) and an esterified epoxy resin composed of a polymer thereof. In other words, the method of producing the esterified epoxy resin described above, that is, the general formula (4) to (6) obtained by the production method including the step (2C): steps (2A) to (2B) is employed. An epoxy resin and a (meth) resin sometimes composed of a polymer thereof The acrylic acid anhydride reaction can obtain a method for producing an esterified epoxy resin which is a step of a resin represented by the general formula (1a) to the general formula (3a) and an esterified epoxy resin which is sometimes composed of a polymer.

The method for producing an esterified epoxy resin of the present invention comprises the following steps (1A), (1B), (1C') and (1D), wherein (1A) has a polyepoxy group having 2 or more in the molecule; a functional epoxy compound, which is reacted with a polyhydroxy compound having 2 or more hydroxyl groups in the molecule in the presence of a metal catalyst to obtain an epoxy ring-opening of a polyfunctional epoxy compound, and (1B) a step (1A) The hydroxy group of the epoxy ring-opening compound of the obtained polyfunctional epoxy compound is subjected to epoxidation to obtain an epoxy resin, and (1C') the epoxy resin obtained in the step (1B) is reacted with (meth)acrylic acid to obtain a partial ester. a step of epoxidizing the epoxy resin, (1D) the partially esterified epoxy resin obtained in the step (1C') with a (meth) propylene sulfhydrylating agent, an alkylating agent, a thiolating agent, a formylating agent Or a step of reacting an acetalizing agent.

<Step (1A)> and <(1B)>

Steps (1A) and (1B) are as described above.

<Step (1C')>

In the step (1C'), the glycidyl group and the methyl glycidyl group of the epoxy resin obtained by the production method comprising the above steps (1A) to (1B) are partially (meth)acryl thiolated. By the manufacturer including the aforementioned steps (1A) to (1B) The epoxy resin obtained by the method is preferably a resin represented by the general formula (4) to the general formula (6) and an epoxy resin sometimes composed of a polymer thereof.

(Meth)acrylic acid is not particularly limited, and for example, commercially available acrylic acid or methacrylic acid can be used.

In the present invention, the step of reacting the epoxy resin obtained by the production method comprising the above steps (1A) to (1B) with (meth)acrylic acid is carried out by including the aforementioned steps (1A) to (1B). The epoxy group obtained by the production method has an epoxy group equivalent of 1 equivalent, and the reacted (meth)acrylic acid is preferably 10 to 90 equivalent %, more preferably 20 to 80 equivalent %, still more preferably 30 to 70 equivalent %. , particularly preferably 40 to 60 equivalent %. In the method for producing a partially esterified epoxy resin, the reaction of the glycidyl group and the methyl glycidyl group with the (meth)acrylic acid is carried out in a quantitative manner, so that the esterification ratio of the obtained partially esterified epoxy resin can be obtained by The epoxy equivalent is estimated.

The reaction of only the unsaturated group is carried out when the (meth)acrylic acid is reacted in the above range with respect to 1 equivalent of the epoxy group of the epoxy resin obtained by the production method of the above steps (1A) to (1B). At the time of polymerization, a resin property which is temporarily fixed can be obtained, and in the case of secondary polymerization, phase separation or the like can be prevented, and a partially esterified epoxy resin which can form a homogeneous polymer can be obtained.

In the present invention, the reaction of the epoxy resin with (meth)acrylic acid may be carried out using the above-mentioned basic catalyst supported by a polymer supported on a basic catalyst or a basic catalyst.

In the production method of the present invention, the temperature in the reaction step of the epoxy resin and (meth)acrylic acid obtained by the production method comprising the above steps (1A) to (1B) is preferably 60 to 120 ° C, more preferably 80~120°C, More preferably 90~110 °C.

In the presence of a catalyst, when the epoxy resin obtained by the production method including the above steps (1A) to (1B) is reacted with (meth)acrylic acid, in order to prevent gelation, the reaction system and the reaction system The oxygen concentration in the gas phase must be properly maintained. For example, when air is actively blown into the reaction system, oxidation of the catalyst may occur, resulting in a decrease in activity, so care must be taken.

Further, a polymerization inhibitor may be added, and examples of the polymerization inhibitor include hydroquinone, p-hexyloxyphenol, and BHT (dibutylhydroxytoluene), and they may be used singly or in combination 2. The amount added is preferably from 50 to 1000 ppm based on the weight of the reaction system.

The partially esterified epoxy resin obtained by the reaction of the epoxy resin obtained by the above-mentioned steps (1A) to (1B) with (meth)acrylic acid is reacted by active energy rays such as ultraviolet rays. Therefore, it is preferred to carry out the reaction in a container that shields ultraviolet rays. Further, by reacting the epoxy resin obtained by the production method of the steps (1A) to (1B) with (meth)acrylic acid, in order to prevent gas phase polymerization, a reflux solvent having a good solvent property for the epoxy resin may be present. The reaction is carried out at this time, and it is necessary to remove the solvent after the completion of the reaction, so that it is preferably carried out without a solvent. The reflux solvent is, for example, acetone, methyl ethyl ketone or the like.

In the production method of the present invention, after the epoxy resin obtained by the production method comprising the steps (1A) to (1B) is reacted with (meth)acrylic acid, the partially esterified epoxy resin is removed by removing the polymer. The basic catalyst comes. a method of removing a polymer-supported alkaline catalyst, as described above, using Filtration or centrifugation is preferred.

The partially esterified epoxy resin obtained in the step (1C') is preferably a general formula (1'), a general formula (2'), and a general formula (3') produced by the general formulas (4) to (6). Representation. In the partially esterified epoxy resin represented by the general formula (1') to the general formula (3'), at least two glycidyl groups of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ , A glycidyl group or a group containing a (meth)acrylinyl group: -CH ₂ -CH(OH)-CH ₂ -OR ⁸ or a group: -CH ₂ -C(CH ₃ )(OH)-CH ₂ - OR ⁸ . In other words, the partially esterified epoxy resin represented by the general formula (1') to the general formula (3') of the present invention is a glycidyl group and a methyl group of the epoxy resin represented by the general formula (4) to the general formula (6). One part of the glycidyl group is a (meth) propylene-based epoxy resin.

