JP7680027B2 - Liquid crystal sealant containing modified resin and method for producing same - Google Patents

Description

The present invention relates to a curable resin composition containing a modified resin.

In the manufacturing method of liquid crystal display elements, the dropping method is a method that can create a panel by directly dropping liquid crystal into a closed loop of a curable resin composition, vacuum laminating, and releasing the vacuum. This dropping method has many advantages, such as reducing the amount of liquid crystal used and shortening the time it takes to inject the liquid crystal into the panel, and is currently the mainstream method for manufacturing liquid crystal panels that use large substrates. In methods that include the dropping method, a seal and liquid crystal are applied and laminated, after which gaps are removed and alignment is performed, and the seal is cured mainly by ultraviolet curing.

Patent Document 1 proposes improving the alignment properties of liquid crystals by partially modifying a bifunctional phenol novolac epoxy resin with a (meth)acrylic acid derivative as a raw material for a sealing agent.

JP 2008-179796 A

According to the findings of the present inventors, the resin described in Patent Document 1 has a problem in that it has low adhesive strength when substrates of a liquid crystal display element are bonded together. Therefore, the present invention aims to provide a curable resin composition containing a modified resin that exhibits high adhesive strength when substrates are bonded together.

The present invention relates to the following [1] to [7].
[1] (A) a modified resin obtained by modifying a part of the epoxy groups of an aromatic ring-containing epoxy resin with (meth)acrylic acid and a carboxylic acid (excluding (meth)acrylic acid), the carboxylic acid including a polyvalent carboxylic acid;
(B) a photopolymerization initiator and/or a heat curing agent;
A curable resin composition comprising:
[2] The curable resin composition of [1], wherein the carboxylic acid is a dicarboxylic acid or a combination of a dicarboxylic acid and a monocarboxylic acid. [3] The curable resin composition of [1] or [2], wherein the carboxylic acid is an aliphatic carboxylic acid.
[4] The curable resin composition according to any one of [1] to [3], wherein the carboxylic acid is a carboxylic acid having 4 to 14 carbon atoms.
[5] The curable resin composition according to any one of [1] to [4], wherein the epoxy resin having an aromatic ring is at least one selected from the group consisting of a bisphenol-type epoxy resin and a resorcinol-type epoxy resin.
[6] The curable resin composition according to any one of [1] to [5], which is a liquid crystal sealing material.
[7] A method for producing a modified resin as defined in [1], comprising a step of reacting an epoxy resin having an aromatic ring with a modifying compound and (meth)acrylic acid, wherein the modifying compound is a carboxylic acid including a polyvalent carboxylic acid (excluding (meth)acrylic acid), the total modification ratio of the (meth)acrylic acid and the modifying compound to the epoxy group of the epoxy resin having an aromatic ring is 10 to 90%, and the ratio of modification of the carboxylic acid to the total modification of the (meth)acrylic acid and the modifying compound is 10 to 80%.

The present invention provides a curable resin composition containing a modified resin that exhibits high adhesive strength when substrates are bonded together.

Preferred embodiments of the present invention will now be described. The term "(meth)acryloyl group" refers to an acryloyl group (CH ₂ ═CH ₂ -C(═O)-) and/or a methacryloyl group (CH ₂ ═CH(CH ₃ )-C(═O)-).

"(A) A modified resin in which a portion of the epoxy groups of an aromatic epoxy resin are modified with (meth)acrylic acid and a carboxylic acid (excluding (meth)acrylic acid), the carboxylic acid including a polycarboxylic acid" is also referred to as "(A) component". The same applies to "(B) a photopolymerization initiator and/or a heat curing agent", etc.

[Curable resin composition]
The curable resin composition comprises: (A) a modified resin in which a portion of the epoxy groups of an epoxy resin having an aromatic ring is modified with (meth)acrylic acid and a carboxylic acid (excluding (meth)acrylic acid), the carboxylic acid including a polyvalent carboxylic acid; and (B) a photopolymerization initiator and/or a heat curing agent.

The curable resin composition can improve adhesive strength even when the amount of filler is small. In addition, depending on the modification ratio of the modified resin with (meth)acrylic acid and carboxylic acid (excluding (meth)acrylic acid), the curable resin composition can have a high epoxy equivalent, which can reduce the amount of curing agent required. Therefore, the content of powder materials such as curing agents and fillers that are commonly used in liquid crystal sealants can be reduced, and workability such as applicability and cleanability can be improved.

<(A) A modified resin in which a portion of the epoxy groups of an epoxy resin having an aromatic ring is modified with (meth)acrylic acid and a carboxylic acid (excluding (meth)acrylic acid), the carboxylic acid including a polycarboxylic acid>

<Epoxy resin having aromatic ring>
An epoxy resin having an aromatic ring is a curable component of a curable resin composition and is also a raw material for a modified resin.
Examples of epoxy resins having an aromatic ring include bisphenol type epoxy resins (e.g., bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, and bisphenol AD type epoxy resins), diglycidyl ethers of bifunctional phenols (e.g., resorcinol type epoxy resins), phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, bisphenol F novolac type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, hydantoin type epoxy resins, isocyanurate type epoxy resins, and phenol novolac type epoxy resins having a triphenolmethane skeleton.
The epoxy resin having an aromatic ring is preferably a di- or higher functional epoxy resin, and particularly preferably a di- to tetra-functional epoxy resin.
The epoxy resin having an aromatic ring is preferably at least one selected from the group consisting of bisphenol type epoxy resins and resorcinol type epoxy resins.
The epoxy resin having an aromatic ring may be one component or two or more components.

<Carboxylic Acid (excluding (meth)acrylic acid)>
Carboxylic acids (excluding (meth)acrylic acid, hereinafter also simply referred to as "carboxylic acids") include polyvalent carboxylic acids. Carboxylic acids are raw materials for modified resins, and are modifying compounds for converting epoxy resins having aromatic rings into modified resins.

The carboxylic acid includes a polycarboxylic acid having two or more carboxyl groups in the molecule. The valence of the polycarboxylic acid is not particularly limited as long as it is divalent or more, and it is preferably a divalent to tetravalent carboxylic acid, and particularly preferably a divalent carboxylic acid. In addition, the carboxylic acid may include a monovalent carboxylic acid having one carboxyl group in the molecule, so long as it includes a polycarboxylic acid having two or more carboxyl groups in the molecule.

The number of carbon atoms of the carboxylic acid is not particularly limited. The number of carbon atoms of a polycarboxylic acid can be 2 or more. Also, the number of carbon atoms of a monocarboxylic acid can be 1 or more.

Examples of the carboxylic acid include an aliphatic carboxylic acid and an aromatic carboxylic acid.
Examples of the aliphatic carboxylic acid include saturated aliphatic carboxylic acids and unsaturated aliphatic carboxylic acids. The aliphatic hydrocarbon group of the saturated aliphatic carboxylic acid and the unsaturated aliphatic carboxylic acid may be either linear or branched, but is preferably linear. The number of unsaturated bonds of the unsaturated aliphatic carboxylic acid is preferably 1 or 2, and more preferably 1. Here, the "unsaturated bond" means an ethylenically unsaturated bond (C=C) and/or an acetylenically unsaturated bond (C≡C), and is preferably an ethylenically unsaturated bond.

The polyvalent aliphatic carboxylic acid is preferably a polyvalent saturated aliphatic carboxylic acid. Examples of polyvalent saturated aliphatic carboxylic acids include divalent saturated aliphatic carboxylic acids such as oxalic acid (C2), succinic acid (C4), adipic acid (C6), suberic acid (C8), sebacic acid (C10), dodecanedioic acid (C12), and tetradecanedioic acid (C14). The number in parentheses indicates the number of carbon atoms in the carboxylic acid.

The monovalent aliphatic carboxylic acid is preferably a monovalent unsaturated aliphatic carboxylic acid, and is particularly preferably a monovalent unsaturated aliphatic carboxylic acid having one unsaturated bond. Examples of such monovalent unsaturated aliphatic carboxylic acids include crotonic acid (C4) and myristoleic acid (C14).

