JP6601633B2 - (Meth) acrylate resin and curable resin composition containing the same - Google Patents

Description

  The present invention relates to a (meth) acrylate resin and a curable resin composition containing the same.

  In the manufacturing method of a liquid crystal display element, the dropping method is a method in which a panel can be formed by directly dropping and bonding liquid crystal in a closed loop of a sealing agent under vacuum and releasing the vacuum. This dripping method has many merits such as a reduction in the amount of liquid crystal used and a time required for injecting the liquid crystal into the panel, and has become the mainstream method for manufacturing a liquid crystal panel using a large substrate. In the method including the dripping method, for example, a sealant is applied using, for example, a dispenser, liquid crystal is dropped and bonded, a gap is formed, alignment is performed, and the sealant is cured by energy ray curing and / or heat curing. It is done by.

  Patent Document 1 proposes improving the alignment characteristics of liquid crystal by partially modifying a bifunctional phenol novolac type epoxy resin with a (meth) acrylic acid derivative as a raw material of the sealing agent. Patent Document 2 discloses that, as a raw material for a sealing agent, a hydroxyl group of an ethylene glycol ring-opened product of an epoxy resin obtained by reacting a bifunctional bisphenol A type epoxy resin and ethylene glycol is glycidyloxylated. And a (meth) acrylate resin obtained by partially modifying the epoxy resin with a (meth) acrylic acid derivative.

JP 2008-179796 A JP 2013-241488 A

  According to the knowledge of the present inventors, the (meth) acrylate resin described in Patent Documents 1 and 2 has a problem that the adhesive strength is low when the substrates of the liquid crystal display element are bonded together. An object of the present invention is to provide a (meth) acrylate resin and a curable resin composition containing the same that exhibit high adhesive strength when the substrates are bonded to each other.

〔式中、
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は、それぞれ独立に、水素原子又はメチル基であり、
Ｒ^２１は、アルケニル基又はアルキニル基であり、
Ｒ^２２及びＲ^２３は、それぞれ独立に、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か、Ｒ^２２及びＲ^２３は、一緒になって、環構造を形成し、
Ｘ^１は、酸素原子又は硫黄原子であり、
Ｒ^２４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^２１、Ｒ^２２及びＲ^２３は、ビニル基又は１−メチルビニル基ではない。〕
［２］（メタ）アクリレート樹脂が、更に、式（３）で表される基を有する、［１］の硬化性樹脂組成物。

〔式中、Ｒ^６は、水素原子又はメチル基である。〕
［３］下記式（５）で表される、（メタ）アクリレート樹脂。
Ａｒ^１（−Ｏ−Ａ^１）_ｎ１ （５）
〔式中、
Ａｒ^１は、炭素原子数、及びヘテロ原子数の合計が５以上であり、且つ１つ以上の芳香環、又はヘテロ芳香環を含むｎ１価の基であり、
ｎ１は、１以上であり、
Ａ^１は、独立に、水素原子、下記式（１）で表される基、下記式（２−１）で表される基、下記式（２−２）で表される基、下記式（２−３）で表される基、下記式（３）で表される基、下記式（４−１）で表される基又は下記式（４−２）で表される基であるが、
但し、分子中に、式（１）で表される基を有する式（４−１）で表される基；式（１）で表される基を有する式（４−２）で表される基；及び式（１）で表される基からなる群より選択される１以上の基を有し、且つ、
式（２−１）で表される基、式（２−２）で表される基又は式（２−３）で表される基を有する式（４−１）で表される基；式（２−１）で表される基、式（２−２）で表される基及び／又は式（２−３）で表される基を有する式（４−２）で表される基；式（２−１）で表される基；式（２−２）で表される基；及び式（２−３）で表される基からなる群より選択される１以上の基を有する。〕

〔式中、
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は、それぞれ独立に、水素原子又はメチル基であり、
Ｒ^２１は、アルケニル基又はアルキニル基であり、
Ｒ^２２及びＲ^２３は、それぞれ独立に、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か、Ｒ^２２及びＲ^２３は、一緒になって、環構造を形成し、
Ｘ^１は、酸素原子又は硫黄原子であり、
Ｒ^２４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^２１、Ｒ^２２及びＲ^２３は、ビニル基又は１−メチルビニル基ではなく、
Ｂ^１は、独立に、アルキレン基であり、ｍ１は、１以上であり、
Ｄ^１は、アリーレン基、アルキレン−アリーレン−アルキレン基、アルキレン−アリーレン基、アリーレン−アルキレン−アリーレン基又は基：−Ｂ^２−（Ｏ−Ｂ^２）_ｍ２−であり、Ｂ^２は、独立に、アルキレン基であり、ｍ２は、０又は１以上であり、
Ｃ^１、Ｃ^２及びＣ^３は、それぞれ独立に、水素原子、式（１）で表される基、式（２−１）で表される基、式（２−２）で表される基、式（２−３）で表される基、又は、式（３）で表される基である。〕
［４］（メタ）アクリレート樹脂が、［３］の樹脂である、［１］又は［２］の硬化性樹脂組成物。
［５］更に、エポキシ樹脂（但し、（メタ）アクリロイル基を有するエポキシ樹脂を除く）、エポキシ樹脂のエポキシ基の一部又は全部が変性化合物で変性された変性エポキシ樹脂、及び、エポキシ樹脂のエポキシ基の一部又は全部が（メタ）アクリル酸で変性された変性エポキシ樹脂からなる群より選択される１以上の樹脂を含み、
ここで前記変性化合物は、不飽和脂肪族カルボン酸（但し、（メタ）アクリル酸を除く）、カルボン酸無水物（但し、（メタ）アクリル酸無水物を除く）、アルコール及びチオールからなる群より選択される１以上の化合物である、［１］、［２］又は［４］の硬化性樹脂組成物。
［６］液晶用シール剤である、［１］、［２］、［４］又は［５］の硬化性樹脂組成物。
［７］エポキシ樹脂と、変性化合物と、（メタ）アクリル酸とを反応させる工程を含み、ここで前記変性化合物は、不飽和脂肪族カルボン酸（但し、（メタ）アクリル酸を除く）、カルボン酸無水物（但し、（メタ）アクリル酸無水物を除く）、アルコール及びチオールからなる群より選択される１以上の化合物である、［３］の（メタ）アクリレート樹脂の製造方法。 The present invention has the following configuration.
[1] The molecule has one or more groups represented by the following formula (1), a group represented by the following formula (2-1), and represented by the following formula (2-2). A (meth) acrylate resin having one or more groups selected from the group consisting of a group and a group represented by the following formula (2-3);
A curable resin composition comprising a thermosetting agent and / or a polymerization initiator.

[Where,
R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or a methyl group,
R ²¹ is an alkenyl group or an alkynyl group,
R ²² and R ²³ are each independently an alkyl group, alkenyl group, alkynyl group or aryl group, or R ²² and R ²³ together form a ring structure;
X ¹ is an oxygen atom or a sulfur atom,
R ²⁴ is an alkyl group, an alkenyl group, an alkynyl group or an aryl group,
However, R ²¹ , R ²² and R ²³ are not a vinyl group or a 1-methylvinyl group. ]
[2] The curable resin composition according to [1], wherein the (meth) acrylate resin further has a group represented by the formula (3).

[Wherein, R ⁶ represents a hydrogen atom or a methyl group. ]
[3] A (meth) acrylate resin represented by the following formula (5).
Ar ¹ (—O—A ¹ ) _n1 (5)
[Where,
Ar ¹ is an n1 valent group having a total number of carbon atoms and heteroatoms of 5 or more, and including one or more aromatic rings or heteroaromatic rings,
n1 is 1 or more,
A ¹ is independently a hydrogen atom, a group represented by the following formula (1), a group represented by the following formula (2-1), a group represented by the following formula (2-2), the following formula ( 2-3), a group represented by the following formula (3), a group represented by the following formula (4-1) or a group represented by the following formula (4-2),
However, in the molecule, the group represented by the formula (4-1) having the group represented by the formula (1); the formula (4-2) having a group represented by the formula (1) A group; and one or more groups selected from the group consisting of groups represented by formula (1), and
A group represented by formula (4-1) having a group represented by formula (2-1), a group represented by formula (2-2), or a group represented by formula (2-3); A group represented by formula (4-2) having a group represented by (2-1), a group represented by formula (2-2) and / or a group represented by formula (2-3); It has one or more groups selected from the group consisting of a group represented by formula (2-1); a group represented by formula (2-2); and a group represented by formula (2-3). ]