In the general formula (1') to the general formula (3'), among the R ¹¹ to R ¹⁶ , three or more are a glycidyl group, a methyl glycidyl group, or a group containing a (meth)acryl fluorenyl group:- CH ₂ -CH(OH)-CH ₂ -OR ⁸ or a group: -CH ₂ -C(CH ₃ )(OH)-CH ₂ -OR ^{8 is} preferred, among R ¹¹ to R ¹⁶ , the general formula (1' And (2'), 3.8 or more, of the general formula (3'), 5.8 or more are glycidyl groups, methyl glycidyl groups, or a group containing a (meth)acryl fluorenyl group: -CH ₂ - CH(OH)-CH ₂ -OR ⁸ or a group: -CH ₂ -C(CH ₃ )(OH)-CH ₂ -OR ^{8 is more} preferable, and among R ¹¹ to R ¹⁶ , all, that is, the general formula (1' And (2'), 4 or more, in the general formula (3'), 6 or more are glycidyl groups, methyl glycidyl groups, or a group containing (meth)acrylinyl group: -CH ₂ -CH(OH)-CH ₂ -OR ⁸ or a group: -CH ₂ -C(CH ₃ )(OH)-CH ₂ -OR ^{8 is} most preferred.

The number of glycidyl groups and methyl glycidyl groups and the number of (meth)acryloyl groups in the general formula (1') to the general formula (3') can be calculated by HPLC. Specifically, peaks corresponding to the number of each epoxy group and the number of each (meth)acryl fluorenyl group can be obtained by HPLC, and the ratio of the respective numbers can be calculated from the respective peak areas. A glycidyl group, a methyl glycidyl group, and a group containing a (meth)acrylinyl group in the general formula (1') to the general formula (3'): -CH ₂ -CH(OH)-CH _{2 can be obtained.} -OR ⁸ or a group: the number of -CH ₂ -C(CH ₃ )(OH)-CH ₂ -OR ⁸ . Further, when the partially esterified epoxy resin represented by the general formulae (1') to (3') is a mixture, the number of glycidyl groups and methyl glycidyl groups, and the group containing a (meth)acryl fluorenyl group: - The number of CH ₂ -CH(OH)-CH ₂ -OR ⁸ or a group: -CH ₂ -C(CH ₃ )(OH)-CH ₂ -OR ⁸ is calculated as the average of the mixture. For example, a mixture of partially esterified epoxy resins sometimes contains a mixture of epoxy resins and a portion of the epoxy groups of which are (meth)acrylonitrile-based resins.

In the partially esterified epoxy resin, a glycidyl group and a methyl glycidyl group and a group containing an acryloyl group and a methacryl group: -CH ₂ -CH(OH)-CH ₂ -OR ⁸ and a group: -CH The ratio of ₂ -C(CH ₃ )(OH)-CH ₂ -OR ⁸ is preferably 20:80 to 80:20, more preferably 25:75 to 75:25. The ratio of epoxy groups to (meth) acrylonitrile groups can be determined by HPLC and epoxy equivalents. Specifically, the amount of esterification of the epoxy equivalent of the epoxy resin which only increases the raw material can be calculated to some extent by esterification by measuring the epoxy equivalent of the partially esterified epoxy resin. Further, by mass spectrometry (LC-MS) of each peak of HPLC, the molecular weight and the ratio of each component, and the ratio of the epoxy group and the acrylonitrile group per component can be determined.

In the present invention, the number average molecular weight of the partially esterified epoxy resin The amount is preferably from 500 to 10,000, more preferably from 800 to 5,000.

The partially esterified epoxy resin represented by the general formula (1') contains, for example, a dimethacrylate compound, Further, a monomethacrylate, a trimethacrylate, a tetramethacrylate or a polymer of such a dimer, a trimer or the like may be contained.

<Step (1D)>

Step 1D is carried out by partially esterifying the epoxy resin obtained in the step (1C') with a (meth) propylene oximation agent, an alkylating agent, a thiolating agent, a formylating agent or an acetalizing agent. The step of the reaction.

The (meth)acrylonitrile grouping agent may be, for example, a (meth)acrylic acid chloride, a (meth)acrylic acid bromide or the like (meth)acrylic acid halide, or a (meth)acrylic anhydride, or a (meth) group. A (meth) acrylate such as methyl acrylate, ethyl (meth) acrylate or propyl (meth) acrylate.

The alkylating agent may be, for example, an alkyl halide such as an alkyl chloride, an alkyl bromide or an alkyl iodide.

The thiolating agent may be, for example, a mercapto halide such as mercapto chloride or mercapto bromide, or an acid anhydride or an ester.

The formylating agent may be, for example, a trialkylformamidine alkyl halide such as a trialkylformamidine alkyl chloride or a trialkylformamidine alkyl bromide.

The acetal grouping agent may, for example, be an alkoxymethyl halide such as trimethoxymethyl chloride or ethoxymethyl chloride, or an alkyl vinyl ether such as tetrahydropyran or ethyl vinyl ether. .

The reaction of the partially esterified epoxy resin with a (meth) propylene sulfhydrylating agent, an alkylating agent, a formylating agent or an acetalizing agent can be carried out by a conventional method.

In the step 1D, it is preferred that the partially esterified epoxy resin is a resin represented by the general formula (1') to (3') and a partially esterified epoxy resin sometimes composed of a polymer thereof, and the resin is Reacting a (meth) propylene thiolating agent, an alkylating agent, a thiolating agent, a formylating agent or an acetalizing agent to obtain a resin represented by the general formulas (1) to (3) and sometimes An esterified epoxy resin composed of a polymer thereof.