The aromatic carboxylic acid is not particularly limited as long as it is a carboxylic acid having an aromatic ring. Specific examples of aromatic carboxylic acids include polyvalent aromatic carboxylic acids such as terephthalic acid and isophthalic acid; and monovalent aromatic carboxylic acids such as benzoic acid and 3-phenylpropionic acid.

(Preferred embodiment)
The carboxylic acid is preferably a dicarboxylic acid or a combination of a dicarboxylic acid and a monocarboxylic acid.
The carboxylic acid is preferably an aliphatic carboxylic acid. The polycarboxylic acid is preferably a polyaliphatic carboxylic acid, and more preferably a divalent aliphatic carboxylic acid (aliphatic dicarboxylic acid). The monocarboxylic acid is preferably a monovalent aliphatic carboxylic acid, and more preferably a monovalent unsaturated aliphatic carboxylic acid.
The carboxylic acid preferably comprises a carboxylic acid having 4 to 14 carbon atoms, and preferably consists of a carboxylic acid having 4 to 14 carbon atoms.
The carboxylic acid may be one component or two or more components.

(Meth)acrylic acid
The (meth)acrylic acid is at least one selected from the group consisting of acrylic acid and methacrylic acid.

<<Transmutation>>
In the component (A), "a part of the epoxy groups of the epoxy resin having an aromatic ring is modified with (meth)acrylic acid and a carboxylic acid (excluding (meth)acrylic acid)" means that all the carboxyl groups of the polycarboxylic acid are involved in the modification of the epoxy groups of the epoxy resin having an aromatic ring. That is, in the component (A), a part of the epoxy groups of the epoxy resin having an aromatic ring is modified with (meth)acrylic acid, and a part of the epoxy groups of the epoxy resin having an aromatic ring modified with the (meth)acrylic acid is modified with a polycarboxylic acid. Here, the remaining carboxyl groups of the polycarboxylic acid that are not involved in the modification of the epoxy resin having an aromatic ring modify a part of the epoxy groups of the epoxy resin having a further aromatic ring.

Such modified resins may contain, for example, a component having a structure shown in formula (1) below.

〔式中、
Ｘ^１は、ｎ１価の炭化水素基であり、
ｎ１は、２以上であり、
Ｂ^１は、それぞれ独立に、下記式（２）で示される基であって、式（２）中のエステル基がＸ^１に結合し、
Ａｒ^１は、それぞれ独立に、ｎ２＋１価の芳香環を有する基であり、
ｎ２は、それぞれ独立に、１以上であり、
Ａ^１は、それぞれ独立に、下記式（３）で表される基又は下記式（４）で表される基であるが、但し、分子中に、式（３）で表される基、及び、式（４）で表される基を有し、
Ｒ^１は、それぞれ独立に、水素原子又はメチル基であり、
＊は、結合位置を意味する。〕

[During the ceremony,
^X1 is a n1-valent hydrocarbon group;
n1 is 2 or more,
^B1 each independently represents a group represented by the following formula (2), in which the ester group in formula (2) is bonded to ^X1 :
Each Ar ¹ is independently a group having an (n2+1)-valent aromatic ring;
Each n2 is independently 1 or more;
A ¹ is each independently a group represented by the following formula (3) or a group represented by the following formula (4), provided that A 1 has a group represented by the formula (3) and a group represented by the formula (4) in the molecule,
Each R ¹ is independently a hydrogen atom or a methyl group;
* indicates the bond position.

^X1 , n1
^X1 is a n1-valent hydrocarbon group. ^X1 is a residue obtained by removing a carboxyl group from a polycarboxylic acid. The n1-valent hydrocarbon group may be an aliphatic group or an aromatic group.
n1 is 2 or more and corresponds to the valence of the polycarboxylic acid. n1 may be 2 to 4, or may be 2.
When n1 is divalent, examples of ^X1 include ^X11 described below. When n1 is trivalent or more, examples of ^X1 include groups in which one or more hydrogen atoms have been removed from ^X11 described below.

・^B1
Each ^B1 is independently a group represented by formula (2), and the ester group in formula (2) is bonded to ^X1 . ^B1 has a structure in which an epoxy group of an aromatic ring-containing epoxy resin reacts with a carboxyl group of a polyvalent carboxylic acid to open the epoxy group.

Ar ¹ , n2
Each Ar ¹ is independently a group having an aromatic ring with a valence of n2+1. Ar ¹ corresponds to the aromatic ring portion of the aromatic ring-containing epoxy resin.
Each n2 is independently 1 or more, and corresponds to the "epoxy functionality number - 1" of the aromatic ring-containing epoxy resin. n1 may be 1 to 3, or may be 1.

The aromatic ring contained in Ar ¹ may be a heteroaromatic ring. The aromatic ring contained in Ar ¹ may be one type alone or two or more types, and may have a monocyclic structure or a condensed ring structure.

Specific examples of aromatic rings include a benzene ring, a naphthalene ring, a fluorene ring, an anthracene ring, a furan ring, a pyrrole ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a thiazine ring, and rings having a substituent bonded thereto. Examples of the substituent include an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkylmercapto group, a cycloalkyl group, and a halogen atom.

In addition, a plurality of aromatic rings may be present, linked directly or via a linking group. Specific examples of the linking group include an alkylene group having 1 to 4 carbon atoms, an alkylidene group having 2 to 4 carbon atoms, an ether group, an ester group, a keto group, a sulfide group, and a sulfonyl group. In addition, in formula (1), the oxygen atom bonded to Ar ¹ and the aromatic ring contained in Ar ¹ may be bonded via this linking group, but it is preferable that the aromatic ring contained in Ar ¹ is directly bonded to the oxygen atom bonded to Ar ¹ .

Specific examples of Ar ¹ when the valence of n2+1 is divalent include an arylene group, an arylene-alkylene-arylene group, or an arylene-O-(R ⁵¹ -O) _m1 -arylene group (wherein R ⁵¹ is an alkylene group and m1 is 0 or an integer of 1 to 6), and preferably a group in which two hydroxyl groups have been removed from a bisphenol, such as a phenylene group (a group in which two hydroxyl groups have been removed from resorcinol), a phenylene-isopropylidene-phenylene group (a group in which two hydroxyl groups have been removed from bisphenol A), a phenylene-methylene-phenylene group (a group in which two hydroxyl groups have been removed from bisphenol F), or a phenylene-ethylidene-phenylene group (a group in which two hydroxyl groups have been removed from bisphenol AD).

Specific examples of Ar ¹ when the n2+1 valency is trivalent include the following formulae: In this case, * indicates the bonding position.

Specific examples of Ar ¹ when the n2+1 valency is tetravalent include the following formulae: In this case, * indicates the bonding position.

〔式中、Ｒ^６１は、独立に、水素原子、炭素原子数１～４のアルキル基であり、ｍ４は、０又は１以上であり、Ｒ^６２は、独立に、結合位置又は水酸基であり、Ｒ^６２における結合位置の数は、Ａｒ^１の価数に一致する。〕 Specific examples of Ar ¹ when the valence of n2+1 is 2 or more include phenol novolaks represented by the following formula:

[In the formula, R ⁶¹ is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m4 is 0 or 1 or more, R ⁶² is independently a bonding position or a hydroxyl group, and the number of bonding positions in R ⁶² corresponds to the valence of Ar ^1. ]

Specific examples of Ar ¹ when the n2+1 valence is 5 or more include groups in which 4 or more hydrogen atoms bonded to aromatic carbon atoms have been removed, such as a phenyl group, a biphenylyl group, a naphthyl group, a terphenylyl group, an anthracenyl group, or a fluorenyl group; groups in which 3 or more hydrogen atoms bonded to aromatic carbon atoms have been removed from the specific examples of Ar ¹ when the n2+1 valence is 2; groups in which 2 or more hydrogen atoms bonded to aromatic carbon atoms have been removed from the aromatic group of the specific examples of Ar ¹ when the n2+1 valence is trivalent; and groups in which 1 or more hydrogen atoms bonded to aromatic carbon atoms have been removed from the specific examples of Ar ¹ when the n2+1 valence is tetravalent.