[Where,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group,
R ²¹ is an alkenyl group or an alkynyl group,
R ²² and R ²³ are each independently an alkyl group, alkenyl group, alkynyl group or aryl group, or R ²² and R ²³ together form a ring structure;
X ¹ is an oxygen atom or a sulfur atom,
R ²⁴ is an alkyl group, an alkenyl group, an alkynyl group or an aryl group,
However, R ²¹ , R ²² and R ²³ are not vinyl groups or 1-methylvinyl groups,
B ¹ is independently an alkylene group, m 1 is 1 or more,
D ¹ is an arylene group, an alkylene-arylene-alkylene group, an alkylene-arylene group, an arylene-alkylene-arylene group or a group: —B ² — (O—B ² ) _m2 —, and B ² is independently An alkylene group, m2 is 0 or 1 or more,
C ¹ , C ² and C ³ are each independently a hydrogen atom, a group represented by formula (1), a group represented by formula (2-1), or a group represented by formula (2-2). , A group represented by formula (2-3), or a group represented by formula (3). ]
[4] The curable resin composition of [1] or [2], wherein the (meth) acrylate resin is a resin of [3].
[5] Further, an epoxy resin (excluding an epoxy resin having a (meth) acryloyl group), a modified epoxy resin in which part or all of the epoxy groups of the epoxy resin are modified with a modifying compound, and an epoxy resin epoxy Including one or more resins selected from the group consisting of modified epoxy resins in which part or all of the groups are modified with (meth) acrylic acid,
Here, the modifying compound is selected from the group consisting of unsaturated aliphatic carboxylic acids (excluding (meth) acrylic acid), carboxylic anhydrides (excluding (meth) acrylic anhydride), alcohols and thiols. The curable resin composition according to [1], [2] or [4], which is one or more selected compounds.
[6] The curable resin composition according to [1], [2], [4] or [5], which is a liquid crystal sealant.
[7] including a step of reacting an epoxy resin, a modifying compound, and (meth) acrylic acid, wherein the modifying compound is an unsaturated aliphatic carboxylic acid (excluding (meth) acrylic acid), carboxylic acid The method for producing a (meth) acrylate resin according to [3], which is one or more compounds selected from the group consisting of acid anhydrides (excluding (meth) acrylic anhydride), alcohols, and thiols.

  ADVANTAGE OF THE INVENTION According to this invention, when a base material is bonded together, the (meth) acrylate resin which exhibits high adhesive strength, and the curable resin composition containing the same are provided.

Hereinafter, preferred embodiments of the present invention will be described.
[Definition of statement]
In the present specification, the “glycidyl group” means a 2,3-epoxypropyl group. In the present specification, the “methyl glycidyl group” means a 2,3-epoxy-2-methylpropyl group. In this specification, the “epoxy group” includes at least one of a glycidyl group and a methylglycidyl group. In this specification, “(meth) acryloyl group” means an acryloyl group (CH ₂ ═CH ₂ —C (═O) —) and a methacryloyl group (CH ₂ ═CH (CH ₃ ) —C (═O) —). At least one of the above. “Optionally substituted” means “substituted or unsubstituted”.

  In the present specification, a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. In the present specification, the amount of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. To do. In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. .

  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 1-20, more preferably 1-18, still more preferably 1-10, and particularly preferably 1-4. The alkyl group is methyl group, ethyl group, propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n- A heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, etc. are mentioned.

  In this specification, alone or in combination with other terms, an “alkylene group” is a divalent group that is linear or branched. The number of carbon atoms of the alkylene group is preferably 1-20, and particularly preferably 1-8. The alkylene group includes 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), and a propylidene group (propane-1,1-diyl group). ), Isopropylidene group (propane-2,2-diyl group), tetramethylene group, butylidene group (butane-1,1-diyl group), isopropylidene group (2-methylpropane-1,1-diyl group), penta Examples include methylene group, 2-methylpentane-1,5-diyl group, hexamethylene group, 2-ethylhexane-1,6-diyl group, heptamethylene group, octamethylene group and the like.

  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 that the alkenyl group has is preferably 1 to 5, particularly preferably 1 or 2. The alkenyl group preferably has 2 to 20 carbon atoms, more preferably 3 to 20 carbon atoms, still more preferably 3 to 15 carbon atoms, and particularly preferably 3 to 10 carbon atoms. When the alkenyl group includes a vinyl group or a 1-methylvinyl group, the alkenyl group may have 2 to 20 carbon atoms, 2 to 15 carbon atoms, or 2 to 10 carbon atoms. Good. Alkenyl groups are vinyl, 1-methylvinyl, 1-propenyl, 2-propenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 2-butenyl, and 3-butenyl. 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 9-decenyl group and the like.

  As used herein, alone or in combination with other terms, an “alkynyl group” is a monovalent group that is linear or branched. The number of carbon atoms of the alkynyl group is preferably 2-20, and particularly preferably 2-15. Alkynyl group includes ethynyl group, propargyl group, 2-butynyl group, 3-butynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 2-hexynyl group, 3-hexynyl group, 4-hexynyl group, 5-hexynyl group etc. are mentioned.

  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, alone or in combination with other terms, the “aryl group” is a monovalent group having a monocyclic or polycyclic aromatic ring. The aryl group preferably has 6 to 20 carbon atoms. Examples of the aryl group include a phenyl group, a biphenylyl group, a naphthyl group, a terphenylyl group, an anthracenyl group, a fluorenyl group, and the like, and a phenyl group is preferable.

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

  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 alkyl mercapto group, a cycloalkyl group, and a halogen atom. The alkyl group preferably has 1 to 4 carbon atoms. The alkyl part in 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 moiety in the alkylcarbonyl group and the alkyl mercapto 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 the alkyl mercapto group include methyl mercapto group, ethyl mercapto group, propyl mercapto group, i-propyl mercapto group, butyl mercapto group, i-butyl mercapto group, sec-butyl mercapto group, tert-butyl mercapto group and the like. The cycloalkyl group is a monocyclic or polycyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, and includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, A cyclododecyl group, an adamantyl group, etc. are mentioned.

〔式中、
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は、それぞれ独立に、水素原子又はメチル基であり、
Ｒ^２１は、アルケニル基又はアルキニル基であり、
Ｒ^２２及びＲ^２３は、それぞれ独立に、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か、Ｒ^２２及びＲ^２３は、一緒になって、環構造を形成し、
Ｘ^１は、酸素原子又は硫黄原子であり、
Ｒ^２４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^２１、Ｒ^２２及びＲ^２３は、ビニル基又は１−メチルビニル基ではない。〕 [Curable resin composition]
The curable resin composition has one or more groups represented by the following formula (1) in the molecule, and a group represented by the following formula (2-1), the following formula (2-2). A (meth) acrylate resin having at least one group selected from the group consisting of the group represented by formula (2) and the group represented by the following formula (2-3), and a thermosetting agent and / or a polymerization initiator. contains.

[Where,
R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or a methyl group,
R ²¹ is an alkenyl group or an alkynyl group,
R ²² and R ²³ are each independently an alkyl group, alkenyl group, alkynyl group or aryl group, or R ²² and R ²³ together form a ring structure;
X ¹ is an oxygen atom or a sulfur atom,
R ²⁴ is an alkyl group, an alkenyl group, an alkynyl group or an aryl group,
However, R ²¹ , R ²² and R ²³ are not a vinyl group or a 1-methylvinyl group. ]

((Meth) acrylate resin)
The (meth) acrylate resin has one or more groups represented by the formula (1) in the molecule, and is represented by the group represented by the formula (2-1) or the formula (2-2). And one or more groups selected from the group consisting of groups represented by formula (2-3) (hereinafter also referred to as “first (meth) acrylate resin”).

  In addition to the group represented by Formula (1), the first (meth) acrylate resin includes a group represented by Formula (2-1), a group represented by Formula (2-2), and Formula (2). -3) having one or more groups selected from the group consisting of groups, in addition to the properties as a (meth) acrylate resin, a modified compound (that is, an unsaturated aliphatic carboxylic acid (however, Further properties imparted by (excluding (meth) acrylic acid), carboxylic anhydrides (excluding (meth) acrylic anhydride), one or more compounds selected from the group consisting of alcohols and thiols) Can have.

  The group represented by Formula (1), the group represented by Formula (2-1), the group represented by Formula (2-2), and the group represented by Formula (2-3) are monovalent. Group, and “*” in these groups means a bonding position. A group represented by Formula (3), a group represented by Formula (4-1), a group represented by Formula (4-2), a group represented by Formula (4-3), and a formula ( The same applies to the group represented by 4-4).