The curable composition of the present invention contains one or more of the esterified epoxy resin or the esterified epoxy resin produced by any of the above methods. The curable composition may be a liquid crystal sealing agent, particularly a liquid crystal sealing agent for a dropping method.

The component contained in the curable composition of the present invention may be, for example, a curing agent, a polymerization initiator, a filler or a coupling agent in addition to the esterified epoxy resin of the present invention.

The hardener is not particularly limited, and a known compound can be used as the hardener. The hardener is, for example, an amine hardener, an organic acid diterpene compound, imidazole and a derivative thereof, dicyandiamide, an aromatic amine, an epoxy modified polyamine, and Polyaminourea, etc., particularly preferably VDH (1,3-bis(decylcarboxyethyl)-5-isopropylethyl fluorene) of organic acid diterpene, calcium carbonate (dioxalate adipic acid) ), UDH (Carbohydrazide, 7,11-octadecadiene-1,18-dicarbonate) and LDH (octadecane-1,18-dicarboxylic acid dioxime). These hardeners may be used singly or in combination. The amount of the curing agent is preferably from 1 to 25 parts by weight, more preferably from 5 to 15 parts by weight, per 100 parts by weight of the epoxy resin and the partially esterified epoxy resin.

The polymerization initiator refers to a compound which is activated by absorption of energy of light to generate a radical. The polymerization initiator is not particularly limited, and a known compound can be used as the polymerization initiator. The polymerization initiators are, for example, benzoin, acetophenone, benzophenone, thioxanthone, α-methoxyethyl ester, phenylglyoxylate, benzil A polymerization initiator of a azo compound, a diphenylthio compound, a mercaptophosphine oxide compound, a benzoin, a benzoin ether, and an anthracene, preferably having solubility in a liquid crystal It is low and has a reactive base which does not gasify when the light is irradiated. The preferred polymerization initiator of the present invention is, for example, EY resin KR-2 (manufactured by k-s-m). The amount of the polymerization initiator to be added is preferably 0.1 to 5 parts by weight, more preferably 1 to 5 parts by weight, per 100 parts by weight of the epoxy resin and the partially esterified epoxy resin.

The filler is added for the purpose of improving the viscosity control of the curable composition, the strength of the cured product after the curable composition is cured, or the subsequent reliability of the curable composition by suppressing the linear expansion property. As the filler, a known inorganic filler and an organic filler which are used for the composition containing an epoxy resin can be used. Inorganic fillers such as calcium carbonate, magnesium carbonate, sulfuric acid Bismuth, magnesium sulfate, aluminum citrate, titanium oxide, aluminum oxide, zinc oxide, cerium oxide, kaolin, talc, glass beads, sericite activated clay, bentonite, aluminum nitride, and tantalum nitride. The organic filler is, for example, polymethyl methacrylate, polystyrene, a copolymer obtained by copolymerizing these monomers with other monomers, polyester fine particles, polyurethane fine particles, and rubber fine particles. In the present invention, inorganic fillers such as cerium oxide and talc are particularly preferred. The amount of the filler is preferably from 2 to 40 parts by weight based on 100 parts by weight of the epoxy resin and the partially esterified epoxy resin. More preferably 5 to 30 parts by weight.

The coupling agent is added in order to improve the adhesion to the liquid crystal display substrate. The coupling agent is not particularly limited, and examples thereof include γ-aminopropyltrimethoxydecane, γ-hydrothiopropyltrimethoxydecane, γ-isocyanatepropyltrimethoxydecane, and 3-glycidoxy (glycidoxy). ) propyl trimethoxy decane, and the like. These decane coupling agents may be used alone or in combination of two or more. The blending amount of the decane coupling agent is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 2 parts by weight, per 100 parts by weight of the epoxy resin and the partially esterified epoxy resin.

The curable composition of the present invention is cured by irradiation with an energy ray such as ultraviolet rays, heating, or by heating an energy ray such as ultraviolet rays. Thereby, the cured product of the curable composition of the present invention can be obtained. Therefore, the method of hardening the curable composition containing the epoxy resin of the present invention and the partially esterified epoxy resin includes irradiating ultraviolet rays to the curable composition containing the epoxy resin of the present invention and the partially esterified epoxy resin. The step of heating the energy line or heating or irradiating the energy line such as ultraviolet rays.

The esterified epoxy resin of the present invention maintains the property of extremely low elution property to liquid crystals, has low viscosity, and is excellent in liquid stability when mixed with a latent curing agent, and thus is particularly suitable as a sealing agent for liquid crystals in a dropping method. use.

[Examples]

Next, specific aspects of the invention will be described in more detail by way of examples, but the invention is not limited to the embodiments.

<Synthesis of epoxy resin A>

Epoxy resin A (in general formula (4), X is an isopropylidene group, the bonding position of X is 4,4'-position, R ²¹ is hydrogen, and Y is a stretching ethyl group)

500 g of ethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.0 g of a 45% aqueous solution of tin (II) borohydride (manufactured by Morita Chemical Industry Co., Ltd.) were placed in an eggplant-shaped flask. 340 g of bisphenol A type epoxy resin (EXA850 CRP, manufactured by DIC Co., Ltd.) was gradually added thereto at 80 ° C for 1 hour while stirring, and after the addition was completed, the mixture was stirred at 80 ° C for 1 hour. The reaction mixture was cooled to room temperature, and 1 L of chloroform was added thereto, and the mixture was washed 6 times with 1 L of water. The solvent of the obtained organic phase is removed by distillation under reduced pressure to obtain a ring-opening product of a colorless transparent viscous material (Compound 1a: a glycol open-loop of a bisphenol A type epoxy resin, in the general formula (7b), X is an isopropylidene group, and the bonding position of X is 4,4'-position, R ²¹ is hydrogen, and Y is a compound of an ethyl group extending) 410 g. Further, by high-speed liquid chromatography (HPLC), the peak of the epoxy resin of the starting material and the compound after ring-opening of only one epoxy group disappeared, and it was confirmed that all the epoxy groups were ring-opened.

