TW202106746A - Sealant for liquid crystal dropping method - Google Patents

Abstract

The present invention relates to a sealant for a liquid crystal dropping method which imparts a cured product having excellent adhesiveness to an alignment film and low moisture permeability, the sealant comprising a curable resin, a photoinitiator, and a thermosetting agent, wherein: the curable resin includes an oligomer A and an oligomer B; the oligomer A is a compound obtained by subjecting an epoxy resin, having an epoxy equivalent of 200 g/epo or more and having an amount of aromatic rings of 0.43 or more, to a partial (meth)acrylic modification; and the oligomer B is at least one selected from the group consisting of a compound obtained by subjecting a bisphenol-A-type epoxy resin, a bisphenol-F-type epoxy resin, a bisphenol-AD-type epoxy resin, or a bisphenol-A-type epoxy resin to a partial (meth)acrylic modification, a compound obtained by subjecting a bisphenol-F-type epoxy resin to a partial (meth)acrylic modification, and a compound obtained by subjecting a bisphenol-AD-type epoxy resin to a partial (meth)acrylic modification.

Description

Sealant for liquid crystal dropping method

The present invention relates to a sealing compound for liquid crystal dropping method.

Among the manufacturing methods of liquid crystal display elements, the dropping method is a method of manufacturing a panel by directly dropping liquid crystal into a closed loop of the sealant under vacuum, bonding, and releasing the vacuum. This dropping method has many advantages such as reducing the amount of liquid crystal used and shortening the injection time into the liquid crystal panel, and is becoming the mainstream of the current manufacturing method of liquid crystal panels using large substrates. In the method including the dropping method, a sealant and liquid crystal are applied and bonded together, and then a gap is set to perform positioning, and the sealant is cured mainly by ultraviolet curing.

Patent Document 1 proposes an epoxy resin in which an alkylene carbonate or a halohydrin compound is added to a phenol compound having one or more phenolic hydroxyl groups, and the glycidyl ether is further etherified to be used as one of the sealants for the liquid crystal dropping method. Raw materials; and modified epoxy resin in which the epoxy resin is modified with carboxylic acid, carboxylic anhydride, or phenol compound (Patent Document 1). [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2017-002246 A

[The problem to be solved by the invention]

In recent years, with the narrowing of the frame of the liquid crystal panel, the sealant and the alignment film tend to overlap. Therefore, adhesion to the alignment film is required. In addition, the line width of the sealant tends to be narrow at the same time. Therefore, low moisture permeability is required.

Therefore, the subject of the present invention is to provide a sealing compound for a liquid crystal dropping method, which produces a cured product having excellent adhesion to an alignment film and excellent low moisture permeability. [Means used to solve the problem]

The present invention has the following constitution. [1] "A sealing compound for liquid crystal dropping method, which is a sealing compound for liquid crystal dropping method containing a curable resin, a photoinitiator, and a thermosetting agent, and The curable resin contains oligomer A and oligomer B, The oligomer A is a compound that modifies the (meth)acrylic resin part of the epoxy resin having an epoxy equivalent of 200 g/epo or more and an aromatic ring weight of 0.43 or more, The oligomer B is selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, and a compound that partially modifies (meth)acrylic acid of bisphenol A epoxy resin, One or more of the group consisting of the compound which modified the bisphenol F type epoxy resin part (meth)acrylic acid and the compound which modified the bisphenol AD type epoxy resin part (meth)acrylic acid. [2] "The sealing compound for liquid crystal dropping methods as in [1], wherein the oligomer A has 3 or more benzene rings in one molecule. [3] "The sealing compound for liquid crystal dropping methods as in [1] or [2], wherein the oligomer A has a bisphenol F type structure. [4] "The sealing compound for liquid crystal dropping methods as in any one of [1] to [3], wherein the oligomer B is a part of bisphenol F epoxy resin or bisphenol F epoxy resin (methyl) Acrylic modified compound. [Effects of Invention]

According to the present invention, it is possible to provide a sealant for liquid crystal dropping methods, which produces a cured product having excellent adhesion to an alignment film and excellent low moisture permeability.