In the formula (2-2), R ²² and R ²³ which together form a ring structure are a C (═O) OC ^* CH ₂ OC (═O) group to which R ²² and R ²³ are bonded. It means to form a ring structure together. Here, C ^* is a carbon atom to which R ⁴ is bonded. In this case, -R ²² R ²³ -is not particularly limited, but is an alkylene group; an alkenylene group; an alkynylene group; an arylene group; a cycloalkylene group; an alkylene group, an alkenylene group interrupted by an arylene group or a cycloalkylene group, or Alkynylene group etc. are mentioned. Here, examples of the alkenylene group and the alkynylene group include groups obtained by removing one hydrogen atom from an alkenyl group and an alkynyl group.

〔式中、Ｒ^６は、水素原子又はメチル基である。〕 The first (meth) acrylate resin may further have a group represented by the following formula (3).

[Wherein, R ⁶ represents a hydrogen atom or a methyl group. ]

  When the first (meth) acrylate resin has a group represented by the formula (3), the first (meth) acrylate resin also has characteristics as an epoxy resin.

  In the first (meth) acrylate resin, a group represented by the formula (1), a group represented by the formula (2-1), a group represented by the formula (2-2), a formula (2-3) The portion other than the group represented by formula (3) and the group represented by formula (3) is arbitrary, and can be, for example, an aromatic or aliphatic group.

〔式中、
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は、それぞれ独立に、水素原子又はメチル基であり、
Ｒ^２１は、アルケニル基又はアルキニル基であり、
Ｒ^２２及びＲ^２３は、それぞれ独立に、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か、Ｒ^２２及びＲ^２３は、一緒になって、環構造を形成し、
Ｘ^１は、酸素原子又は硫黄原子であり、
Ｒ^２４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^２１、Ｒ^２２及びＲ^２３は、ビニル基又は１−メチルビニル基ではなく、
Ｂ^１は、独立に、アルキレン基であり、ｍ１は、１以上であり、
Ｄ^１は、アリーレン基、アルキレン−アリーレン−アルキレン基、アルキレン−アリーレン基、アリーレン−アルキレン−アリーレン基又は基：−Ｂ^２−（Ｏ−Ｂ^２）_ｍ２−であり、Ｂ^２は、独立に、アルキレン基であり、ｍ２は、０又は１以上であり、
Ｃ^１、Ｃ^２及びＣ^３は、それぞれ独立に、水素原子、式（１）で表される基、式（２−１）で表される基、式（２−２）で表される基、式（２−３）で表される基、又は、式（３）で表される基である。〕 Examples of the first (meth) acrylate resin include a (meth) acrylate resin represented by the following formula (5) (hereinafter also referred to as “second (meth) acrylate resin”).
Ar ¹ (—O—A ¹ ) _n1 (5)
[Where,
Ar ¹ is an n1 valent group having a total number of carbon atoms and heteroatoms of 5 or more, and including one or more aromatic rings or heteroaromatic rings,
n1 is 1 or more,
A ¹ is independently a hydrogen atom, a group represented by the following formula (1), a group represented by the following formula (2-1), a group represented by the following formula (2-2), the following formula ( 2-3), a group represented by the following formula (3), a group represented by the following formula (4-1) or a group represented by the following formula (4-2),
However, in the molecule, the group represented by the formula (4-1) having the group represented by the formula (1); the formula (4-2) having a group represented by the formula (1) A group; and one or more groups selected from the group consisting of groups represented by formula (1), and
A group represented by formula (4-1) having a group represented by formula (2-1), a group represented by formula (2-2), or a group represented by formula (2-3); A group represented by formula (4-2) having a group represented by (2-1), a group represented by formula (2-2) and / or a group represented by formula (2-3); It has one or more groups selected from the group consisting of a group represented by formula (2-1); a group represented by formula (2-2); and a group represented by formula (2-3). ]

[Where,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group,
R ²¹ is an alkenyl group or an alkynyl group,
R ²² and R ²³ are each independently an alkyl group, alkenyl group, alkynyl group or aryl group, or R ²² and R ²³ together form a ring structure;
X ¹ is an oxygen atom or a sulfur atom,
R ²⁴ is an alkyl group, an alkenyl group, an alkynyl group or an aryl group,
However, R ²¹ , R ²² and R ²³ are not vinyl groups or 1-methylvinyl groups,
B ¹ is independently an alkylene group, m 1 is 1 or more,
D ¹ is an arylene group, an alkylene-arylene-alkylene group, an alkylene-arylene group, an arylene-alkylene-arylene group or a group: —B ² — (O—B ² ) _m2 —, and B ² is independently An alkylene group, m2 is 0 or 1 or more,
C ¹ , C ² and C ³ are each independently a hydrogen atom, a group represented by formula (1), a group represented by formula (2-1), or a group represented by formula (2-2). , A group represented by formula (2-3), or a group represented by formula (3). ]

  In Formula (5), n1 is preferably 1 to 8, and particularly preferably 1 to 4.

In Formula (5), the number of carbon atoms contained in Ar ¹ is 4 to 40, the number of oxygen atoms is 0 to 5, the number of nitrogen atoms is 0 to 5, and the number of sulfur atoms is 0 to 5. And the number of ring structures contained in Ar ¹ is preferably 1 to 5.

The ring structure (aromatic ring and heteroaromatic ring) contained in Ar ¹ may be one kind alone, or two or more kinds may be present, and the ring structure may be a monocyclic structure or a condensed ring structure. There may be. A plurality of these ring structures may be bonded to each other through a direct bond or a linking group.

Examples of this 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. Further, in the equation (5), the ring structure included in the oxygen atom and the Ar ¹ that binds to Ar ^1, the ring structure may be bonded via a linking group, but contained in Ar ¹ is, Ar ¹ It is preferably directly bonded to an oxygen atom bonded to.

  Moreover, these ring structures may each independently have a substituent. Examples of such a substituent include an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkyl mercapto group, a cycloalkyl group, and a halogen atom.

Examples of the ring structure contained in Ar ¹ include benzene ring, naphthalene ring, fluorene ring, anthracene ring, furan ring, pyrrole ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, thiazine ring, and these And those having the above substituents bonded to the ring.

Specific examples of Ar ¹ when n1 is 1 include a phenyl group, a biphenylyl group, a naphthyl group, a terphenylyl group, an anthracenyl group, a fluorenyl group, and the like.

Specific examples of Ar ¹ when n1 is 2 include arylene groups having 6 to 20 carbon atoms, arylene groups having 6 to 20 carbon atoms, alkylene groups having 1 to 6 carbon atoms, and arylene groups having 6 to 20 carbon atoms. or arylene ^-O- (R 51 _{-O) m3} having 6 to 20 carbon atoms - arylene group wherein 6 to 20 carbon ^{atoms, R 51} is an alkylene group having 1 to 8 carbon atoms, m3 is 0 or an integer of 1-6. 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), a phenylene-ethylidene-phenylene group A group obtained by removing two hydroxyl groups from bisphenols such as (a group obtained by removing two hydroxyl groups from bisphenol AD) is preferred.

The following formula is mentioned as a specific example of Ar ¹ when n1 is 3. Here, * indicates a binding position.

The following formula is mentioned as a specific example of Ar ¹ when n1 is 4. Here, * indicates a binding 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。〕 As a specific example of Ar ¹ when n1 is 2 or more, a phenol novolak represented by the following formula may also be mentioned.

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

In addition, as a specific example of Ar ¹ when n1 is 5 or more, a group in which 4 or more hydrogen atoms bonded to the aromatic carbon atom of the specific example of Ar ¹ when n1 is 1 is removed, or n1 is 2 3 above except groups and the hydrogen atoms bonded to aromatic carbon atoms of the examples of Ar ¹ in the case where, bonded to aromatic carbon atoms of the aromatic group examples of Ar ¹ when n1 is 3 And a group in which one or more hydrogen atoms bonded to the aromatic carbon atom of the specific example of Ar ¹ when n1 is 4 are removed.

In the formula (5), “independently” in the definition of A ¹ means that, for example, when n1 is 2 or more, options (for example, A ¹ ) are independently defined in each case. That is, when n1 is 2 or more, the options defined by the formula (5) (for example, A ¹ ) may be different or the same. The same applies to formula (6) and the like described later.

In Formula (4-1), m1 is preferably an integer of 1 to 6. In Formula (4-2), when m2 is 1 or more, it is preferably an integer of 1 to 6. Specific examples of D ¹ include a specific example of Ar ¹ when n 1 is 2.