232 g of the compound 1a (EXA850 CRP-ethylene glycol ring-opening), 590 g of epichlorohydrin (manufactured by Wako Pure Chemical Industries, Ltd.), and 50 g of benzyltrimethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) were placed in a mechanical stirrer. Thermometer, thermostat, condenser, Dean-Stark. Trap and a 2 L three-neck round bottom flask with a funnel. Next, the mixture was stirred under a high vacuum of 70 torr while heating to about 50 to 55 ° C to rapidly reflux the epichlorohydrin. 160 g of 48% solution NaOH (manufactured by Kanto Chemical Co., Ltd.) was slowly added to the mixture for 2 hours. As the azeotrope is produced, the epichlorohydrin is returned to the reaction system in the water/epichlorohydrin mixture and stirring is continued. After the addition was completed, stirring was continued for 3 hours. Next, the reaction mixture was cooled to room temperature, and 1 L of chloroform was added thereto, and the mixture was washed 6 times with 1 L of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 245 g of glycidyl ether (epoxy resin A) as a pale yellow transparent viscous material. Epoxy equivalent 188g / eq, viscosity 13,000mPa. s (3°×R14 rotor, 10 rpm), [M+NH ₄ ] ⁺ = 706, [M+2NH ₄ ] ²⁺ /2=619 was determined by molecular weight measurement.

[Example 1] Synthesis of esterified epoxy resin A

Epoxy resin A (50 g, 0.266 equivalent/epoxy group), methacrylic anhydride 10.25 g (0.0665 equivalent), benzyltrimethylammonium chloride 493 mg, BHT (12 mg) were placed in an eggplant-shaped flask at 90 Stir at ° C for 5 hours. The reaction mixture was cooled to 40 ° C or lower, and 150 ml of chloroform was added thereto, and the mixture was washed five times with 250 ml of water, and then washed once with 150 ml of saturated brine. Magnesium sulfate was added to the obtained organic phase, and after drying, the solid fraction was filtered by filtration or the like, and the solvent of the obtained organic phase was distilled off under reduced pressure to give an esterified epoxy resin A (54 g) as a yellow viscous material. Esterified Epoxy Resin A is a general formula (1a), X is an isopropylidene group, X is bonded to the 4,4'-position, R ²¹ is hydrogen, Y is an exoethyl group, and is present in the group:- In R _{2 in} CH ₂ —CH(OR′)—CH ₂ —OR ⁸ , the hydrogen is on average 0.3 or less, and in R ¹¹ , R ¹² , R ¹⁴ and R ¹⁵ , the hydrogen is almost zero on average, and glycidol is present. The theoretical ratio of the average number of bases to the base: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ is 75:25. Epoxy equivalent 293g / eq, viscosity 23,450mPa. s (3°×R14 rotor, 10 rpm), measured by molecular weight (A-1): [M+NH ₄ ] ⁺ = 706, (A-2): [M+NH ₄ ] ⁺ =860, (A -3): [M+NH ₄ ] ⁺ = 1015, (A-4): [M+NH ₄ ] ⁺ =1169, (A-5): [M+2NH ₄ ] ²⁺ /2=696, ( A-6): [M+2NH ₄ ] ²⁺ /2=773.

[Example 2] Synthesis of esterified epoxy resin B

In Example 1, except that methacrylic anhydride was set to 13.6 g (0.0886 equivalent), the same procedure was carried out to obtain an esterified epoxy resin B (57 g) of a yellow viscous material. Esterified Epoxy Resin B is a general formula (1a), X is an isopropylidene group, the bonding position of X is 4,4'-position, R ²¹ is hydrogen, Y is an ex-ethyl group, and is present in the group: In R' of -CH ₂ -CH(OR')-CH ₂ -OR ⁸ , the hydrogen is on average 0.3 or less, and in R ¹¹ , R ¹² , R ¹⁴ and R ¹⁵ , the hydrogen is almost zero on average, and shrinks. The theoretical ratio of the average number of glycerol groups to the base: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ is 65:35. Epoxy equivalent 368g / eq, viscosity 32,100mPa. s (3°×R14 rotor, 10 rpm), measured by molecular weight (A-1): [M+NH ₄ ] ⁺ = 706, (A-2): [M+NH ₄ ] ⁺ =860, (A -3): [M+NH ₄ ] ⁺ = 1015, (A-4): [M+NH ₄ ] ⁺ =1169, (A-5): [M+2NH ₄ ] ²⁺ /2=696, ( A-6): [M+2NH ₄ ] ²⁺ /2=773, (A-7): [M+NH ₄ ] ⁺ =1323.

In addition to (A-1)~(A-6), contains

[Example 3] Synthesis of esterified epoxy resin C

In Example 1, except that methacrylic anhydride was set to 20.5 g (0.133 equivalent), an esterified epoxy resin C (63 g) of a yellow viscous material was obtained in the same manner. Esterified Epoxy Resin C is a general formula (1a), X is an isopropylidene group, the bonding position of X is 4,4'-position, R ²¹ is hydrogen, Y is an exoethyl group, and is present in the group: In R' of -CH ₂ -CH(OR')-CH ₂ -OR ⁸ , the hydrogen is on average 0.3 or less, and in R ¹¹ , R ¹² , R ¹⁴ and R ¹⁵ , the hydrogen is almost zero on average, and shrinks. The theoretical ratio of the average number of glycerol groups to the base: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ is 50:50. Epoxy equivalent weight 528g / eq, viscosity 40,200mPa. s (3°×R14 rotor, 10 rpm), measured by molecular weight (A-1): [M+NH ₄ ] ⁺ = 706, (A-2): [M+NH ₄ ] ⁺ =860, (A -3): [M+NH ₄ ] ⁺ = 1015, (A-4): [M+NH ₄ ] ⁺ =1169, (A-5): [M+2NH ₄ ] ²⁺ /2=696, ( A-6): [M+2NH ₄ ] ²⁺ /2=773, (A-7): [M+NH ₄ ] ⁺ =1323.