The following describes suitable embodiments of the present invention. In this specification, "glycidyl" means 2,3-epoxypropyl. "Methylglycidyl" means 2,3-epoxy-2-methylpropyl. The "epoxy group" includes at least one of a glycidyl group and a methylglycidyl group. "(Meth)acrylic acid group" includes acrylic acid group (CH ₂ =CH ₂ -C(=O)-) and methacrylic acid group (CH ₂ =CH(CH ₃ )-C(=O)-) At least one of. "Substitutable" means "replaced or unsubstituted."

[Sealant for liquid crystal dropping method] The sealing compound for the liquid crystal dropping method contains a curable resin, a photoinitiator, and a thermosetting agent. The curable resin contains oligomer A and oligomer B. The oligomer A has an epoxy equivalent of 200 g/epo or more, and The epoxy resin part (meth)acrylic modified compound with an aromatic ring content of 0.43 or more, and the oligomer B is selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol AD type epoxy resin Resin, a compound that modifies the bisphenol A epoxy resin part (meth)acrylic acid, a compound that modifies the bisphenol F epoxy resin part (meth)acrylic acid, and a bisphenol AD epoxy resin part ( One or more of the group consisting of meth)acrylic acid-modified compounds.

(Curable resin) The curable resin contains oligomer A and oligomer B.

＜oligomer A＞ The oligomer A is a compound obtained by partially (meth)acrylic modified epoxy resin having an epoxy equivalent of 200 g/epo or more and an aromatic ring weight of 0.43 or more (hereinafter also referred to as "raw epoxy resin"). Here, "partially (meth)acrylic modification" of epoxy resin means that part of epoxy group of epoxy resin is modified by (meth)acrylic acid.

＜＜Raw material epoxy resin＞＞ ＜＜＜Epoxy equivalent＞＞＞ The epoxy equivalent of the raw material epoxy resin is 200 g/epo or more. By using the raw material epoxy resin having such an epoxy equivalent, the concentration of the functional group in one molecule of the oligomer A becomes low, and a sealing compound for liquid crystal dropping methods having excellent adhesion to the alignment film can be obtained. The epoxy equivalent of the raw material epoxy resin is preferably 200-400g/epo, preferably 230-330g/epo, and particularly preferably 260-320g/epo. In this specification, the epoxy equivalent can be obtained in accordance with JISK7236:2001 (corresponding to ISO3001:1999).

＜＜＜Aromatic ring amount＞＞＞ The amount of aromatic rings of the raw material epoxy resin is 0.43 or more. By combining the oligomer A obtained by using the raw material epoxy resin having such an aromatic ring content and the oligomer B described later, a sealing compound for liquid crystal dropping methods having excellent low moisture permeability can be obtained. The amount of aromatic ring of the raw material epoxy resin is preferably 0.43 to 0.60, 0.43 to 0.55 is more preferred, and 0.48 to 0.53 is particularly preferred.

In this specification, the aromatic ring amount means the ratio of the aromatic ring structure in the raw epoxy resin. That is, the amount of aromatic rings is a value obtained by the following formula (numeral 1). Aromatic ring weight = the total number of molecular weights of the aromatic ring structure in one molecule of the raw epoxy resin ÷ the molecular weight of one molecule of the raw epoxy resin (number 1)

In addition, the molecular weight of the aromatic ring structure is calculated based on the weight of the carbon atoms constituting the aromatic ring. For example, a benzene ring such as a phenyl group and a phenylene ring is a single group, which is the total of the molecular weights of the carbon atoms constituting the benzene ring (ring having 6 carbon atoms) (that is, 72). In addition, the group of a condensed ring such as a naphthalene ring (a ring with 10 carbon atoms) and an anthracene ring (a ring with 14 carbon atoms) is the sum of the molecular weights of the carbon atoms constituting the condensed ring (that is, 120 and 168 ). In addition, when the aromatic ring is a heteroaromatic ring, the molecular weight of the aromatic ring structure is calculated based on the weight of the heteroatoms and carbon atoms constituting the heteroaromatic ring. The aromatic ring group constituting the oligomer A preferably does not contain heteroatoms.

＜＜＜Appropriate raw material epoxy resin condition＞＞＞ Such a raw material epoxy resin is preferably an epoxy resin represented by the following formula (1).