Each ^A1 is independently a group represented by the above formula (3) or a group represented by the above formula (4). The group represented by formula (3) corresponds to an epoxy group of an epoxy resin having an aromatic ring. The group represented by formula (4) corresponds to a structure formed by reacting an epoxy group of an epoxy resin having an aromatic ring with (meth)acrylic acid and/or a carboxylic acid.
Each R ¹ is independently a hydrogen atom or a methyl group. When modified with acrylic acid, R ¹ is a hydrogen atom. When modified with methacrylic acid, R ¹ is a methyl group.

When the epoxy resin having an aromatic ring is a bifunctional epoxy resin and the polycarboxylic acid is a dicarboxylic acid, the representative structure of component (A) is preferably represented by the following formula (5).

〔式中、
Ｘ^１１は、アルキレン基、アルケニレン基又はＡｒ^１１と同義であり、
Ａｒ^１１及びＡｒ^１２は、それぞれ独立に、アリーレン基、アリーレン－アルキレン－アリーレン基、又は、アリーレン－Ｏ－（Ｒ^５１－Ｏ）_ｍ１－アリーレン基（式中、Ｒ^５１は、アルキレン基であり、ｍ１は、０又は１～６の整数である）であり、
Ａ^１１及びＡ^１２は、それぞれ独立に、式（３）で表される基又は式（４）で表される基であるが、但し、分子中に、式（３）で表される基、及び、式（４）で表される基を有する。

[During the ceremony,
X ¹¹ is an alkylene group, an alkenylene group, or has the same meaning as Ar ¹¹ ;
Ar ¹¹ and Ar ¹² each independently represent an arylene group, an arylene-alkylene-arylene group, or an arylene-O-(R ⁵¹ -O) _m1 -arylene group (wherein R ⁵¹ is an alkylene group and m1 is 0 or an integer of 1 to 6);
A ¹¹ and A ¹² are each independently a group represented by formula (3) or a group represented by formula (4), provided that the molecule contains a group represented by formula (3) and a group represented by formula (4).

In addition, when the carboxylic acid contains a monovalent carboxylic acid, the modified resin has a group in which an epoxy group is modified with a monovalent carboxylic acid. An example of such a group is a group represented by the following formula (6). A ¹ in the above formula (1) (A ¹¹ and A ¹² in the above formula (5)) contains formula (6).

〔式中、Ｒ^２は、アルキル基、アルケニル基、アルキニル基又はアリール基であるが、但し、Ｒ^２は、ビニル基又は１－メチルビニル基ではなく、＊は、結合位置を意味する。〕

(In the formula, ^R2 is an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, provided that ^R2 is not a vinyl group or a 1-methylvinyl group, and * indicates the bonding position.)

In this specification, alone or in combination with other terms, an "alkyl group" is a monovalent group that is linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 18, even more preferably 1 to 10, and particularly preferably 1 to 4. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, and an n-dodecyl group.

As used herein, alone or in combination with other terms, an "alkylene group" is a divalent group that is linear or branched. The number of carbon atoms in the alkylene group is preferably 1 to 20, and particularly preferably 1 to 8. Examples of the alkylene group include a methylene group, an ethylene group, an ethylidene group (ethane-1,1-diyl group), a trimethylene group, a propylene group (propane-1,2-diyl group), a propylidene group (propane-1,1-diyl group), an isopropylidene group (propane-2,2-diyl group), a tetramethylene group, a butylidene group (butane-1,1-diyl group), an isobutylidene group (2-methylpropane-1,1-diyl group), a pentamethylene group, a 2-methylpentane-1,5-diyl group, a hexamethylene group, a 2-ethylhexane-1,6-diyl group, a heptamethylene group, and an octamethylene group.

In this specification, alone or in combination with other terms, an "alkenyl group" is a monovalent group that is linear or branched. The number of unsaturated bonds in the alkenyl group is preferably 1 to 5, and particularly preferably 1 or 2. The number of carbon atoms in the alkenyl group is preferably 2 to 20, more preferably 3 to 20, even more preferably 3 to 15, and particularly preferably 3 to 10. In addition, when the alkenyl group contains a vinyl group or a 1-methylvinyl group, the number of carbon atoms in the alkenyl group may be 2 to 20, 2 to 15, or 2 to 10. Examples of alkenyl groups include vinyl groups, 1-methylvinyl groups, 1-propenyl groups, 2-propenyl groups, 1-methyl-1-propenyl groups, 2-methyl-1-propenyl groups, 2-butenyl groups, 3-butenyl groups, 2-pentenyl groups, 3-pentenyl groups, 4-pentenyl groups, 2-hexenyl groups, 3-hexenyl groups, 4-hexenyl groups, 5-hexenyl groups, and 9-decenyl groups.

In this specification, alone or in combination with other terms, an "alkynyl group" is a monovalent group that is linear or branched. The number of carbon atoms in the alkynyl group is preferably 2 to 20, and particularly preferably 2 to 15. Examples of the alkynyl group include an ethynyl group, a propargyl group, a 2-butynyl group, a 3-butynyl group, a 2-pentynyl group, a 3-pentynyl group, a 4-pentynyl group, a 2-hexynyl group, a 3-hexynyl group, a 4-hexynyl group, and a 5-hexynyl group.

The alkyl group, alkylene group, alkenyl group, and alkynyl group may be substituted with a substituent. The substituent is not particularly limited, and examples thereof include a halogen atom and an amino group.

In this specification, an "aryl group", alone or in combination with other terms, is a monovalent group having a monocyclic or polycyclic aromatic ring. The number of carbon atoms in the aryl group is preferably 6 to 20. Examples of the aryl group include a phenyl group, a biphenylyl group, a naphthyl group, a terphenylyl group, an anthracenyl group, and a fluorenyl group, and the phenyl group is preferred.

In this specification, an "arylene group", alone or in combination with other terms, is a divalent group having a monocyclic or polycyclic aromatic ring. The number of carbon atoms in the arylene group is preferably 6 to 20. Examples of the arylene group include a phenylene group, a naphthylene group, an anthranylene group, and a phenanthranylene group, with a phenylene group and a naphthylene group being preferred.

The aryl group and the arylene group may be substituted with a substituent. The substituent is not particularly limited, and examples thereof include an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkylmercapto group, a cycloalkyl group, and a halogen atom. The alkyl group preferably has 1 to 4 carbon atoms. The alkyl portion of the alkoxy group is preferably an alkyl group having 1 to 4 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an i-butoxy group, a sec-butoxy group, and a tert-butoxy group. The alkyl portion of the alkylcarbonyl group and the alkylmercapto group is preferably an alkyl group having 1 to 4 carbon atoms. Examples of the alkylcarbonyl group include an acetyl group, a propanoyl group, a 2-methylpropanoyl group, and a butanoyl group. Examples of alkyl mercapto groups include methyl mercapto groups, ethyl mercapto groups, propyl mercapto groups, i-propyl mercapto groups, butyl mercapto groups, i-butyl mercapto groups, sec-butyl mercapto groups, and tert-butyl mercapto groups. Examples of cycloalkyl groups are monocyclic or polycyclic aliphatic hydrocarbon groups having 3 to 20 carbon atoms, such as cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, cyclooctyl groups, cyclodecyl groups, cyclododecyl groups, and adamantyl groups.

[Method of producing modified resin]
The method for producing the modified resin is not particularly limited as long as the modified resin can be obtained. For example, the method for producing the modified resin includes a method including a step of reacting an epoxy resin having an aromatic ring, a modifying compound (i.e., a carboxylic acid including a polycarboxylic acid (excluding (meth)acrylic acid)), and (meth)acrylic acid.