Contains (A-1)~(A-7).

[Comparative Example 1] Synthesis of partially esterified epoxy resin A

Epoxy resin A (376 g, 2.0 equivalent/epoxy group), 88.7 g (1.0 equivalent) of methacrylic acid, 0.52 g of triphenylphosphine, and BHT (90 mg) were mixed, and stirred at 100 ° C for 6 hours to obtain a portion. Esterified epoxy resin A (460 g). Partially esterified epoxy resin A is a general formula (1a), X is an isopropylidene group, the bonding position of X is 4,4'-position, R ²¹ is hydrogen, Y is an ethylidene group, and is present in the group. In R-' in -CH ₂ -CH(OR')-CH ₂ -OR ⁸ , the hydrogen is theoretically 1.0 on average, and in R ¹¹ , R ¹² , R ¹⁴ and R ¹⁵ , the average hydrogen is almost 0. The theoretical ratio of the average number of glycidyl groups to the average number of bases: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ is 50:50. Epoxy equivalent 470g / eq, viscosity 100,000mPa. s (3° × R7.7 rotor, 10 rpm).

[Comparative Example 2] Partially esterified epoxy resin B

A partially esterified bisphenol A type epoxy resin (manufactured by Daicel ucp Co., Ltd.) was used in a 50% acrylonitrile group. The bisphenol A type glycidyl epoxy resin is a bifunctional epoxy resin, but a resin in which a monofunctional epoxy group is methylated with methacrylic acid. Partially esterified epoxy resin B is of the following formula: (wherein R is a glycidyl group or a group: -CH ₂ -CHOH-CH ₂ -O-CO-C(CH ₃ )=CH ₂ , the average number of glycidyl groups and a group: group: -CH ₂ - The theoretical ratio of the average number of CHOH-CH ₂ -O-CO-C(CH ₃ )=CH ₂ is 50:50).

[Test Example 1] Measurement of viscosity, epoxy equivalent, and molecular weight

For the resins obtained in Examples 1 to 3 and Comparative Examples 1 and 2, and the epoxy resin A, an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.) was used. RE105U), the viscosity measured at 25 ° C, and the epoxy equivalent measured by JIS K7236:2001 are shown in Table 1. Mass analysis was performed using a Quattro micro manufactured by Waters.

[Test Example 2] Measurement of Ni point

For the resins obtained in Examples 1 to 5 and Comparative Examples 1 and 2 and the epoxy resin A, the Ni dots were measured by the following methods. The dissolution property to the liquid crystal was evaluated by the phase transition temperature of the liquid crystal, that is, the change in the Nematic-Isotropic point. The Ni dot of the liquid crystal is determined by the mixed composition of the components of the liquid crystal, and is an inherent value in each blending. In general, impurities (other components) are mixed in these liquid crystals, and the Ni dots are known to be reduced, and it is possible to mix impurities by Ni.

[Method for measuring Ni point]

0.1 g of each epoxy resin was placed in an ampoule, and 1 g of liquid crystal (MLC-11900-080, manufactured by Merck) was added. The bottle was placed in an oven at 120 ° C for 1 hour, and then allowed to stand at room temperature. After returning to room temperature (25 ° C), the liquid crystal portion was taken out and filtered through a 0.2 μm filter to obtain a liquid crystal sample for evaluation. The measurement of the Ni point was carried out by using a differential scanning calorimeter (DSC, manufactured by Perkin-Elmer Co., Ltd., PYRIS6), and 10 mg of the liquid crystal sample for evaluation was sealed in an aluminum sample box, and the temperature was measured at a temperature elevation rate of 5 ° C /min. The measurement results are shown in Tables 1 and 2.

[Test Example 3] Determination of viscosity increase rate

5 parts by weight of each resin was mixed in the same manner as the epoxy equivalent and the active hydrogen equivalent, and the rate of change of the viscosity value before and after standing at 25 ° C for one week was measured. AJICURE VDH is used in an amount of 0.84 parts by weight relative to 5 parts by weight of the partially esterified epoxy resin A, and 1.25 parts by weight is used for AJICURE VDH with respect to 5 parts by weight of the esterified epoxy resin A, relative to the esterified epoxy resin B. 5 parts by weight, AJICURE VDH is used in an amount of 1.10 parts by weight, based on 5 parts by weight of the esterified epoxy resin C, 0.71 parts by weight of AJICURE VDH, and 0.92 part by weight of AJICURE VDH with respect to 5 parts by weight of the partially esterified epoxy resin B. Share. The measurement results are shown in Tables 1 and 2.

[Example 4] Esterified epoxy resin D

Epoxy resin A (50 g, 0.266 equivalent/epoxy group), methacrylic anhydride 10.25 g (0.0665 equivalent), PS-TBD (polystyrene-1,5,7-triazabicyclo[4.4.0]癸-5-ene) 806 mg, BHT (12 mg) was placed in an eggplant-shaped flask, and stirred at 100 ° C for 5 hours. The solid fraction was filtered to give an esterified epoxy resin D (50 g) as a yellow viscous material. Esterified epoxy resin D is a general formula (1a), X is an isopropylidene group, the bonding position of X is 4,4'-position, R ²¹ is hydrogen, Y is an ethylidene group, and is present in the group: In R' of -CH ₂ -CH(OR')-CH ₂ -OR ⁸ , the hydrogen is on average 0.3 or less, and in R ¹¹ , R ¹² , R ¹⁴ and R ¹⁵ , the hydrogen is almost zero on average, and shrinks. the average number of glycidyl _{group: -CH 2 -CH (OR ')} - the average number ratio of theory CH ₂ -OR ⁸ of 75:25. Epoxy equivalent 272g / eq, viscosity 18,200mPa. s (3°×R14 rotor, 10 rpm), measured by molecular weight (A-1): [M+NH ₄ ] ⁺ = 706, (A-2): [M+NH ₄ ] ⁺ =860, (A -3): [M+NH ₄ ] ⁺ = 1015, (A-4): [M+NH ₄ ] ⁺ =1169, (A-5): [M+2NH ₄ ] ²⁺ /2=696, ( A-6): [M+2NH ₄ ] ²⁺ /2=773.