<Preferred embodiment>
When R ²¹ is an alkenyl group, the number of carbon atoms is preferably from 3 to 20, more preferably from 3 to 10 from the viewpoint of further increasing the adhesive strength, and a 1-propenyl group, 2-propenyl group, 1 -Methyl-1-propenyl, 2-methyl-1-propenyl, 3-butenyl and 9-decenyl are particularly preferred. When R ²² and R ²³ are alkyl groups, the number of carbon atoms is preferably 1 to 18, more preferably 1 to 4, and particularly preferably a butyl group. When R ²⁴ is an alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 4, and particularly preferably a methyl group. When R ²⁴ is an aryl group, a phenyl group is particularly preferable. The first (meth) acrylate resin is preferably a second (meth) acrylate resin.

[Method for producing (meth) acrylate resin]
The method for producing the (meth) acrylate resin is not particularly limited as long as the first (meth) acrylate resin is obtained. The method for producing a (meth) acrylate resin is, for example, a production method including a step of reacting an epoxy resin, a modified compound, and (meth) acrylic acid, wherein the modified compound is an unsaturated aliphatic carboxylic acid. Production method, which is one or more compounds selected from the group consisting of acids (excluding (meth) acrylic acid), carboxylic anhydrides (excluding (meth) acrylic anhydride), alcohols and thiols Is mentioned. In addition, the method for producing a (meth) acrylate resin includes a step of forming a group represented by the formula (1) by reacting a compound having a hydroxyl group with glycidyl (meth) acrylate, for example. Is mentioned. The method for producing a (meth) acrylate resin is preferably a method for producing a second (meth) acrylate resin. Hereinafter, a method for producing a (meth) acrylate resin will be described with reference to an example of a production method including a step of reacting an epoxy resin, a modifying compound, and (meth) acrylic acid.

〔式中、Ｒ^６は、前記のとおりであり；Ｂ^３は、Ｂ^１と同義であり；ｍ５は、ｍ１と同義であり；Ｒ^８は、Ｒ^７と同義であり；Ｄ^２は、Ｄ^１と同義であり；Ｃ^４、Ｃ^５及びＣ^６は、それぞれ独立に、水素原子又は式（３）で表される基である。〕 <Epoxy resin>
The epoxy resin is not particularly limited as long as it is a resin having two or more epoxy groups in one molecule. Here, when the manufacturing method of (meth) acrylate resin is a manufacturing method of 2nd (meth) acrylate resin, as an epoxy resin, the epoxy resin represented by following formula (6) is mentioned, for example.
Formula: Ar ² (—O—A ² ) _n2 (6)
[Where,
Ar ² is synonymous with Ar ¹ ,
n2 is synonymous with n1,
A ² is independently a hydrogen atom; a group represented by the following formula (3); a group represented by the following formula (4-3); or a group represented by the following formula (4-4). But,
However, it has 2 or more epoxy groups in the molecule. ]

[Wherein R ⁶ is as defined above; B ³ is synonymous with B ¹ ; m 5 is synonymous with m 1; R ⁸ is synonymous with R ⁷ ; D ² is D ¹ and C ⁴ , C ⁵ and C ⁶ are each independently a hydrogen atom or a group represented by the formula (3). ]

The epoxy resin represented by the formula (6) has two or more epoxy groups in one molecule, and this epoxy group is an epoxy group possessed by the group represented by the formula (3). Therefore, if n2 is 1, ^{A 2} is a group represented by the formula (4-4), a ^{group C 5} and ^{C 6} are represented by the formula (3).

Further, the formula any structure Ar ² epoxy resin represented by (6) (e.g., an aromatic or aliphatic group) With, or as a manufacturing method of the first (meth) acrylate resin.

  Such a resin having two or more epoxy groups in one molecule is not particularly limited, and is bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy. Resin, bisphenol A novolac type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy Examples thereof include resins and phenol novolac type epoxy resins having a triphenolmethane skeleton. In addition, diglycidyl etherified products of difunctional phenols, diglycidyl etherified products of difunctional alcohols and their halides, hydrogenated products, and the like can also be used.

  Epoxy resins are commercially available or can be prepared according to known methods. The epoxy resin having a group represented by the formula (4-3) can be obtained, for example, by the method described in JP-A-8-333356 or a method similar thereto. Moreover, the epoxy resin which has group represented by Formula (4-4) can be obtained by the method described in Unexamined-Japanese-Patent No. 2012-070220 and Unexamined-Japanese-Patent No. 2013-241488, or a method similar to it, for example. it can.

<Modified compound>
The modifying compound is selected from the group consisting of unsaturated aliphatic carboxylic acids (excluding (meth) acrylic acid), carboxylic anhydrides (excluding (meth) acrylic anhydride), alcohols and thiols. One or more compounds. A modification compound may be used individually by 1 type, respectively, or may be used in combination of 2 or more type.

Unsaturated aliphatic carboxylic acids (where (meth) excluding acrylic acid) as the ^formula: R 41 -COOH ^{wherein, R 41} has ^the same meaning as ^{R 21.} ] The compound represented by this is mentioned. By using an unsaturated aliphatic carboxylic acid (excluding (meth) acrylic acid), a (meth) acrylate resin having a group represented by the formula (2-1) can be obtained. In this case, R ³ is a hydrogen atom when the epoxy group of the epoxy resin represented by formula (6) is a glycidyl group, and the epoxy group of the epoxy resin represented by formula (6) is methyl glycidyl. When it is a group, it is a methyl group.

Carboxylic anhydride (excluding (meth) acrylic anhydride) has the formula R ⁴² —C (═O) —O—C (═O) —R ⁴³ [wherein R ⁴² and R ⁴³ Is synonymous with R ²² and R ²³ . ] The compound represented by this is mentioned. By using a carboxylic acid anhydride (excluding (meth) acrylic anhydride), a (meth) acrylate resin having a group represented by the formula (2-2) is obtained. R ²² and R ²³ which together form a ring structure are a reaction between an epoxy group in an epoxy resin and a dicarboxylic anhydride such as succinic anhydride, maleic anhydride, phthalic anhydride, etc. It is formed by. In these cases, R ⁴ is the same as R ³ .

The alcohols and thiols, ^formula: R 44 ^-X 2 -H ^{[wherein, R 44 has} the same meaning as ^{R 24, X 2} has the same meaning as ^{X 1.} ] The compound represented by this is mentioned. By using one or more compounds selected from the group consisting of alcohol and thiol, a (meth) acrylate resin having a group represented by Formula (2-3) is obtained. In this case, R ⁵ is the same as R ³ .

<(Meth) acrylic acid>
(Meth) acrylic acid is one or more selected from the group consisting of acrylic acid and methacrylic acid. By reacting the epoxy group in the epoxy resin with (meth) acrylic acid, a (meth) acrylate resin having a group represented by the formula (1) is obtained. In this case, R ¹ is a hydrogen atom when the (meth) acrylic acid is acrylic acid, and a methyl group when the (meth) acrylic acid is methacrylic acid. R ² is the same as R ³ .

In addition, in the (meth) acrylate resin obtained, when an epoxy group that has not reacted with (meth) acrylic acid and the modifying compound is present, the (meth) acrylate resin has a group represented by the formula (3). In this case, R ⁶ is the same as R ³ .

<Reaction conditions>
As reaction conditions for obtaining a (meth) acrylate resin, known conditions used by 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. As a basic catalyst and an acid catalyst, the well-known basic catalyst and acid catalyst used by reaction with an epoxy resin and a modified compound are mentioned.

  Basic catalysts include alkali metal hydroxides (sodium hydroxide, potassium hydroxide, etc.), alkali metal carbonates (sodium carbonate, potassium carbonate, etc.), alkali metal alkoxides (sodium methoxide, etc.), trivalent organic compounds. Phosphorus compounds and / or amine compounds are preferred. A polymer-supported basic catalyst in which a basic catalyst is supported on a polymer can also be used.

  Examples of the trivalent organic phosphorus compound include alkylphosphines such as triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine and salts thereof, triphenylphosphine, tri-m-tolylphosphine, tris- (2 , 6-dimethoxyphenyl) phosphine, arylphosphines such as bis [2- (diphenylphosphino) phenyl] ether and salts thereof, phosphorous acid such as triphenylphosphite, triethylphosphite, tris (nonylphenyl) phosphite Examples include triesters and salts thereof. Trivalent phosphine / ethyl bromide, triphenyl phosphine / butyl bromide, triphenyl phosphine / octyl bromide, triphenyl phosphine / decyl bromide, triphenyl phosphine / isobutyl bromide, triphenyl phosphine / Examples thereof include propyl chloride, triphenylphosphine / pentyl chloride, triphenylphosphine / hexyl bromide and the like.