<Reaction conditions>
As the reaction conditions for obtaining the modified resin, known conditions used in the reaction of an epoxy resin, a modifying compound, and (meth)acrylic acid can be appropriately applied.

The reaction can be carried out in the presence or absence of a basic catalyst and/or an acid catalyst. Examples of the basic catalyst and acid catalyst include known basic catalysts and acid catalysts used in the reaction of an epoxy resin with a modifying compound.

The basic catalyst is preferably an alkali metal hydroxide (sodium hydroxide, potassium hydroxide, etc.), an alkali metal carbonate (sodium carbonate, potassium carbonate, etc.), an alkali metal alkoxide (sodium methoxide, etc.), a trivalent organic phosphorus compound, and/or an amine compound. It is also possible to use a polymer-supported basic catalyst in which the basic catalyst is supported on a polymer.

Examples of trivalent organic phosphorus compounds include alkyl phosphines such as triethylphosphine, tri-n-propylphosphine, and tri-n-butylphosphine, and their salts; aryl phosphines such as triphenylphosphine, tri-m-tolylphosphine, tris-(2,6-dimethoxyphenyl)phosphine, and bis[2-(diphenylphosphino)phenyl]ether, and their salts; and phosphorous triesters such as triphenylphosphite, triethylphosphite, and tris(nonylphenyl)phosphite, and their salts. Examples of salts of trivalent organic phosphorus compounds include triphenylphosphine ethyl bromide, triphenylphosphine butyl bromide, triphenylphosphine octyl bromide, triphenylphosphine decyl bromide, triphenylphosphine isobutyl bromide, triphenylphosphine propyl chloride, triphenylphosphine pentyl chloride, and triphenylphosphine hexyl bromide.

Examples of amine compounds include secondary amines such as diethanolamine, tertiary amines such as triethanolamine, dimethylbenzylamine, trisdimethylaminomethylphenol, and trisdiethylaminomethylphenol, and strongly basic amines such as 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (Me-TBD), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 6-dibutylamino-1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), and 1,1,3,3-tetramethylguanidine, and salts thereof. Of these, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) is preferred. Examples of salts of amine compounds include benzyltrimethylammonium chloride and benzyltriethylammonium chloride.

Examples of the acid catalyst include sulfuric acid, sulfonic acids such as trifluoromethanesulfonic acid, graphite oxide, and antimony fluoride. The acid catalyst may also be a cation exchanger (e.g., Amberlyst is a commercially available product). The acid catalyst may be used for the reaction of an epoxy resin with one or more compounds selected from the group consisting of alcohols and thiols.

The reaction can be carried out in the presence or absence of a solvent. Inert solvents such as hydrocarbons, ethers, or ketones can be used in the reaction, but these solvents are not essential if an excess of epoxy resin is used, as the resin also functions as a solvent.

The reaction temperature can be appropriately set by a person skilled in the art depending on the catalyst and raw material compounds used. For example, when the catalyst is a basic catalyst and (meth)acrylic acid and one or more modified compounds selected from the group consisting of carboxylic acids (excluding (meth)acrylic acid) and carboxylic acid anhydrides (excluding (meth)acrylic anhydride) are used, the reaction temperature is preferably 60 to 120°C, more preferably 80 to 120°C, even more preferably 90 to 120°C, and particularly preferably 100°C to 120°C.

In the method for producing modified resins, the total modification ratio of (meth)acrylic acid and the modifying compound to the epoxy groups of the epoxy resin having an aromatic ring is more than 0% and less than 100%, and preferably 10 to 90%. In addition, the ratio of modification of carboxylic acid to the total modification of (meth)acrylic acid and the modifying compound is more than 0% and less than 100%, and preferably 10 to 80%. In the method for producing modified resins, the reaction between the epoxy groups and the (meth)acrylic acid and the modifying compound proceeds quantitatively, so the modification ratio of the obtained modified resin can also be estimated from the epoxy equivalent.

The (meth)acrylic acid and the modifying compound may be simultaneously reacted with an epoxy resin having an aromatic ring to obtain a modified resin. Alternatively, an epoxy resin having an aromatic ring may be reacted with a modifying compound to obtain an epoxy resin partially modified with the modifying compound, and the epoxy resin partially modified with the modifying compound may be reacted with (meth)acrylic acid to obtain a modified resin. Alternatively, an epoxy resin having an aromatic ring may be reacted with (meth)acrylic acid to obtain an epoxy resin partially modified with (meth)acrylic acid, and the epoxy resin partially modified with (meth)acrylic acid may be reacted with a modifying compound to obtain a modified resin.

The modified resin obtained by the manufacturing method of the modified resin may be obtained as a resin mixture containing resins having the same skeleton. Here, the skeleton in the modified resin refers to the portion obtained by removing the epoxy group from an epoxy resin having an aromatic ring. For example, when the epoxy resin is a bisphenol-type epoxy resin, the skeleton may be a group obtained by removing two hydroxyl groups from a bisphenol, such as a phenylene-isopropylidene-phenylene group (a group obtained by removing two hydroxyl groups from bisphenol A), a phenylene-methylene-phenylene group (a group obtained by removing two hydroxyl groups from bisphenol F), or a phenylene-ethylidene-phenylene group (a group obtained by removing two hydroxyl groups from bisphenol AD).

The (A) component may be one or a combination of two or more. That is, the modified resin may be composed of only one component, or may be a mixture of two or more components in which at least one of X ¹ , A ¹ , and Ar ¹ in formula (1) is different, depending on the type of epoxy resin having an aromatic ring, (meth)acrylic acid, and carboxylic acid (excluding (meth)acrylic acid). For example, when the epoxy resin having an aromatic ring is a bifunctional epoxy resin and the carboxylic acid is a combination of a divalent carboxylic acid and a monovalent carboxylic acid, the modified resin may be a mixture of components represented by formula (5) in which A ¹¹ and A ¹² have a group represented by formula (3), a group represented by formula (4), and a group represented by formula (6) in formula (5). In addition, when the modified resin obtained by the method for producing a modified resin is a resin mixture, it may be a mixture of two or more types of (A) components, in which at least one of X ¹ and A ¹ in formula (1) (X ¹ , A ¹¹ , and A ¹² in formula (5)) is different, depending on the types of the epoxy resin having an aromatic ring, the modifying compound, and the (meth)acrylic acid.

<(B) Photopolymerization initiator and/or heat curing agent>
The photopolymerization initiator is a component that can turn the curable resin composition into a photopolymerizable curable composition. The heat curing agent is a component that can turn the curable resin composition into a heat curable composition. The photopolymerization initiator and/or heat curing agent can be appropriately selected depending on the type of the curable resin contained in the curable resin composition and the desired curing conditions (energy ray curing and/or heat curing). Thus, the (B) component can be a photopolymerization initiator, a heat curing agent, or a combination of a photopolymerization initiator and a heat curing agent.

<Photopolymerization initiator>
The photopolymerization initiator may include a radical polymerization initiator, an anionic polymerization initiator, and/or a cationic polymerization initiator.

Radical polymerization initiators include benzoins, acetophenones, benzophenones, thioxanthones, α-acyloxime esters, phenylglyoxylates, benzils, azo compounds, diphenyl sulfide compounds, acylphosphine oxide compounds, benzoin ethers, anthraquinones, and organic peroxides. Radical polymerization initiators are preferably those that have low solubility in liquid crystals and have reactive groups that do not gasify the decomposition products when irradiated with light. In addition, as the radical polymerization initiator, a polymerization initiator that is a mixture of a polyether compound having a dialkylaminobenzoyl group and a polyether compound having a group in which one hydrogen atom has been removed from thioxanthone, as described in JP-A-2020-076794, is preferred, and a polymerization initiator that is a mixture of a compound obtained by reacting a compound having at least two epoxy groups with dimethylaminobenzoic acid and a compound obtained by reacting a compound having at least two epoxy groups with hydroxythioxanthone is particularly preferred.