Contains (A-1)~(A-6).

[Example 5] Esterified Epoxy Resin E

Epoxy resin A (50 g, 0.266 equivalent/epoxy group), methacrylic anhydride 10.25 g (0.0665 equivalent), PS-TPP (polystyrene-triphenylphosphine) 434 mg, BHT (12 mg) were placed in an eggplant shape The flask was stirred at 100 ° C for 7 hours. The solid fraction was filtered to give an esterified epoxy resin E (50 g) as a yellow viscous material. Esterified Epoxy Resin E is a general formula (1a), X is an isopropylidene group, the bonding position of X is 4,4'-position, R ²¹ is hydrogen, Y is an ex-ethyl group, and is present in the group: In R' of -CH ₂ -CH(OR')-CH ₂ -OR ⁸ , the hydrogen is on average 0.3 or less, and in R ¹¹ , R ¹² , R ¹⁴ and R ¹⁵ , the hydrogen is almost zero on average, and shrinks. The theoretical ratio of the average number of glycerol groups to the base: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ is 75:25. Epoxy equivalent 295g / eq, viscosity 19,150mPa. s (3°×R14 rotor, 10 rpm), measured by molecular weight (A-1): [M+NH ₄ ] ⁺ = 706, (A-2): [M+NH ₄ ] ⁺ =860, (A -3): [M+NH ₄ ] ⁺ = 1015, (A-4): [M+NH ₄ ] ⁺ =1169, (A-5): [M+2NH ₄ ] ²⁺ /2=696, ( A-6): [M+2NH ₄ ] ²⁺ /2=773.

Contains (A-1)~(A-6).

The measurement results of the esterified epoxy resins D and E obtained in Examples 4 and 5 are shown in Table 2.

[Industrial availability]

The esterified epoxy resin of the present invention can be used as a preparation material for a liquid crystal sealing agent because it maintains low solubility and elution property to the liquid crystal, reduces the viscosity of the sealant, and improves the liquid stability of the sealant.

Claims (8)