  Examples of the amine compound include secondary amines such as diethanolamine, tertiary amines such as triethanolamine, dimethylbenzylamine, trisdimethylaminomethylphenol, trisdiethylaminomethylphenol, 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] Examples include strongly basic amines such as non-5-ene (DBN) and 1,1,3,3-tetramethylguanidine, and salts thereof. Among these, 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD) is preferable. Examples of the salt of the amine compound include benzyltrimethylammonium chloride and benzyltriethylammonium chloride.

  Examples of the acid catalyst include sulfonic acid such as sulfuric acid and trifluoromethanesulfonic acid, graphite oxide, and antimony fluoride. Moreover, you may use a cation exchanger (For example, amber list is mentioned as a commercial item) as an acid catalyst. The acid catalyst can be used for the reaction of the 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. In the reaction, a solvent inert to the reaction such as hydrocarbon, ether or ketone can be used. However, when an excessive amount of epoxy resin is used, the resin also functions as a solvent. is not.

  The reaction temperature can be appropriately set by those skilled in the art according to the catalyst and the raw material compound used. For example, the catalyst is a basic catalyst, (meth) acrylic acid, and carboxylic acid (excluding (meth) acrylic acid) and carboxylic acid anhydride (excluding (meth) acrylic acid anhydride) as the modifying compound When one or more selected from the group consisting of) is used, the reaction temperature is preferably 60 to 120 ° C, more preferably 80 to 120 ° C, still more preferably 90 to 120 ° C, and particularly preferably 100 ° C to 120 ° C. For example, when the catalyst is an acid catalyst and alcohol is used as the modifying compound, the reaction temperature is preferably 0 to 100 ° C, more preferably 10 to 90 ° C, and particularly preferably 25 to 80 ° C.

  The total reaction amount of (meth) acrylic acid and the modifying compound with respect to 1 equivalent of epoxy group of the epoxy resin is more than 0 and 100 equivalent%, preferably 10 to 90 equivalent%, more preferably 20 to 80. Equivalent%, particularly preferably 30 to 70 equivalent%. In the method for producing a (meth) acrylate resin, the reaction between the epoxy group, (meth) acrylic acid and the modifying compound proceeds quantitatively, and therefore the modification rate of the obtained (meth) acrylate resin is estimated from the epoxy equivalent. You can also.

  (Meth) acrylic acid and the modifying compound may be reacted with an epoxy resin at the same time to obtain a (meth) acrylate resin. Moreover, the epoxy resin and the modified compound are reacted to obtain an epoxy resin partially modified with the modified compound, and the epoxy resin partially modified with the modified compound and (meth) acrylic acid are reacted to obtain (meth) An acrylate resin may be obtained, and an epoxy resin partially modified with (meth) acrylic acid is obtained by reacting an epoxy resin with (meth) acrylic acid, and the epoxy resin partially modified with (meth) acrylic acid is modified. A (meth) acrylate resin may be obtained by reacting with a compound.

In addition, (meth) acrylate resin obtained by the manufacturing method of (meth) acrylate resin may be obtained as a resin mixture containing resin which has the same frame | skeleton. Here, the skeleton in the second (meth) acrylate resin refers to a portion of Ar ¹ . The skeleton in the first (meth) acrylate resin is a group represented by the formula (1), a group represented by the formula (2-1), a group represented by the formula (2-2), and It means a part other than the group represented by formula (2-3).

(Thermosetting agent and / or polymerization initiator)
A thermosetting agent and / or a polymerization initiator can be suitably selected according to the component contained in curable resin composition. By using a thermosetting agent, a curable resin composition can be made into a thermosetting resin composition. By using a polymerization initiator, the curable resin composition can be made into a radical polymerization curable, anionic polymerization curable and / or cationic polymerization curable resin composition.

<Thermosetting agent>
The thermosetting agent is not particularly limited, and examples thereof include amine thermosetting agents such as organic acid dihydrazide compounds, amine adducts, imidazoles and derivatives thereof, dicyandiamide, aromatic amines, epoxy-modified polyamines, and polyaminoureas. 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin), ADH (adipic acid dihydrazide), UDH (7,11-octadecadien-1,18-dicarbohydrazide) and LDH (octadecane-1, Organic acid dihydrazide such as 18-dicarboxylic acid dihydrazide); polyamine compounds sold as ADEKA HARDNER EH5030S etc. from ADEKA Corporation; from Ajinomoto Fine Techno Co., Ltd., Amicure PN-23, Amicure PN-30, Amicure Y-24, preferably an amine adduct commercially available as Amicure MY-H, and the like. These thermosetting agents may be used alone or in combination.

<Polymerization initiator>
Examples of the polymerization initiator include a radical polymerization initiator, an anionic polymerization initiator and / or a cationic polymerization initiator. The polymerization initiator is a component that becomes a radical generation source when radically polymerizing a curable component contained in the curable resin composition, an anion generation source when anionic polymerization is performed, and a cation generation source when cationic polymerization is performed.

  As radical polymerization initiators, benzoins, acetophenones, benzophenones, thioxanthones, α-acyloxime esters, phenylglyoxylates, benzyls, azo compounds, diphenyl sulfide compounds, acylphosphine oxide compounds, Examples include benzoin ethers, anthraquinones, and organic peroxides. The radical polymerization initiator preferably has a low solubility in the liquid crystal and a reactive group that itself does not gasify the decomposition product when irradiated with light. Further, as a radical polymerization initiator, a compound obtained by reacting a compound having at least two epoxy groups with dimethylaminobenzoic acid described in WO2012 / 0777720, and at least two epoxy groups A polymerization initiator which is a mixture of a compound obtained by reacting the compound having a compound with hydroxythioxanthone is preferable.

  Examples of the anionic polymerization initiator include imidazoles, amines, phosphines, organic metal salts, metal chlorides, and organic peroxides.

  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, Examples thereof include carboxylic acid esters, sulfonic acid esters, amine imides, sulfone compounds, sulfonic acid esters, sulfonimides, disulfonyldiazomethanes, and amines.

  The polymerization initiator is commercially available or can be prepared according to a known method. Each of the radical polymerization initiator, the anionic polymerization initiator and the cationic polymerization initiator may be used alone or in combination of two or more. The polymerization initiator can be appropriately used according to desired curing conditions (energy ray curing and / or heat curing).

(Further ingredients)
The curable resin composition includes one or more additional components selected from the group consisting of a further resin (excluding the first (meth) acrylate resin), a photosensitizer, a filler, and a coupling agent. be able to.

<Further resin>
The additional resin is not particularly limited as long as it is a resin other than the first (meth) acrylate resin, and is a conventional resin having an unsaturated group and / or an epoxy group used as a main component of a liquid crystal sealant, and unsaturated. And resins having neither a group nor an epoxy group. Here, the “unsaturated group” means an ethylenically unsaturated group and / or an acetylenically unsaturated group.

<< resin having an unsaturated group >>
Examples of the resin having an unsaturated group include (meth) acrylate compounds, aliphatic acrylamide compounds, alicyclic acrylamide compounds, aromatic acrylamide compounds, N-substituted acrylamide compounds, diene polymers (for example, polybutadiene polymers, poly Isoprene polymer). The functionality of the (meth) acrylate compound can be monofunctional, bifunctional or trifunctional or higher polyfunctional.

  Monofunctional (meth) acrylate compounds include hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isooctyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate , Dicyclopentanyl (meth) acrylate, cyclohexyloxyethyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isomyristyl (meth) acrylate, lauryl (meth) Acrylate, tert-butyl (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate Relate, and one or more compounds selected from the group consisting of ethoxylated phenyl (meth) acrylate.

  Examples of the bifunctional (meth) acrylate compound include tricyclodecane dimethanol di (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, EO-modified 1,6-hexanediol di (meth) acrylate, and EO-modified. Bisphenol A di (meth) acrylate, PO-modified bisphenol A di (meth) acrylate, polyester di (meth) acrylate (for example, ARONIX M-6100, manufactured by Toagosei Co., Ltd.), polyethylene glycol di (meth) acrylate (for example, 4G And one or more compounds selected from the group consisting of silicon di (meth) acrylate (for example, EBECRYL 350, manufactured by Daicel Ornex Co., Ltd.). Here, “EO” means ethylene oxide, and “PO” means propylene oxide.

  Trifunctional or higher polyfunctional (meth) acrylate compounds include EO-modified glycerol tri (meth) acrylate (trifunctional), PO-modified glycerol tri (meth) acrylate (trifunctional), pentaerythritol tri (meth) acrylate ( One or more compounds selected from trifunctional), dipentaerythritol hexa (meth) acrylate (hexafunctional) and pentaerythritol tetra (meth) acrylate (tetrafunctional) are preferred.

  Furthermore, as the resin having an unsaturated group, all of the epoxy groups of the epoxy resin are modified with (meth) acrylic acid, and all of the epoxy groups of the epoxy resin are modified with a modifying compound having an unsaturated group. An epoxy resin is mentioned.