[In the formula, G ¹ and G ^{2 are} independently a glycidyl group or a methyl glycidyl group, R ¹¹ is a hydrogen atom or a methyl group, and X ¹ is an optionally substituted aromatic group with 6 to 20 carbon atoms -O- Group, optionally substituted aromatic group with 6 to 20 carbon atoms -(OR ¹ ) _n1 -O- group (where R ¹ is an alkylene group with 1 to 6 carbon atoms, n1 is an integer of 1 to 10 ), or a substituted heteroaromatic group with a total number of 5-30 atoms, Y ¹ is an arylene group with 6-20 carbon atoms, an alkylene group with 1 to 4 carbon atoms-a group with 6-20 carbon atoms Arylene, alkylene having 1 to 4 carbon atoms-arylene having 6 to 20 carbon atoms-alkylene having 1 to 4 carbon atoms, arylene having 6 to 20 carbon atoms-carbon atom An alkylene group of 1 to 4-an arylene group or group with 6 to 20 carbon atoms: -R ² -(OR ² ) _n2- (where R ² is an alkylene group of 1 to 6 carbon atoms , N2 is 0 or an integer of 1 to 6), but the number of benzene rings in the molecule is 3 or more]

In formula (1), G ¹ and G ^{2 are} independently glycidyl or methylglycidyl. From the viewpoint of easy synthesis, it is ^{preferable that G 1} and G ² are both glycidyl groups.

In the formula (1), R ¹¹ is a hydrogen atom or a methyl group. From the viewpoint of easy synthesis, R ¹¹ is preferably a hydrogen atom.

In formula (1), X ¹ is an optionally substituted aromatic group having 6 to 20 carbon atoms -O- group, and an optionally substituted aromatic group having 6 to 20 carbon atoms -(OR ¹ ) _n1 -O- group (In the formula, R ¹ is an alkylene group having 1 to 6 carbon atoms, and n1 is an integer of 1 to 10), or a substituted heteroaromatic group having 5 to 30 atoms in total.

Aromatic groups with 6 to 20 carbon atoms include monocyclic or polycyclic aromatic hydrocarbon groups, phenyl, biphenyl, naphthyl, triphenyl, anthracenyl, fluorenyl, etc., and phenyl and biphenyl Base is better.

The substituent of the aromatic group having 6 to 20 carbon atoms is not particularly limited, and examples thereof include an alkyl group having 1 to 4 carbon atoms, an alkoxy group, an alkylcarbonyl group, an alkyl mercapto group, and a cycloalkyl group.

The alkyl group having 1 to 4 carbon atoms includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, and a tertiary butyl group.

Examples of the alkyl moiety in the alkoxy group include the aforementioned examples of the alkyl group having 1 to 4 carbon atoms. The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an isobutoxy group, a second butoxy group, and a third butoxy group. Examples of the alkyl group in the alkylcarbonyl group and the alkylmercapto group include the aforementioned examples of the alkyl group having 1 to 4 carbon atoms. Examples of the alkylcarbonyl group include acetyl, propionyl, 2-methylpropionyl, butyryl and the like. The alkyl mercapto group includes methyl mercapto, ethyl mercapto, propyl mercapto, isopropyl mercapto, butyl mercapto, isobutyl mercapto, second butyl mercapto, tertiary butyl mercapto, and the like. Cycloalkyl groups include monocyclic or polycyclic aliphatic hydrocarbon groups with 3 to 20 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, Cyclododecyl, adamantyl, etc.

The alkylene group having 1 to 4 carbon atoms includes methylene, ethylene, trimethylene, propylene (propane-1,2-diyl), propylene (propane-1,1-diyl) Base), isopropylene (propane-2,2-diyl), tetramethylene, butylene (butane-1,1-diyl), isobutylene (2-methylprop-1,1- Second base) and so on. In addition, the alkylene having 1 to 6 carbon atoms includes pentamethylene, 2-methylpentane-1,5-diyl, and hexamethylene in addition to the aforementioned alkylene having 1 to 4 carbon atoms. Alkylene groups with 5 and 6 carbon atoms such as methylene group.