A liquid crystal sealing agent for a dropping method, characterized by containing the general formula (1): a resin represented by an esterified epoxy resin sometimes composed of a polymer thereof, or a general formula (2): a resin represented by an esterified epoxy resin sometimes composed of a polymer thereof, or a general formula (3): An esterified epoxy resin composed of a resin and a polymer thereof, in each formula, X-type -O-, an alkyl group having 1 to 4 carbon atoms, or a carbon number of 2 to 4 Alkylene group, Y-type alkyl group having 1 to 4 carbon atoms - aryl group having 6 to 20 carbon atoms - alkyl group having 1 to 4 carbon atoms, alkyl group having 1 to 4 carbon atoms - An extended aryl group having 6 to 20 carbon atoms or a group: -R ⁷ -(OR ⁷ ) _n - (wherein R ⁷ is an alkylene group having 1 to 4 carbon atoms, and n is 0 or 1 to 6 Integer), each R ^{21 is} each independently hydrogen or methyl, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently hydrogen, glycidyl, methyl glycidyl, (A Alkyl, alkyl, fluorenyl, silyl, acetal, or a group: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ or a group: -CH _{2 -C (CH 3) (oR '} ) - CH 2 -OR 8 ( wherein, R' is hydrogen, (meth) Bing Xixi, alkyl, acyl, alkyl methyl silicone, or an acetal group, R ⁸ Is a (meth) propylene fluorenyl group, but is present in the group: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ in R', the hydrogen is less than 0.8 on average), and is present in the general formula (1) And (2) of R ¹¹ , R ¹² , R ¹⁴ and R ¹⁵ Oil-based and methyl glycidyl groups and groups: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ and base: -CH ₂ -C(CH ₃ )(OR')-CH ₂ -OR ⁸ The average number is 2 or more, the average number of glycidyl groups and methyl glycidyl groups and the group: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ and the group: -CH ₂ -C(CH ₃ ) The ratio of the average number of (OR')-CH ₂ -OR ⁸ is 10:90 to 90:10, which is present in R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ^{16 of the} general formula (3). Medium, glycidyl group and methyl glycidyl group with: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ and group: -CH ₂ -C(CH ₃ )(OR')-CH ₂ -OR The total number of ⁸ is more than 2, the average number of glycidyl groups and methyl glycidyl groups and the group: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ and the group: -CH ₂ -C(CH ₃ ) The ratio of the average number of (OR')-CH ₂ -OR ⁸ is 10:90~90:10]. A liquid crystal sealing agent for dropping method, which is characterized by the general formula (1a): a resin represented by an esterified epoxy resin sometimes composed of a polymer thereof, or a general formula (2a): a resin represented by an esterified epoxy resin sometimes composed of a polymer thereof, or a general formula (3a): An esterified epoxy resin composed of a resin and a polymer thereof, in each formula, X-type -O-, an alkyl group having 1 to 4 carbon atoms, or a carbon number of 2 to 4 Alkylene group, Y-type alkyl group having 1 to 4 carbon atoms - aryl group having 6 to 20 carbon atoms - alkyl group having 1 to 4 carbon atoms, alkyl group having 1 to 4 carbon atoms - An extended aryl group having 6 to 20 carbon atoms or a group: -R ⁷ -(OR ⁷ ) _n - (wherein R ⁷ is an alkylene group having 1 to 4 carbon atoms, and n is 0 or 1 to 6 Integer), each R ^{21 is} each independently hydrogen or methyl, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently hydrogen, glycidyl, methyl glycidyl, (A Acryl fluorenyl, or a group: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ or a group: -CH ₂ -C(CH ₃ )(OR')-CH ₂ -OR ⁸ (wherein R' is hydrogen or (meth) propylene fluorenyl group, and R ⁸ is a (meth) acryl fluorenyl group, which is present in R' of the group: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ , Hydrogen has an average of less than 0.8), which is present in R ¹¹ , R ¹² , R ¹⁴ and R ¹⁵ in the general formulae (1a) and (2a), glycidyl and methyl glycidyl groups and groups: -CH _{2 -CH (OR ') - CH 2} -OR 8 and _{group: -CH 2 -C (CH 3)} (OR') - CH 2 -OR 8 Total average of two or more, glycidyl and methyl glycidyl groups with the average number of _{glycidyl: -CH 2 -CH (OR ')} - CH 2 -OR 8 group, and: -CH ₂ -C (CH ₃₎ The ratio of the average number of (OR')-CH ₂ -OR ⁸ is 10:90 to 90:10, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R existing in the general formula (3a) ^{In 16} , a glycidyl group and a methyl glycidyl group with a group: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ and a group: -CH ₂ -C(CH ₃ )(OR')-CH ₂ - The total number of OR ⁸ is 2 or more on average, and the average number of glycidyl groups and methyl glycidyl groups is related to: -CH ₂ -CH(OR')-CH ₂ -OR ⁸ and base: -CH ₂ -C ( The ratio of the average number of CH ₃ )(OR')-CH ₂ -OR ⁸ is 10:90~90:10]. A method for producing a liquid crystal sealing agent for a dropping method, which comprises an esterified epoxy resin obtained by the production method comprising the following steps (1A) to (1C), and a hardened epoxy resin according to item 2 of the patent application scope, and hardening a step of mixing the agent, (1A) a polyfunctional epoxy compound having 2 or more epoxy groups in the molecule, and reacting with a polyhydroxy compound having 2 or more hydroxyl groups in the molecule in the presence of a metal catalyst to obtain a plurality of a step of a ring-opened form of a functional epoxy compound, (1B) epoxidizing a hydroxyl group of an epoxy ring-opening compound of the polyfunctional epoxy compound obtained in the step (1A) to obtain an epoxy resin Step, (1C) a step of reacting the epoxy resin obtained in the step (1B) with (meth)acrylic anhydride. A method for producing a liquid crystal sealing agent for a dropping method, characterized in that it is contained to contain a general formula (4): a resin represented by an epoxy resin sometimes composed of a polymer thereof, or a general formula (5): a resin represented by an epoxy resin sometimes composed of a polymer thereof, or a general formula (6): The resin represented by the resin and the epoxy resin sometimes composed of the polymer thereof (wherein X is -O-, an alkylene group having 1 to 4 carbon atoms, or an alkylene group having 2 to 4 carbon atoms) , Y is an alkyl group having 1 to 4 carbon atoms - an exoaryl group having 6 to 20 carbon atoms - an alkyl group having 1 to 4 carbon atoms, and an alkyl group having 1 to 4 carbon atoms 6 to 20 of an extended aryl group, or a group: -R ⁷ -(OR ⁷ ) _n - (wherein, R ⁷ is an alkylene group having 1 to 4 carbon atoms, and n is an integer of 0 or 1 to 6), Each of R ^{21 is} independently hydrogen or methyl, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently hydrogen, glycidyl, or methyl glycidyl, but are present in general. At least two of R ¹ , R ² , R ⁴ and R ^{5 in} the formulae (4) and (5) are glycidyl groups or methyl glycidyl groups, and R ¹ and R ² are present in the general formula (6). Esterification as in the second aspect of the patent application, which is obtained by a method for producing a reaction of (meth) at least two of R ³ , R ⁴ , R ⁵ and R ⁶ with a glycidyl group or a methyl glycidyl group. An epoxy resin and a step of mixing with a hardener. A method for producing a liquid crystal sealing agent for a dropping method according to the fourth aspect of the patent application, which