<< Resin having epoxy group >>
The resin having an epoxy group is not particularly limited as long as it has one or more epoxy groups. Examples of the resin having one epoxy group include aromatic epoxy resins and aliphatic epoxy resins. Examples of the resin having two or more epoxy groups include those described above as the epoxy resin. Moreover, the partially modified epoxy resin by which a part of epoxy resin epoxy group was modified | denatured with the modification compound is mentioned.

<< Resin having unsaturated group and epoxy group >>
As a resin having an unsaturated group and an epoxy group, a partially modified epoxy resin in which a part of the epoxy group of the epoxy resin is modified with a compound having an unsaturated group (for example, a portion modified with a (meth) acrylic acid compound) (Meth) acrylate-modified epoxy resin).

<< Resin having neither unsaturated group nor epoxy group >>
As a resin having neither an unsaturated group nor an epoxy group, all of the epoxy groups of the epoxy resin are modified with a modified compound having no unsaturated group, a hydroxyl group-containing compound and an isocyanate group-containing compound. The urethane resin etc. which are formed are mentioned.

<< Preferred Further Resin >>
Further resins include an epoxy resin (except for an epoxy resin having a (meth) acryloyl group), a modified epoxy resin in which part or all of the epoxy group of the epoxy resin is modified with (meth) acrylic acid, and an epoxy A modified epoxy resin in which part or all of the epoxy group of the resin is modified with a modifying compound, wherein the modifying compound is an unsaturated aliphatic carboxylic acid (except for (meth) acrylic acid), carboxylic acid A resin that is one or more compounds selected from the group consisting of anhydrides (excluding (meth) acrylic anhydride), alcohols, and thiols is preferred.

  Here, the epoxy resin (excluding an epoxy resin having a (meth) acryloyl group) may be a raw material epoxy resin for obtaining a (meth) acrylate resin. In addition, a modified epoxy resin in which part or all of the epoxy group of the epoxy resin is modified with (meth) acrylic acid is a component that can be obtained as a component other than the (meth) acrylate resin by the production method of the (meth) acrylate resin It is. A modified epoxy resin in which part or all of the epoxy groups of the epoxy resin are modified with a modifying compound, wherein the modifying compound is an unsaturated aliphatic carboxylic acid (except (meth) acrylic acid), carboxylic acid anhydride Modified epoxy resin, which is one or more compounds selected from the group consisting of products (excluding (meth) acrylic anhydride), alcohols and thiols, depending on the method for producing (meth) acrylate resin, It is a component that can be obtained as a component other than the resin.

<Photosensitizer>
The curable resin composition may further contain a photosensitizer in order to increase sensitivity to light during photocuring. Examples of the photosensitizer include carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreducible dyes from the viewpoint of curability. Specific examples of the photosensitizer include an acridone derivative such as N-methylacridone and N-butylacridone; in addition, α, α-diethoxyacetophenone, benzyl, fluorenone, xanthone, uranyl compound and the like. Some of the polymerization initiators function as photosensitizers. A photosensitizer may be used individually by 1 type, or may be used in combination of 2 or more type.

<Filler>
The purpose of the filler is to improve the adhesive reliability of the curable resin composition by controlling the viscosity of the curable resin composition, improving the strength of the cured product obtained by curing the curable resin composition, or suppressing linear expansion. Is added. A filler is not specifically limited, An inorganic filler and an organic filler are mentioned. Inorganic fillers include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, titanium oxide, alumina, zinc oxide, silicon dioxide, kaolin, talc, glass beads, sericite activated clay, bentonite, aluminum nitride, and nitriding Silicon may be mentioned. Examples of the organic filler include polymethyl methacrylate, polystyrene, a copolymer obtained by copolymerizing the monomer and other monomers, polyester fine particles, polyurethane fine particles, rubber fine particles, and a copolymer having a high glass transition temperature. Examples thereof include core-shell type particles composed of a shell containing a polymer and a copolymer core having a low glass transition temperature. A commercial item can be used for a filler. Examples of commercially available silicon dioxide particles include the Seahoster KE series (KE-C50, etc.). Moreover, as a core-shell type particle | grain, Zefiac series (F-351 grade | etc., Aika Industrial Co., Ltd. product) etc. are mentioned. A filler may be used individually by 1 type, respectively, or may be used in combination of 2 or more type.

<Silane coupling agent>
The silane coupling agent is added for the purpose of further increasing the adhesive strength. The silane coupling agent is not particularly limited, and examples thereof include γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane. A silane coupling agent may be used independently and may be used in combination of 2 or more type.

(Use of curable resin composition)
The curable resin composition is preferably a sealant, and more preferably a sealant used for a display element, a light amount adjusting element, a focus variable element, a light modulation element, and the like. In addition, the curable resin composition is a liquid crystal display (or liquid crystal display element) including a module-type display, a three-dimensional display, a head-mounted display, a projection-type display, etc .; a dimming filter, a dimming shutter, an anti-glare mirror, a spatial light quantity Light modulation liquid crystal elements such as modulators; variable focus liquid crystal elements such as liquid crystal lenses; and light modulation liquid crystals such as optical deflectors, optical demultiplexers, phase control, polarization control, holograms, diffraction gratings, wavelength filters, and frequency filters More preferably, it is a liquid crystal sealant used in the element; and a liquid crystal dropping method sealant is particularly preferable.

  The curable resin composition can be cured by applying heat by irradiation with energy rays such as ultraviolet rays, or by applying heat before, after or simultaneously with irradiation of energy rays such as ultraviolet rays.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Resins used in Examples and Comparative Examples were produced as follows.

[Comparative Synthesis Example 1] Comparative (meth) acrylate resin 1 (partially methacrylated bisphenol A type epoxy resin)
Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 340.0 g, methacrylic acid (Tokyo Chemical Industry Co., Ltd.) 86.1 g, and triphenylphosphine (Tokyo Chemical Industry Co., Ltd.) 500 mg were mixed and mixed. Stir at 6 ° C. for 6 hours. 418.0g of comparative (meth) acrylate resin 1 of the pale yellow transparent viscous substance was obtained.

[Synthesis Example 1] (Meth) acrylate resin 1
170.0 g of bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation), 21.5 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 21.5 g of crotonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and triphenyl 262 mg of phosphine (Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at 100 ° C. for 4 hours. 201.9g of (meth) acrylate resin 1 of the yellow transparent viscous substance was obtained.

[Synthesis Example 2] (Meth) acrylate resin 2
Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.8 g, 3-butenoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.8 g, and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at 100 ° C. for 5 hours. 105.2g of (meth) acrylate resin 2 of a yellow transparent viscous substance was obtained.

[Synthesis Example 3] (Meth) acrylate resin 3
Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.8 g, sorbic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 14.0 g, and triphenyl 130 mg of phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at 100 ° C. for 5 hours. 107.6g of (meth) acrylate resin 3 of a yellow transparent viscous substance was obtained.

[Synthesis Example 4] (Meth) acrylate resin 4
Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.8 g, 3-methylcrotonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 12.5 g, And 130 mg of triphenylphosphine (Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100 ° C. for 5 hours. 104.1g of (meth) acrylate resin 4 of yellow transparent viscous substance was obtained.

[Synthesis Example 5] (Meth) acrylate resin 5
Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.8 g, 10-undecenoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 23.0 g, and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at 100 ° C. for 5 hours. 117.7g of (meth) acrylate resin 5 of a yellow transparent viscous substance was obtained.

[Synthesis Example 6] (Meth) acrylate resin 6
Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.8 g, 4-pentenoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 12.5 g, and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at 100 ° C. for 5 hours. 105.1g of (meth) acrylate resin 6 of a yellow transparent viscous substance was obtained.

[Synthesis Example 7] (Meth) acrylate resin 7
Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.8 g, tiglic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 12.5 g, and triphenyl 130 mg of phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at 100 ° C. for 5 hours. 107.4g of (meth) acrylate resin 7 of a yellow transparent viscous substance was obtained.

[Synthesis Example 8] (Meth) acrylate resin 8
Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 170.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 32.3 g, crotonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.7 g, and triphenyl 262 mg of phosphine (Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at 100 ° C. for 5 hours. 205.2g of (meth) acrylate resin 8 of a yellow transparent viscous substance was obtained.

[Synthesis Example 9] (Meth) acrylate resin 9
Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 16.1 g, 3-butenoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.4 g, and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at 100 ° C. for 5 hours. 100.4g of (meth) acrylate resin 9 of the yellow transparent viscous substance was obtained.