Anionic polymerization initiators include imidazoles, amines, phosphines, organic metal salts, metal chlorides, organic peroxides, etc.

Examples of cationic polymerization initiators include onium salts, iron allene complexes, titanocene complexes, arylsilanol aluminum complexes, Lewis acid compounds, Bronsted acid compounds, benzylsulfonium salts, thiophenium salts, thiolanium salts, benzylammonium, pyridinium salts, hydrazinium salts, carboxylate esters, sulfonate esters, amine imides, sulfone compounds, sulfonate esters, sulfonimides, disulfonyldiazomethanes, and amines.

The photopolymerization initiators are commercially available or can be prepared according to known methods.
The photopolymerization initiator may be one type or a combination of two or more types.

<Heat curing agent>
The heat curing agent is not particularly limited, but examples thereof include amine-based heat curing agents, such as organic acid dihydrazide compounds, amine adducts, imidazole and its derivatives, dicyandiamide, aromatic amines, epoxy-modified polyamines, and polyaminoureas. Examples of suitable heat curing agents include VDH (1,3-bis(hydrazinocarboethyl)-5-isopropylhydantoin), ADH (adipic acid dihydrazide), UDH (7,11-octadecadiene-1,18-dicarbohydrazide), and the like. Preferred are organic acid dihydrazides such as LDH (octadecane-1,18-dicarboxylic acid dihydrazide) and IDH (isophthalic acid dihydrazide); polyamine compounds sold by ADEKA Corporation under the name ADEKA HARDNER EH-5030S, etc.; and amine adducts sold by Ajinomoto Fine-Techno Co., Ltd. under the names Amicure PN-23, Amicure PN-30, Amicure MY-24, Amicure MY-H, etc.
The heat curing agent may be one type or a combination of two or more types.

<Other ingredients>
The curable resin composition may contain a curable resin other than the component (A) (component (C)) and/or another component other than the component (C) (component (D)) depending on the purpose, as long as the effect of the present invention is not impaired. Examples of the component (D) include a silane coupling agent, a polymerization inhibitor, an organic filler, and an inorganic filler. Note that the components (C) and (D) are not the above-mentioned components (A) and (B).

<<Curable resin other than component (A) (component (C))>>
Examples of the component (C) include (C-1) a difunctional or higher epoxy resin, (C-2) an epoxy (meth)acrylate resin in which a part or all of the epoxy groups in the component (C-1) have been modified with (meth)acrylic acid and/or (meth)acrylic anhydride, and (C-3) other curable resins (excluding the components (C-1) and (C-2)).

<(C-1) Di- or higher functional epoxy resin>
The (C-1) component is not particularly limited, and examples thereof include the resins described above as epoxy resins having an aromatic ring. Examples of trifunctional and tetrafunctional epoxy resins include the epoxy resins described in JP 2012-077202 A. The number of epoxy functions of the (C-1) component is not particularly limited, but is preferably 2 to 4. The (C-1) component is preferably an epoxy resin having a bisphenol structure, and is particularly preferably one or more selected from the group consisting of bisphenol A type epoxy resins and bisphenol F type epoxy resins.
The component (C-1) may be one type or a combination of two or more types.

<(C-2) Epoxy (meth)acrylate resin>
The component (C-2) is an epoxy (meth)acrylate resin in which some or all of the epoxy groups of the component (C-1) have been modified with (meth)acrylic acid and/or (meth)acrylic anhydride. That is, the component (C-2) has both epoxy groups and (meth)acryloyl groups in the resin, or has no epoxy groups and has (meth)acryloyl groups in the resin. Here, the component (C-1), including the preferred ones, is as described above.
The component (C-2) is particularly preferably an epoxy (meth)acrylate resin in which some of the epoxy groups of a difunctional epoxy resin have been modified with (meth)acrylic acid and/or (meth)acrylic anhydride.
The component (C-2) may be one type or a combination of two or more types.

<(C-3) Other curable resins>
The (C-3) component is not particularly limited as long as it is a curable resin other than the (A), (C-1) and (C-2) components, and examples thereof include a resin having a conventional unsaturated group and/or an epoxy group, a resin having one epoxy group, and a resin having neither an unsaturated group nor an epoxy group, which are used as the main agent of a curable resin composition. Here, the "unsaturated group" means an ethylenically unsaturated group and/or an acetylenically unsaturated group. The (C-3) component is appropriately selected from a cationic polymerizable resin, a radically polymerizable resin and/or an anionic polymerizable resin according to the type of polymerization initiator and/or heat curing agent contained in the curable resin composition.

Examples of resins having unsaturated groups include (meth)acrylate compounds, aliphatic acrylamide compounds, alicyclic acrylamide compounds, acrylamide compounds containing aromatic groups, N-substituted acrylamide compounds, and diene polymers (e.g., polybutadiene polymers, polyisoprene polymers, etc.). The functionality of the (meth)acrylate compound can be monofunctional, bifunctional, or polyfunctional (i.e., trifunctional or higher), and is preferably bifunctional or trifunctional or higher.

As the bifunctional (meth)acrylate compound, one or more compounds selected from the group consisting of tricyclodecane dimethanol di(meth)acrylate, dimethylol dicyclopentane di(meth)acrylate, EO-modified 1,6-hexanediol di(meth)acrylate, EO-modified bisphenol A di(meth)acrylate, PO-modified bisphenol A di(meth)acrylate, polyester di(meth)acrylate (e.g., ARONIX M-6100, manufactured by Toa Gosei Co., Ltd.), polyethylene glycol di(meth)acrylate (e.g., 4G, manufactured by Shin-Nakamura Chemical Co., Ltd.), and silicon di(meth)acrylate (e.g., EBECRYL 350, manufactured by Daicel-Allnex Corporation) are preferred. Here, "EO" means ethylene oxide and "PO" means propylene oxide.

As the polyfunctional (meth)acrylate compound having three or more functionalities, one or more compounds selected from EO-modified glycerol tri(meth)acrylate (trifunctional), PO-modified glycerol tri(meth)acrylate (trifunctional), pentaerythritol tri(meth)acrylate (trifunctional), dipentaerythritol hexa(meth)acrylate (hexafunctional) and pentaerythritol tetra(meth)acrylate (tetrafunctional) are preferred.

Further, examples of the resin having an unsaturated group include epoxy resins in which all of the epoxy groups of the epoxy resin have been modified with a modifying compound having an unsaturated group (excluding (meth)acrylic acid and acrylic anhydride).
Resins having one epoxy group include aromatic epoxy resins and aliphatic epoxy resins.
Examples of resins having neither an unsaturated group nor an epoxy group include modified epoxy resins in which all of the epoxy groups of an epoxy resin have been modified with a modifying compound having no unsaturated groups, and urethane resins formed from a hydroxyl group-containing compound and an isocyanate group-containing compound.
The component (C-3) may be one type or a combination of two or more types.

The (C) component may be one type or a combination of two or more types. For example, the (C) component may be a combination of one or more (C-1) components and one or more (C-2) components.

<<Other components other than component (C) (component (D))>>
Examples of the component (D) include a silane coupling agent, a polymerization inhibitor, an organic filler, and an inorganic filler.

<Silane coupling agent>
Examples of the silane coupling agent include a silane compound having one or more reactive functional groups selected from the group consisting of epoxy group, alkenyl group (e.g., vinyl group), (meth)acryloyl group, primary or secondary amino group, mercapto group, isocyanato group, ureido group and halogen atom, or an alkyl group substituted with said group, and one or more alkoxy groups, and may have an unsubstituted alkyl group.The reactive functional group may be bonded to the silicon atom of the silane compound as the alkyl group substituted with said reactive functional group.