is produced by the method comprising the following steps (2A) to (2B), wherein the general formula (4) to the general formula (6) are used. A resin represented by a resin and sometimes composed of a polymer thereof, (2A) is given by the general formula (7a): Or general formula (8a): Or general formula (9a): [In the formula, X and R ²¹ are as defined in the fourth paragraph of the patent application], in the presence of a metal catalyst, and the following general formula (10): HO-Y-OH (10) (In the formula, Y is as defined in the fourth paragraph of the patent application scope), the dihydroxy compound is reacted to obtain the general formula (7b): a resin represented by an epoxy ring ring sometimes composed of a polymer thereof, or a general formula (8b): a resin represented by an epoxy ring ring sometimes composed of a polymer thereof, or a general formula (9b): a step of forming a resin and an epoxy ring-opening material (hereinafter, X, Y, and R ²¹ are as defined above) composed of a polymer thereof, and (2B) obtaining the step (2A) The step of epoxidizing the resin represented by any one of the general formula (7b) to the general formula (9b) and the hydroxyl group of the epoxy ring-opening material composed of the polymer. A method for producing a liquid crystal sealing agent for a dropping method, characterized in that it comprises a manufacturing method comprising the following steps (1A), (1B), (1C') and (1D) as claimed in claim 1 a step of mixing an esterified epoxy resin with a curing agent, and (1A) a polyfunctional epoxy compound having 2 or more epoxy groups in the molecule, and having 2 or more in the presence of a metal catalyst and in the molecule The polyhydroxy compound of a hydroxyl group is reacted to obtain an epoxy ring-opening compound of a polyfunctional epoxy compound, and (1B) the hydroxyl group of the epoxy ring-opening compound of the polyfunctional epoxy compound obtained in the step (1A) is epoxidized to obtain a ring. a step of oxyresin, (1C') a step of reacting the epoxy resin obtained in the step (1B) with (meth)acrylic acid to obtain a partially esterified epoxy resin, and (1D) a partial ester obtained in the step (1C') The step of reacting the epoxy resin with a (meth) propylene hydrazide, an alkylating agent, a thiolating agent, a formylating agent, or an acetalizing agent. A method for producing a liquid crystal sealing agent for a dropping method, which is to contain a general formula (1'): a resin and a partially esterified epoxy resin sometimes composed of a polymer thereof, or in the general formula (2'): a resin and a partially esterified epoxy resin sometimes composed of a polymer thereof, or in the general formula (3'): a resin represented by a resin and a partially esterified epoxy resin sometimes composed of a polymer thereof (in the formula, X-O-, an alkyl group having 1 to 4 carbon atoms, or a carbon number of 2 to 4) An alkylene group, Y is an alkylene group having 1 to 4 carbon atoms, an extended aryl group having 6 to 20 carbon atoms, an alkylene group having 1 to 4 carbon atoms, and an alkylene group having 1 to 4 carbon atoms. An extended aryl group having 6 to 20 carbon atoms or a group: -R ⁷ -(OR ⁷ ) _n - (wherein R ⁷ is an alkylene group having 1 to 4 carbon atoms, and n is 0 or 1 to 6 Integer), each R ^{21 is} each independently hydrogen or methyl, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently hydrogen, glycidyl, methyl glycidyl, or :-CH ₂ -CH(OH)-CH ₂ -OR ⁸ (wherein R ⁸ is a propylene fluorenyl group or a methacryl fluorenyl group), and R ^{11 is} present in the general formulae (1') and (2') And at least two of R ¹² , R ¹⁴ and R ¹⁵ are glycidyl, methyl glycidyl, or a group: -CH ₂ -CH(OH)-CH ₂ -OR ⁸ or a group: -CH ₂ -C ( CH ₃ )(OH)-CH ₂ -OR ⁸ , the average number of glycidyl groups and methyl glycidyl groups and the group: -CH ₂ -CH(OH)-CH ₂ -OR ⁸ and the group: -CH ₂ - The ratio of the average number of C(CH ₃ )(OH)-CH ₂ -OR ⁸ is 10:90 to 90:10, at least two of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ which are present in the general formula (3') are glycidyl groups, methyl glycidyl groups, Or an average of -CH ₂ -CH(OH)-CH ₂ -OR ⁸ or a group: -CH ₂ -C(CH ₃ )(OH)-CH ₂ -OR ⁸ , glycidyl and methyl glycidyl The ratio of the number to the base: -CH ₂ -CH(OH)-CH ₂ -OR ⁸ and the base: -CH ₂ -C(CH ₃ )(OH)-CH ₂ -OR ⁸ is 10:90 ~90:10] A method for producing a reaction with a (meth) propylene hydrazide, an alkylating agent, a thiolating agent, a formylating agent, or an acetalizing agent, as claimed in the patent application A step of mixing an esterified epoxy resin with a hardener. A method for producing a liquid crystal sealing agent for a dripping method according to the seventh aspect of the patent application, which is produced by a method comprising the following steps (2A) to (2C), wherein the general formula (1') to the general formula (3) A resin represented by any of ') and a partially esterified epoxy resin sometimes composed of a polymer thereof, (2A) is given by the general formula (7a): General formula (8a): Or general formula (9a): [In the formula, X and R ²¹ are as defined in the scope of claim 7], in the presence of a metal catalyst, and the following general formula (10): HO-Y-OH (10) (In the formula, Y is as defined in the seventh paragraph of the patent application scope), the dihydroxy compound is reacted to obtain the general formula (7b): An epoxy ring or a general formula (8b) which is represented by a resin and sometimes a polymer thereof: An epoxy ring or a general formula (9b) which is represented by a resin and sometimes a polymer thereof: a resin represented by the epoxy ring-opening compound (wherein, X, Y and R ²¹ are as defined above), and (2B) a general formula obtained by the step (2A) 7b)~ The resin represented by any one of the general formula (9b) and the hydroxyl group of the epoxy ring-opening material which is sometimes composed of the polymer are epoxidized to obtain the general formula (4): The resin represented by the resin and sometimes the polymer thereof, or the general formula (5): Resin represented by epoxy resin and sometimes composed of its polymer, or general formula (6): The resin represented by the resin and the epoxy resin sometimes composed of the polymer thereof (wherein X is -O-, an alkylene group having 1 to 4 carbon atoms, or an alkylene group having 2 to 4 carbon atoms) , Y is an alkyl group having 1 to 4 carbon atoms - an exoaryl group having 6 to 20 carbon atoms - an alkyl group having 1 to 4 carbon atoms, and an alkyl group having 1 to 4 carbon atoms 6 to 20 of an extended aryl group, or a group: -R ⁷ -(OR ⁷ ) _n - (wherein, R ⁷ is an alkylene group having 1 to 4 carbon atoms, and n is an integer of 0 or 1 to 6), Each of R ^{21 is} independently hydrogen or methyl, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently hydrogen, glycidyl, or methyl glycidyl, but are present in general. At least two of R ¹ , R ² , R ⁴ and R ^{5 in} the formulae (4) and (5) are glycidyl groups or methyl glycidyl groups, and R ¹ and R ² are present in the general formula (6). , at least two of R ³ , R ⁴ , R ⁵ and R ⁶ are glycidyl or methyl glycidyl groups, and (2C) is the general formula (4) to (6) obtained by the step (2B). A resin represented by a resin and a resin composed of a polymer thereof and a (meth)acrylic acid.