[Synthesis Example 10] (Meth) acrylate resin 10
Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 16.1 g, 10-undecenoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 11.5 g, and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at 100 ° C. for 5 hours. 107.1g of (meth) acrylate resin 10 of yellow transparent viscous substance was obtained.

[Synthesis Example 11] (Meth) acrylate resin 11
Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.4 g, crotonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 16.1 g, and triphenyl 130 mg of phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at 100 ° C. for 5 hours. 97.8g of (meth) acrylate resin 11 of a yellow transparent viscous substance was obtained.

[Synthesis Example 12] (Meth) acrylate resin 12
Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (Tokyo Chemical Industry Co., Ltd.) 5.4 g, 3-butenoic acid (Tokyo Chemical Industry Co., Ltd.) 16.1 g, and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at 100 ° C. for 5 hours. 101.7g of (meth) acrylate resin 12 of yellow transparent viscous substance was obtained.

[Synthesis Example 13] (Meth) acrylate resin 13
Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.4 g, 10-undecenoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 34.5 g, and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at 100 ° C. for 6 hours. 120.1g of (meth) acrylate resin 13 of a yellow transparent viscous substance was obtained.

[Synthesis Example 14] (Meth) acrylate resin 14
Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 16.1 g, crotonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.7 g, and triphenyl 130 mg of phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at 100 ° C. for 7 hours. 108.5g of (meth) acrylate resin 14 of a yellow transparent viscous substance was obtained.

[Synthesis Example 15] (Meth) acrylate resin 15
Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 21.5 g, crotonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.7 g, and triphenyl 130 mg of phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at 100 ° C. for 7 hours. 112.0g of (meth) acrylate resin 15 of the yellow transparent viscous substance was obtained.

[Synthesis Example 16] (Meth) acrylate resin 16
Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 14.3 g, crotonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 14.3 g, and triphenyl 130 mg of phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at 100 ° C. for 7 hours. 111.2g of (meth) acrylate resin 16 of the yellow transparent viscous substance was obtained.

[Synthesis Example 17] (Meth) acrylate resin 17
Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methanol (manufactured by Kanto Chemical Co., Ltd.) 425.0 g, sodium methoxide (manufactured by Kanto Chemical Co., Ltd.) 2.7 g were mixed at 50 ° C. After stirring for 60 minutes, 50.0 g of 3% hydrochloric acid was added, methanol was distilled off under reduced pressure, 300 mL of ethyl acetate was added, and the mixture was washed 4 times with 300 mL of water. Magnesium sulfate is added to the obtained organic phase, and after drying, the solid content is separated by filtration, etc., the solvent of the obtained organic phase is distilled off by distillation under reduced pressure, and partially modified with a transparent viscous methanol. As a result, 87.0 g of an epoxy resin was obtained. 79.6 g of epoxy resin partially modified with methanol, 10.8 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 116 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100 ° C. for 2 hours. 87.3g of (meth) acrylate resin 17 of a yellow transparent viscous substance was obtained.

[Synthesis Example 18] (Meth) acrylate resin 18
425.0 g of 1-butanol (manufactured by Kanto Chemical Co., Ltd.) and 2.7 g of sodium methoxide (manufactured by Kanto Chemical Co., Ltd.) were mixed and stirred at 70 ° C. for 3 hours. The reaction mixture was cooled to 50 ° C., 85.0 g of bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) was added and stirred for 50 minutes, 50.0 g of 3% hydrochloric acid was added, and 1-butanol was distilled under reduced pressure. After leaving, 300 mL of ethyl acetate was added and washed 4 times with 300 mL of water. Magnesium sulfate is added to the obtained organic phase, and after drying, the solid content is separated by filtration, etc., and the solvent of the obtained organic phase is distilled off by distillation under reduced pressure. 81.4 g of a modified epoxy resin was obtained.
73.7 g of an epoxy resin partially modified with 1-butanol, 8.4 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 102 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100 ° C. for 2 hours. . 79.2g of (meth) acrylate resin 18 of a yellow transparent viscous substance was obtained.

[Synthesis Example 19] (Meth) acrylate resin 19
1-decanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 150.0 g and sodium methoxide (manufactured by Kanto Chemical Co., Ltd.) 2.2 g were mixed and stirred at 70 ° C. for 2 hours. The reaction mixture was cooled to 50 ° C., 34.0 g of bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) was added and stirred for 50 minutes, 40.0 g of 3% hydrochloric acid was added, and 300 mL of ethyl acetate was added. Washed 4 times with 300 mL water. Magnesium sulfate is added to the obtained organic phase, and after drying, the solid content is separated by filtration, etc., and the solvent of the obtained organic phase is distilled off by distillation under reduced pressure, and partially with 1-decanol as a transparent viscous product. 41.5 g of a modified epoxy resin was obtained.
30.0 g of epoxy resin partially modified with 1-decanol, 3.1 g of methacrylic acid (Tokyo Chemical Industry Co., Ltd.) and 37 mg of triphenylphosphine (Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100 ° C. for 4 hours. . 31.7g of (meth) acrylate resin 19 of a yellow transparent viscous substance was obtained.

[Synthesis Example 20] (Meth) acrylate resin 20
Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, phenol (Tokyo Chemical Industry Co., Ltd.) 11.8 g and triphenylphosphine (Tokyo Chemical Industry Co., Ltd.) 130 mg are mixed at 100 ° C. Stir for 15 hours. 18.8 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100 ° C. for 7 hours. 102.2g of (meth) acrylate resin 20 of a yellow transparent viscous substance was obtained.

[Synthesis Example 21] (Meth) acrylate resin 21
Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.7 g, acetic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) 12.7 g, and tri 130 mg of phenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at 100 ° C. for 6 hours. 102.3g of (meth) acrylate resin 21 of yellow transparent viscous substance was obtained.

[Synthesis Example 22] (Meth) acrylate resin 22
Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.7 g, butyric anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) 19.8 g, and tri 130 mg of phenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at 100 ° C. for 6 hours. 108.3g of (meth) acrylate resin 22 of a yellow transparent viscous substance was obtained.

[Synthesis Example 23] (Meth) acrylate resin 23
Bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.7 g, crotonic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) 19.3 g, and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at 100 ° C. for 6 hours. 99.5g of (meth) acrylate resin 23 of the yellow transparent viscous substance was obtained.

[Reference Synthesis Example 1] Epoxy resin A
(Reference Synthesis Example 1-1) Synthesis of EXA-850CRP ethylene glycol ring-opened product 500.0 g of ethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 45% tin borofluoride (II) aqueous solution (manufactured by Morita Chemical Co., Ltd.) ) 1.0 g was placed in an eggplant flask. 340.0 g of bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) was gradually added over 1 hour while stirring at 80 ° C., and stirred at 80 ° C. for 1 hour from the end of the addition. The reaction mixture was cooled to room temperature, 1 L of chloroform was added, 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 410.0 g of colorless and transparent viscous EXA-850CRP-ethylene glycol ring-opened product.
(Reference Synthesis Example 1-2) Synthesis of Epoxy Resin A 400.0 g of EXA-850CRP-ethylene glycol ring-opened product, 1017.0 g of epichlorohydrin (manufactured by Osaka Soda Co., Ltd.), and benzyltrimethylammonium chloride (Tokyo Chemical Industry) 51.0 g) was put into a 2 L 3-neck round bottom flask equipped with a mechanical stirrer, thermometer, temperature controller, condenser, Dean-Stark trap and dropping funnel. The mixture was then heated to about 50-55 ° C. with stirring under a high vacuum of 70 torr to vigorously reflux the epichlorohydrin. 137.0 g of 48% aqueous sodium hydroxide (manufactured by Kanto Chemical Co., Inc.) was slowly added to the mixture over 2 hours. As soon as the azeotrope was formed, stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. Stirring was continued for 3 hours after the addition. The reaction mixture was then cooled to room temperature, 1 L of chloroform was added, 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 506.0 g of a light yellow transparent viscous epoxy resin A (epoxy equivalent 228 g / eq, viscosity 27,600 mPa · s).

[Comparative Synthesis Example 2] Comparative (meth) acrylate resin 2
228.0 g of epoxy resin A, 43.0 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 262 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100 ° C. for 7 hours. Comparison (meth) acrylate resin 2 of yellow transparent viscous material 265.0g was obtained.

[Synthesis Example 24] (Meth) acrylate resin 24
114.0 g of epoxy resin A, 10.8 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.8 g of crotonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed. Stir at 100 ° C. for 7 hours. 128.0g of (meth) acrylate resin 24 of a yellow transparent viscous substance was obtained.