A heteroaromatic group with a total number of 5 to 30 atoms, in addition to carbon atoms, a monocyclic or polycyclic heterocyclic group containing at least one heteroatom selected from the group consisting of oxygen atoms, sulfur atoms and nitrogen atoms Examples include phthalimide, imidazolyl, xanthenyl, thioxanthyl, thienyl, dibenzofuranyl, chromenyl, isothiochromenyl, phenoxathiyl, pyrrolyl, pyrazolyl , Pyrazinyl, pyrimidinyl, pyridazinyl, indolazinyl, isoindolyl, indolyl, indazolyl, purinyl, quinazinyl, isoquinolinyl, quinolinyl, phthalazinyl, Naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridine, carbazolyl, β-carbolinyl, phenanthridinyl, acridinyl, pyridinyl, phenantholinyl, phenanthrazine Group, isothiazolyl, phenothiazinyl, isoxazolyl, furyl, etc. Examples of the substituents of the heteroaromatic group having 5 to 30 total atoms include the aforementioned substituents of the aryl group having 6 to 20 carbon atoms.

X ^{1 is} represented by phenoxy group, 4-tert-butyl-phenoxy group, biphenyl-2-yloxy group, phthalimide group, phenyl-(OCH ₂ CH ₂ ) _n1a -O- group (formula Among them, n1a represents an integer of 2-10), preferably phenoxy.

In the formula (1), Y ¹ is an arylene group having 6 to 20 carbon atoms, an alkylene group having 1 to 4 carbon atoms-an arylene group having 6 to 20 carbon atoms, and an arylene group having 1 to 4 carbon atoms. Alkyl group-arylene group with 6 to 20 carbon atoms-alkylene group with 1 to 4 carbon atoms, arylene group with 6 to 20 carbon atoms-alkylene group with 1 to 4 carbon atoms-number of carbon atoms 6-20 arylene group, or group: -R ² -(OR ² ) _n2- (in the formula, R ² is an alkylene group with 1 to 6 carbon atoms, and n2 is an integer of 0 or 1 to 6) .

The arylene group having 6 to 20 carbon atoms includes monocyclic or polycyclic aromatic groups, phenylene, naphthylene, and anthracenyl, and phenylene is preferred.

Examples of the alkylene group having 1 to 4 carbon atoms-arylene having 6 to 20 carbon atoms and the alkylene group having 1 to 4 carbon atoms and the arylene group having 6 to 20 carbon atoms are as described above. The alkylene group having 1 to 4 carbon atoms-the arylene group having 6 to 20 carbon atoms is preferably an ethylene-1,4-phenylene group. The bonding sequence of each group in the alkylene group with 1 to 4 carbon atoms-arylene group with 6 to 20 carbon atoms can be any one, but the oxygen bonded to the group ^{containing X 1} The arylene group having 6 to 20 carbon atoms in the alkylene group having 1 to 4 carbon atoms-arylene group having 6 to 20 carbon atoms is preferably bonded to the atom.

C1-C4 alkylene group-C6-C20 arylene group-C1-C4 alkylene group, C1-C4 alkylene group and C6-C6 alkyl group Examples of the arylene group of 20 are as described above. Alkylene having 1 to 4 carbon atoms-arylene having 6 to 20 carbon atoms-Alkylene having 1 to 4 carbon atoms, with 1,3-phenylene bismethylene (interminyl) ) And 1,4-phenylene bismethylene (p-stubble group) are preferred.

(式中，R²¹ 及R²² 互相獨立，氫原子、甲基、乙基、三氟甲基或苯基)

為特佳。Arylene group having 6 to 20 carbon atoms-alkylene group having 1 to 4 carbon atoms-alkylene group having 1 to 4 carbon atoms and 6 to carbon atoms in an arylene group having 6 to 20 carbon atoms Examples of the arylene group of 20 are as described above. The arylene group having 6 to 20 carbon atoms-alkylene group having 1 to 4 carbon atoms-arylene group having 6 to 20 carbon atoms are preferably the following groups:

(In the formula, R ²¹ and R ^{22 are} independent of each other, a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group or a phenyl group)

It is especially good.

In formula (1), Y ^{1 is} an arylene group having 6 to 20 carbon atoms, an alkylene group having 1 to 4 carbon atoms-an arylene group having 6 to 20 carbon atoms, and an arylene group having 1 to 4 carbon atoms. Alkyl group-arylene group with 6 to 20 carbon atoms-alkylene group with 1 to 4 carbon atoms, or arylene group with 6 to 20 carbon atoms-alkylene group with 1 to 4 carbon atoms-carbon atom Arylene groups of 6 to 20 are preferred. In a suitable epoxy compound ^{having Y 1 , any one of X 1} and Y ¹ has an aromatic ring. If ^{an epoxy compound in which both X 1} and Y ¹ have an aromatic ring is used, the resulting cured product will have excellent low moisture permeability.