Specific examples of the silane coupling agent include silane compounds having an epoxy group and an alkoxy group, and which may have an alkyl group, such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; silane compounds having an alkenyl group and an alkoxy group, and which may have an alkyl group, such as vinyltrimethoxysilane and p-styryltrimethoxysilane; silane compounds having a (meth)acrylic group and an alkoxy group, and which may have an alkyl group, such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(a [0043] Examples of such silane compounds include silane compounds having a primary or secondary amino group and an alkoxy group, and optionally having an alkyl group, such as N-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, and N-phenyl-3-aminopropyltrimethoxysilane; and silane compounds having one or more groups selected from the group consisting of a mercapto group, an isocyanato group, a ureido group, and a halogen atom, and one or more alkoxy groups, and optionally having an alkyl group, such as 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, and 3-isocyanatopropyltriethoxysilane.
The silane coupling agent may be used alone or in combination of two or more kinds.

Inorganic fillers include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, titanium oxide, alumina, zinc oxide, silicon dioxide (precipitated silica, fumed silica, etc.), kaolin, talc, glass beads, sericite activated clay, aluminum hydroxide, asbestos powder, copper oxide, copper hydroxide, iron oxide, lead oxide, magnesium oxide, tin oxide, carbon, mica, smectite, carbon black, bentonite, aluminum nitride, and silicon nitride. The inorganic fillers may be one type or a combination of two or more types.

Examples of organic fillers include acrylic particles, polymethyl methacrylate, polystyrene (polystyrene beads), copolymers obtained by copolymerizing the monomers constituting these (i.e., methyl methacrylate or styrene) with other monomers, polyethylene particles, polysiloxane resin particles, polyamide particles, polyester fine particles, polyurethane fine particles, and rubber fine particles (acrylic rubber particles, isoprene rubber particles). The organic filler may have a core-shell structure. The organic filler may be one type or a combination of two or more types.

The average particle size of the inorganic filler and the organic filler is not particularly limited, but is preferably 0.01 μm to 10 μm, and particularly preferably 1 μm to 5 μm. The average particle size of the inorganic filler and the organic filler can be measured using a laser diffraction particle size distribution measuring device.

The polymerization inhibitor includes hydroquinone, paramethoxyphenol, 2,6-di-t-butyl-4-cresol, and the like.
Components other than those described above can be appropriately selected from known components used in curable resin compositions.

The (D) component may be one or a combination of two or more. For example, the (D) component may be a combination of one or more silane coupling agents and one or more polymerization inhibitors.

<Method for preparing curable resin composition>
The curable resin composition can be produced by mixing the respective components.

<Curing method>
The curable resin composition can be cured by irradiation with energy rays such as ultraviolet rays, by application of heat, or by application of heat before, after, or simultaneously with irradiation with energy rays such as ultraviolet rays. Thus, the curable resin composition is a photo (energy ray) curable, heat curable, or energy ray and heat curable composition.

<Application>
The curable resin composition has a suppressed solubility in liquid crystal, and can prevent contamination of the liquid crystal. Therefore, the curable resin composition can be used as a liquid crystal sealant (such as a liquid crystal sealant for display elements and a liquid crystal sealant for dimming), and as a sealant for various flexible displays such as organic EL. The curable resin composition may also be a liquid crystal sealant used in liquid crystal displays (or liquid crystal display elements) including module displays, three-dimensional displays, head-mounted displays, projection displays, and the like; light-quantity adjusting liquid crystal elements such as dimming filters, dimming shutters, anti-glare mirrors, and spatial light quantity modulators; focus-variable liquid crystal elements such as liquid crystal lenses; and light-modulating liquid crystal elements such as optical deflectors, optical splitters, phase controls, polarization controls, holograms, diffraction gratings, wavelength filters, and frequency filters.

The cured product of the curable resin composition is used to seal a liquid crystal display. Therefore, the present invention also covers a liquid crystal display sealed with a curable resin composition. Examples of methods for manufacturing a liquid crystal display include a step of applying the curable resin composition to one of two transparent substrates with electrodes using a dispenser to form a pattern of the curable resin composition, a step of dropping liquid crystal onto the entire surface inside the frame of the transparent substrate and immediately laminating the other transparent substrate, and a step of curing the seal pattern by irradiating the seal pattern with light such as ultraviolet light, heating the curable resin composition, or applying heat before, after, or simultaneously with irradiation of the seal pattern with energy rays such as ultraviolet light.

The following examples will explain specific aspects of the present invention in more detail, but the present invention is not limited to these examples.

1. Production Example (1) Partially Methacrylated Bisphenol A Type Epoxy Resin 340.0 g of bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation), 86.1 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 524 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100 to 110 ° C. The reaction solution was subjected to acid value titration with an aqueous sodium hydroxide solution (0.01 N), the amount of remaining methacrylic acid was calculated, and the reaction rate was calculated from the amount of methacrylic acid added initially and the amount of remaining methacrylic acid, and the mixture was heated and stirred until the reaction rate reached 99.9% or more. 418.0 g of a partially methacrylated bisphenol A type epoxy resin was obtained as a pale yellow transparent viscous product. The epoxy equivalent of the obtained resin was 470 g / eq.

(2) Partially Methacrylated Bisphenol F Epoxy Resin 320.0 g of bisphenol F epoxy resin (EXA-830CRP, manufactured by DIC Corporation), 86.1 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 524 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100 to 110 ° C. The reaction solution was subjected to acid value titration with an aqueous sodium hydroxide solution (0.01 N), the amount of remaining methacrylic acid was calculated, and the reaction rate was calculated from the amount of methacrylic acid added initially and the amount of remaining methacrylic acid, and the mixture was heated and stirred until the reaction rate reached 99.9% or more. 400.1 g of a partially methacrylated bisphenol F epoxy resin was obtained as a pale yellow, transparent, viscous product. The epoxy equivalent of the obtained resin was 410 g / eq.

(3) Partially Methacrylated Resorcinol-Type Epoxy Resin 35.1 g of resorcinol-type epoxy resin (EX-201, Nagase Quantex Co., Ltd.), 12.9 g of methacrylic acid (Tokyo Chemical Industry Co., Ltd.), and 81 mg of triphenylphosphine (Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100 to 110 ° C. The reaction solution was subjected to acid value titration with an aqueous sodium hydroxide solution (0.01 N) to calculate the amount of remaining methacrylic acid, and the reaction rate was calculated from the amount of methacrylic acid added initially and the amount of remaining methacrylic acid. The reaction was allowed to proceed with heating and stirring until the reaction rate reached 99.9% or more. 42.5 g of a partially methacrylated resorcinol-type epoxy resin was obtained as a pale yellow, transparent, viscous product. The epoxy equivalent of the obtained resin was 330 g/eq.

(4) Modified epoxy resin 1
112.0 g of bisphenol F type epoxy resin (EXA-830CRP, manufactured by DIC Corporation), 12.1 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 4.03 g of dodecanedioic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 275 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100 to 110 ° C. The reaction solution was subjected to acid value titration with an aqueous sodium hydroxide solution (0.01 N), the amount of remaining methacrylic acid was calculated, and the reaction rate was calculated from the amount of methacrylic acid added initially and the amount of remaining methacrylic acid, and the mixture was heated and stirred until the reaction rate reached 99.9% or more. 121.2 g of modified epoxy resin 1 was obtained as a pale yellow transparent viscous product. The epoxy equivalent of the obtained resin was 242 g / eq.

(5) Modified epoxy resin 2
112.0 g of bisphenol F type epoxy resin (EXA-830CRP, manufactured by DIC Corporation), 12.1 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 24.2 g of dodecanedioic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 275 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100 to 110 ° C. The reaction solution was subjected to acid value titration with an aqueous sodium hydroxide solution (0.01 N), the amount of remaining methacrylic acid was calculated, and the reaction rate was calculated from the amount of methacrylic acid added initially and the amount of remaining methacrylic acid, and the mixture was heated and stirred until the reaction rate reached 99.9% or more. 141.7 g of modified epoxy resin 2 was obtained as a pale yellow transparent viscous product. The epoxy equivalent of the obtained resin was 425 g / eq.