[Synthesis Example 25] (Meth) acrylate resin 25
114.0 g of epoxy resin A, 10.8 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.8 g of 3-butenoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) Mix and stir at 100 ° C. for 7 hours. 124.0g of (meth) acrylate resin 25 of a yellow transparent viscous substance was obtained.

[Synthesis Example 26] (Meth) acrylate resin 26
114.0 g of epoxy resin A, 10.8 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 23.0 g of 10-undecenoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) Mix and stir at 100 ° C. for 7 hours. 136.0g of (meth) acrylate resin 26 of the yellow transparent viscous substance was obtained.

[Production of photopolymerization initiator]
The photopolymerization initiator used in Examples and Comparative Examples was produced as follows.
(Production of photopolymerization initiator 1)
26.8 g of diglycidyl ether of PEG400 (Denacol EX-830, manufactured by Nagase ChemteX Corporation), 16.5 g of 4-dimethylaminobenzoic acid, 3.7 g of benzyltrimethylammonium chloride, and 25.0 g of methyl isobutyl ketone (MIBK) Was placed in a flask and stirred at 110 ° C. for 24 hours. The reaction mixture was cooled to room temperature, dissolved in 50.0 g of chloroform, and washed 6 times with 100 mL of water. The solvent of the organic phase was distilled off under reduced pressure to obtain 35.3 g of photopolymerization initiator 1.
(Production of photopolymerization initiator 2)
26.8 g of diglycidyl ether of PEG400 (Denacol EX-830, manufactured by Nagase ChemteX Corporation), 22.8 g of 2-hydroxy-9H-thioxanthen-9-one, 3.7 g of benzyltrimethylammonium chloride, and 40.0 g of MIBK Was placed in a flask and stirred at 110 ° C. for 72 hours. The reaction mixture was cooled to room temperature, dissolved in 50.0 g of chloroform, and washed 6 times with 100 mL of water. The solvent of the organic phase was distilled off under reduced pressure to obtain 36.2 g of photopolymerization initiator 2.

[Examples 1-26 and Comparative Examples 1-2]
Each of (meth) acrylate resin and comparative (meth) acrylate resin produced in Synthesis Example and Comparative Synthesis Example, photopolymerization initiators 1 and 2, filler; core-shell type particles (Zephiac F-351, manufactured by Aika Industry Co., Ltd.) , Filler; silicon dioxide particles (Seahoster KE-C50, manufactured by Nippon Shokubai Co., Ltd.), silane coupling agent; 3-glycidoxypropylmethyldiethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.), curing agent; Using a polyamine compound (EH-5030S, manufactured by ADEKA Corporation, active hydrogen equivalent of 105 g / eq) at the blending amount (parts by weight) shown in Tables 1 to 4 below, a 3-roll mill (C-4 3/4 × 10, manufactured by Inoue Seisakusho Co., Ltd.) to prepare curable resin compositions of Examples and Comparative Examples.

  Each (meth) acrylate resin manufactured in the synthesis example and the comparative synthesis example, and the curable resin compositions of the examples and the comparative examples were evaluated by the following tests.

[Test conditions]
For the (meth) acrylate resin and the comparative (meth) acrylate resin, the epoxy equivalent and the viscosity were measured, the photopolymerization initiators 1 and 2 were measured for the viscosity, and the curable resin compositions produced in Examples and Comparative Examples The adhesive strength was measured.

(1) Epoxy equivalent (WPE) measurement It measured on the conditions of JISK7236: 2001. The unit of epoxy equivalent in the table is g / eq.

(2) Viscosity measurement It measured at 25 degreeC using the E-type viscosity meter (RE105U, the Toki Sangyo Co., Ltd. make).

(3) Adhesive strength measurement A polyimide-based alignment liquid (Sunever SE-7492, manufactured by Nissan Chemical Industries, Ltd.) was dropped onto an ITO substrate (403005XG-10SQ1500A, manufactured by Geomat Co., Ltd.) that had been washed with pure water and dried using an air dispenser. (0.4 MPa, 5.0 seconds), and then, it was uniformly applied under the condition of reaching 5000 rpm in 10 seconds with a spin coater and then keeping for 20 seconds. After uniformly coating, pre-baking (1 minute) on an 85 ° C. hot plate and post-baking (60 minutes) in an oven at 230 ° C., a substrate with a polyimide alignment film was prepared.

Curable resin composition after bonding the curable resin composition to the positions of 15 mm × 3 mm, 15 mm × 21 mm on an ITO substrate with a 6 μm spacer dispersed, a substrate with a polyimide alignment film (30 mm × 30 mm × 0.5 mmt) Spot coating was performed so that the diameter of the object was in the range of 1.5 to 2.5 mmφ. Thereafter, the same type of substrates (23 mm × 23 mm × 0.5 mmt) are bonded together, and ultraviolet rays are irradiated with an integrated light amount of 3000 mJ / cm ² (irradiation apparatus: UVX-01224S1, manufactured by Ushio Electric Co., Ltd.), and cured. And cured for 1 hour to prepare a cured specimen. Using an autograph (TG-2kN, manufactured by Minebea Co., Ltd.), fixing the test piece and punching out a 15 mm × 25 mm position of the substrate at a speed of 5 mm / min, ITO substrates (ITO / ITO) and polyimide substrates The adhesive strength of (PI / PI (TN)) was measured.

  The results of the epoxy equivalent and the viscosity measurement are shown in Tables 1 to 4 together with the blending compositions of the curable resin compositions of Examples 1 to 26 and Comparative Examples 1 and 2. Moreover, the result of the adhesive strength measurement performed about a part of Example and the comparative example is shown to Tables 5-8.

Claims (3)

(Meth) acrylate resin represented by the following formula (5) ;
A sealing agent for liquid crystal, comprising a thermosetting agent and / or a polymerization initiator.
Ar ¹ (—O—A ¹ ) _n1 (5)
[Where,
Ar ¹ is an n1 valent group having a total number of carbon atoms and heteroatoms of 5 or more, and including one or more aromatic rings or heteroaromatic rings,
n1 is 1 or more,
A ¹ is independently a hydrogen atom, a group represented by the following formula (1), a group represented by the following formula (2-1), a group represented by the following formula (2-2), the following formula ( 2-3), a group represented by the following formula (3), a group represented by the following formula (4-1) or a group represented by the following formula (4-2),
However, in the molecule, the group represented by the formula (4-1) having the group represented by the formula (1); the formula (4-2) having a group represented by the formula (1) A group; and one or more groups selected from the group consisting of groups represented by formula (1), and
A group represented by formula (4-1) having a group represented by formula (2-1), a group represented by formula (2-2), or a group represented by formula (2-3); A group represented by formula (4-2) having a group represented by (2-1), a group represented by formula (2-2) and / or a group represented by formula (2-3); A group represented by formula (2-1); a group represented by formula (2-2); and one or more groups selected from the group consisting of groups represented by formula (2-3). ]

[Where,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group,
R ²¹ is an alkenyl group or an alkynyl group,
R ²² and R ²³ are each independently an alkyl group, alkenyl group, alkynyl group or aryl group, or R ²² and R ²³ together form a ring structure;
X ¹ is an oxygen atom or a sulfur atom,
R ²⁴ is an alkyl group, an alkenyl group, an alkynyl group or an aryl group,
However, R ²¹ , R ²² and R ²³ are not vinyl groups or 1-methylvinyl groups,
B ¹ is independently an alkylene group, m 1 is 1 or more,
D ¹ is an arylene group, an alkylene-arylene-alkylene group, an alkylene-arylene group, an arylene-alkylene-arylene group or a group: —B ² — (O—B ² ) _m2 —, and B ² is independently An alkylene group, m2 is 0 or 1 or more,
C ¹ , C ² and C ³ are each independently a hydrogen atom, a group represented by formula (1), a group represented by formula (2-1), or a group represented by formula (2-2). , A group represented by formula (2-3), or a group represented by formula (3). ] The sealing agent for liquid crystals of Claim 1 in which (meth) acrylate resin has group represented by Formula (3) in a molecule | numerator .

[Wherein, R ⁶ represents a hydrogen atom or a methyl group. ] Furthermore, an epoxy resin (excluding an epoxy resin having a (meth) acryloyl group), a modified epoxy resin in which part or all of the epoxy group of the epoxy resin is modified with a modifying compound, and an epoxy group of the epoxy resin Including one or more resins selected from the group consisting of modified epoxy resins, part or all of which are modified with (meth) acrylic acid,
Here, the modifying compound is selected from the group consisting of unsaturated aliphatic carboxylic acids (excluding (meth) acrylic acid), carboxylic anhydrides (excluding (meth) acrylic anhydride), alcohols and thiols. The sealing compound for liquid crystals of Claim 1 or 2 which is one or more selected compounds.