(6) Modified epoxy resin 3
112.0 g of bisphenol F type epoxy resin (EXA-830CRP, manufactured by DIC Corporation), 30.1 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 24.2 g of dodecanedioic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 275 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100 to 110 ° C. The reaction solution was subjected to acid value titration with an aqueous sodium hydroxide solution (0.01 N), the amount of remaining methacrylic acid was calculated, and the reaction rate was calculated from the amount of methacrylic acid added initially and the amount of remaining methacrylic acid, and the mixture was heated and stirred until the reaction rate reached 99.9% or more. 160.3 g of modified epoxy resin 3 was obtained as a pale yellow transparent viscous product. The epoxy equivalent of the obtained resin was 1284 g / eq.

(7) Modified epoxy resin 4
112.0 g of bisphenol F type epoxy resin (EXA-830CRP, manufactured by DIC Corporation), 12.1 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.54 g of sebacic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 275 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100 to 110 ° C. The reaction solution was subjected to acid value titration with an aqueous sodium hydroxide solution (0.01 N), the amount of remaining methacrylic acid was calculated, and the reaction rate was calculated from the amount of methacrylic acid added initially and the amount of remaining methacrylic acid, and the mixture was heated and stirred until the reaction rate reached 99.9% or more. 120.8 g of modified epoxy resin 4 was obtained as a pale yellow transparent viscous product. The epoxy equivalent of the obtained resin was 242 g / eq.

(8) Modified epoxy resin 5
112.0 g of bisphenol F type epoxy resin (EXA-830CRP, manufactured by DIC Corporation), 12.1 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 21.2 g of sebacic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 275 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100 to 110 ° C. The reaction solution was subjected to acid value titration with an aqueous sodium hydroxide solution (0.01 N), the amount of remaining methacrylic acid was calculated, and the reaction rate was calculated from the amount of methacrylic acid added initially and the amount of remaining methacrylic acid, and the mixture was heated and stirred until the reaction rate reached 99.9% or more. 139.9 g of modified epoxy resin 5 was obtained as a pale yellow transparent viscous product. The epoxy equivalent of the obtained resin was 418 g / eq.

(9) Modified epoxy resin 6
112.0 g of bisphenol F type epoxy resin (EXA-830CRP, manufactured by DIC Corporation), 30.1 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 21.2 g of sebacic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 275 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100 to 110 ° C. The reaction solution was subjected to acid value titration with an aqueous sodium hydroxide solution (0.01 N), the amount of remaining methacrylic acid was calculated, and the reaction rate was calculated from the amount of methacrylic acid added initially and the amount of remaining methacrylic acid, and the mixture was heated and stirred until the reaction rate reached 99.9% or more. 158.4 g of modified epoxy resin 6 was obtained as a pale yellow transparent viscous product. The epoxy equivalent of the obtained resin was 1314 g / eq.

(10) Modified epoxy resin 7
112.0 g of bisphenol F type epoxy resin (EXA-830CRP, manufactured by DIC Corporation), 12.1 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.56 g of adipic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 275 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100 to 110 ° C. The reaction solution was subjected to acid value titration with an aqueous sodium hydroxide solution (0.01 N), the amount of remaining methacrylic acid was calculated, and the reaction rate was calculated from the amount of methacrylic acid added initially and the amount of remaining methacrylic acid, and the mixture was heated and stirred until the reaction rate reached 99.9% or more. 118.0 g of modified epoxy resin 7 was obtained as a pale yellow transparent viscous product. The epoxy equivalent of the obtained resin was 239 g / eq.

(11) Modified epoxy resin 8
112.0 g of bisphenol F type epoxy resin (EXA-830CRP, manufactured by DIC Corporation), 12.1 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 15.3 g of adipic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 275 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100 to 110 ° C. The reaction solution was subjected to acid value titration with an aqueous sodium hydroxide solution (0.01 N), the amount of remaining methacrylic acid was calculated, and the reaction rate was calculated from the amount of methacrylic acid added initially and the amount of remaining methacrylic acid, and the mixture was heated and stirred until the reaction rate reached 99.9% or more. 130.7 g of modified epoxy resin 8 was obtained as a pale yellow transparent viscous product. The epoxy equivalent of the obtained resin was 407 g / eq.

(12) Modified epoxy resin 9
119.0 g of bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation), 12.1 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 21.2 g of sebacic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 275 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100 to 110 ° C. The reaction solution was subjected to acid value titration with an aqueous sodium hydroxide solution (0.01 N), the amount of remaining methacrylic acid was calculated, and the reaction rate was calculated from the amount of methacrylic acid added initially and the amount of remaining methacrylic acid, and the mixture was heated and stirred until the reaction rate reached 99.9% or more. 143.2 g of modified epoxy resin 9 was obtained as a pale yellow transparent viscous product. The epoxy equivalent of the obtained resin was 451 g / eq.

(13) Modified epoxy resin 10
Resorcinol type epoxy resin (EX-201, Nagase Mutex Co., Ltd.) 81.9g, methacrylic acid (Tokyo Chemical Industry Co., Ltd.) 12.1g, sebacic acid (Tokyo Chemical Industry Co., Ltd.) 21.2g, and triphenylphosphine (Tokyo Chemical Industry Co., Ltd.) 275mg were mixed and stirred at 100-110 ° C. The reaction solution was acid value titrated with sodium hydroxide aqueous solution (0.01N), the amount of methacrylic acid remaining was calculated, and the reaction rate was calculated from the amount of methacrylic acid added initially and the amount of methacrylic acid remaining, and the reaction was allowed to proceed with heating and stirring until the reaction rate reached 99.9% or more. 109.7g of modified epoxy resin 10 was obtained as a pale yellow transparent viscous product. The epoxy equivalent of the obtained resin was 341g/eq.

(14) Modified epoxy resin 11
Bisphenol F type epoxy resin (EXA-830CRP, manufactured by DIC Corporation) 112.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 12.1 g, sebacic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 21.2 g, crotonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 3.01 g, and triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) 275 mg were mixed and stirred at 100 to 110 ° C. The reaction solution was acid value titrated with an aqueous sodium hydroxide solution (0.01 N), the amount of remaining methacrylic acid was calculated, and the reaction rate was calculated from the amount of methacrylic acid added at the beginning and the amount of remaining methacrylic acid, and the reaction was allowed to proceed with heating and stirring until the reaction rate reached 99.9% or more. 140.7 g of modified epoxy resin 5 was obtained as a pale yellow transparent viscous product. The epoxy equivalent of the obtained resin was 474 g / eq.

(15) Modified epoxy resin 12
Bisphenol F type epoxy resin (EXA-830CRP, manufactured by DIC Corporation) 112.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 12.1 g, sebacic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 21.2 g, crotonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 9.04 g, and triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) 275 mg were mixed and stirred at 100 to 110 ° C. The reaction solution was subjected to acid value titration with an aqueous sodium hydroxide solution (0.01 N), the amount of remaining methacrylic acid was calculated, and the reaction rate was calculated from the amount of methacrylic acid added at the beginning and the amount of remaining methacrylic acid, and the reaction was allowed to proceed with heating and stirring until the reaction rate reached 99.9% or more. 147.6 g of modified epoxy resin 5 was obtained as a pale yellow transparent viscous matter. The epoxy equivalent of the obtained resin was 639 g / eq.

(16) Modified epoxy resin 13
112.0 g of bisphenol F type epoxy resin (EXA-830CRP, manufactured by DIC Corporation), 10.1 g of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.54 g of sebacic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 275 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100 to 110 ° C. The reaction solution was subjected to acid value titration with an aqueous sodium hydroxide solution (0.01 N), the amount of remaining acrylic acid was calculated, and the reaction rate was calculated from the amount of acrylic acid added initially and the amount of remaining acrylic acid, and the mixture was heated and stirred until the reaction rate was 99.9% or more. 120.2 g of modified epoxy resin 13 was obtained as a pale yellow transparent viscous matter. The epoxy equivalent of the obtained resin was 237 g / eq.

(17) Modified epoxy resin 14
112.0 g of bisphenol F type epoxy resin (EXA-830CRP, manufactured by DIC Corporation), 10.1 g of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 21.2 g of sebacic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 275 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100 to 110 ° C. The reaction solution was subjected to acid value titration with an aqueous sodium hydroxide solution (0.01 N), the amount of remaining acrylic acid was calculated, and the reaction rate was calculated from the amount of acrylic acid added initially and the amount of remaining acrylic acid, and the mixture was heated and stirred until the reaction rate was 99.9% or more. 139.2 g of modified epoxy resin 14 was obtained as a pale yellow transparent viscous matter. The epoxy equivalent of the obtained resin was 416 g / eq.

(18) Modified epoxy resin 15
112.0 g of bisphenol F type epoxy resin (EXA-830CRP, manufactured by DIC Corporation), 25.2 g of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 21.2 g of sebacic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 275 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100 to 110 ° C. The reaction solution was subjected to acid value titration with an aqueous sodium hydroxide solution (0.01 N), the amount of remaining acrylic acid was calculated, and the reaction rate was calculated from the amount of acrylic acid added initially and the amount of remaining acrylic acid, and the mixture was heated and stirred until the reaction rate was 99.9% or more. 153.8 g of modified epoxy resin 15 was obtained as a pale yellow transparent viscous matter. The epoxy equivalent of the obtained resin was 1249 g / eq.

(19) Photopolymerization initiator 1
26.8 g (0.1 epoxy equivalent) of polyethylene glycol diglycidyl ether (EX-830, Nagase ChemteX Corporation), 16.5 g (0.1 equivalent) of 4-dimethylaminobenzoic acid, 3.71 g (0.02 equivalent) of benzyltrimethylammonium chloride, and 25 g of MIBK (methyl isobutyl ketone) were placed in a flask and stirred at 110°C for 24 hours using an oil bath. The reaction mixture was cooled to room temperature, dissolved in 50 g of chloroform, and washed six times with 100 ml of water. The solvent in the organic phase was distilled off under reduced pressure, and 35.3 g of photopolymerization initiator 1 was obtained.

(20) Photopolymerization initiator 2
26.8 g (0.1 epoxy equivalent) of polyethylene glycol diglycidyl ether (EX-830, Nagase Chemtex Corporation), 22.83 g (0.1 equivalent) of 2-hydroxy-9H-thioxanthen-9-one, 3.71 g (0.02 equivalent) of benzyltrimethylammonium chloride, and 40 g of MIBK were placed in a flask and stirred at 110°C for 72 hours using an oil bath. The reaction mixture was cooled to room temperature, dissolved in 50 g of chloroform, and washed six times with 100 ml of water. The solvent in the organic phase was distilled off under reduced pressure to obtain 36.2 g of photopolymerization initiator 2.

2. Preparation of Curable Resin Compositions The components shown in the table were mixed in the amounts (parts by mass) shown in the table below, and then thoroughly kneaded using a three-roll mill (C-4 3/4×10, manufactured by Inoue Seisakusho Co., Ltd.) to prepare curable resin compositions of the examples and comparative examples. EH-5030S (polyamine compound, manufactured by ADEKA Corporation, active hydrogen equivalent 105 g/eq) was used as the heat curing agent.

3. Test method (1) Adhesive strength measurement The curable resin composition was dot-applied at 15 mm x 3 mm and 15 mm x 21 mm positions on an ITO substrate (30 mm x 30 mm x 0.5 mmt) on which 6 μm spacers were scattered, so that the diameter of the curable resin composition after lamination was in the range of 1.5 to 2.5 mmφ. Thereafter, the same type of substrate (23 mm x 23 mm x 0.5 mmt) was laminated, and the substrate was cured by irradiating ultraviolet light with an integrated light amount of 3000 mJ/cm ² (irradiation device: UVX-01224S1, manufactured by Ushio Electric Co., Ltd.), and thermally cured in a 120 ° C. oven for 1 hour to prepare a cured product test specimen. Using an autograph (TG-2kN, manufactured by Minebea Co., Ltd.), the test specimen was fixed and punched out at a position of 15 mm x 25 mm of the substrate at a speed of 5 mm/min, and the adhesive strength between the ITO substrates (ITO/ITO) was measured.

(2) NI point change Each sealant of the examples and comparative examples was poured into a mold with a diameter of 5 mm and a thickness of 0.5 mmt, and cured by irradiating ultraviolet light with an integrated light quantity of 3,000 mJ/ ^cm2 to obtain a photocured product of each sealant. Approximately 0.1 g of the obtained photocured product was placed in an ampoule bottle, and liquid crystal (MLC-6609, Merck) was added in an amount 10 times that of the photocured product. This bottle was placed in a 120°C oven for 1 hour, and then left to stand at room temperature to return to room temperature (25°C), after which the liquid crystal portion was removed and filtered through a 0.2 μm filter to obtain a liquid crystal sample for evaluation.

The NI point was measured using a differential scanning calorimeter (DSC, PerkinElmer, PYRIS6) by sealing 10 mg of the liquid crystal sample for evaluation in an aluminum sample pan and performing the measurement at a heating rate of 5°C/min. The blank was the result of sealing 10 mg of the liquid crystal in an aluminum sample pan and performing the measurement at a heating rate of 5°C/min. The blank value was 93.70°C when measuring Examples 1 to 8 and Comparative Examples 1 to 3, 93.61°C when measuring Examples 9 to 12, and 93.62°C when measuring Examples 13 to 15.

The difference between the endothermic peak top (phase transition temperature) TB of the blank and the endothermic peak top (phase transition temperature) TE of the liquid crystal for evaluation; TE-TB, was defined as the NI point change.
The NI point (Nematic-Isotropic point), which is the phase transition temperature of liquid crystal, is determined by the mixture composition of each component of the liquid crystal, and is a unique value for each blend. It is generally known that the NI point changes when some impurity (other component) is mixed into these liquid crystals. From the viewpoint of suppressing the elution of the components contained in the sealant into the liquid crystal, ensuring stable alignment of the liquid crystal, and improving display characteristics, the smaller the absolute value of the NI point change, the more preferable it is.

Claims (6)

(A) a modified resin obtained by modifying a portion of the epoxy groups of an aromatic ring-containing epoxy resin with (meth)acrylic acid and a carboxylic acid (excluding (meth)acrylic acid and excluding an acid anhydride of a carboxylic acid), the carboxylic acid including a polyvalent carboxylic acid;
(B) a photopolymerization initiator and/or a heat curing agent;
A liquid crystal sealant comprising: The liquid crystal sealant according to claim 1, wherein the carboxylic acid is a dicarboxylic acid or a combination of a dicarboxylic acid and a monocarboxylic acid. The liquid crystal sealant according to claim 1 or 2, wherein the carboxylic acid is an aliphatic carboxylic acid. The liquid crystal sealant according to any one of claims 1 to 3, wherein the carboxylic acid is a carboxylic acid having 4 to 14 carbon atoms. The liquid crystal sealant according to any one of claims 1 to 4, wherein the epoxy resin having an aromatic ring is at least one selected from the group consisting of bisphenol-type epoxy resins and resorcinol-type epoxy resins. A method for producing a liquid crystal sealant according to claim 1, comprising the step of mixing a modified resin with a photopolymerization initiator and/or a heat curing agent,
The modified resin is obtained by a manufacturing method including a step of reacting an epoxy resin having an aromatic ring, a modifying compound, and (meth)acrylic acid, wherein the modifying compound is a carboxylic acid including a polyvalent carboxylic acid (excluding (meth)acrylic acid and excluding an acid anhydride of a carboxylic acid), the total modification ratio of the (meth)acrylic acid and the modifying compound to the epoxy group of the epoxy resin having an aromatic ring is 10 to 90% , and the modification ratio of the carboxylic acid to the total modification ratio of the (meth)acrylic acid and the modifying compound is 10 to 80%.