In addition, in formula (1), the total number of benzene rings possessed by ^{X 1} and Y ^{1 is 3 or more.} If ^{an epoxy resin with a total of 2 benzene rings in X 1} and Y ¹ is used, it will not be an epoxy resin with an epoxy equivalent of 200 g/epo or more and an aromatic ring weight of 0.43 or more. When the alignment film has poor adhesion and/or high moisture permeability.

This compound that modifies the (meth)acrylic acid part of the epoxy resin represented by the formula (1) is that a part of G ¹ and/or G ² in the epoxy resin represented by the formula (1) is substituted with a group : -CH ₂ CR ¹³ (OR ³¹ )CH ₂ OZ (where R ¹³ is a hydrogen atom or a methyl group, R ³¹ is a hydrogen atom or a (meth)acryloyl group, and Z is a (meth)acryloyl group) Compound.

The epoxy compound represented by the above formula (1) and the epoxy compound represented by the above formula (1) partially (meth)acrylic modified compound can be modified by the method described in Japanese Patent Application Laid-Open No. 2017-002246 To make.

＜＜Appropriate aspect of oligomer A＞＞ From the viewpoint of low moisture permeability, oligomer A preferably has 3 or more benzene rings in one molecule, preferably 3-6 benzene rings in one molecule, and 4-6 benzene rings in one molecule. A benzene ring is particularly preferred. Here, the group having a condensed ring refers to the number of benzene rings in a single ring constituting the condensed ring. For example, the number of benzene rings in the naphthalene ring is 2, and the number of benzene rings in the pyrene ring is 4. When there are more than three benzene rings in one molecule of the oligomer A, it is preferable that the benzene ring exists independently (that is, does not include a condensed ring).

。 這種特佳的化合物，除了雙酚F型的構造之外，還可列舉具有一個苯基的化合物。In addition, from the viewpoint of low moisture permeability, oligomer A preferably has a bisphenol F type structure, and particularly preferably has three or more benzene rings in one molecule and a bisphenol F type structure. Here, the structure of bisphenol F type refers to the structure shown below:

. In addition to the structure of the bisphenol F type, compounds having one phenyl group can be cited as such particularly preferred compounds.

The oligomer A may be one type or a combination of two or more types. In addition, oligomer A does not correspond to the component of oligomer B mentioned later. That is, oligomer A is not a compound that modifies bisphenol A epoxy resin part (meth)acrylic acid, a compound that modifies bisphenol F epoxy resin part (meth)acrylic acid, and bisphenol AD Type epoxy resin partially modified by (meth)acrylic acid.

＜oligomer B＞ Oligomer B is selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin and part of (meth) acrylic modified compounds (that is, bisphenol A type epoxy resin). Resin part (meth)acrylic modification compound, bisphenol F type epoxy resin part (meth)acrylic acid modification compound, and bisphenol AD type epoxy resin part (meth)acrylic modification compound) One or more types in the formed group. Here, the bisphenol A type epoxy resin is an epoxy resin which is a condensation product of bisphenol A (2,2-bis(4-hydroxyphenyl)propane) and epichlorohydrin. Bisphenol F type epoxy resin is an epoxy resin which is a condensation product of bisphenol F (bis(4-hydroxyphenyl)methane) and epichlorohydrin. Bisphenol AD type epoxy resin is an epoxy resin which is a condensation product of bisphenol AD (1,1-bis(4-hydroxyphenyl)ethane) and epichlorohydrin.

From the viewpoint of adhesion to the alignment film, the oligomer B is selected from the group consisting of bisphenol F epoxy resins and compounds that partially modify (meth)acrylic acid of bisphenol F epoxy resins. More than one of them is preferred. The oligomer B may be one type or a combination of two or more types.

＜Other curable resin＞ Curable resins other than oligomer A and oligomer B (hereinafter also referred to as "oligomer C") are not particularly limited, and examples include conventional ethylene resins used as the main agent of sealants for liquid crystal dropping methods. Resins of sexually unsaturated groups and/or epoxy groups.

The oligomer C of the resin having an epoxy group is not particularly limited as long as it has one or more epoxy groups. Examples of such epoxy-containing resins include raw epoxy resins and epoxy resins other than raw epoxy resins. Here, "epoxy resins other than raw material epoxy resins" refers to epoxy resins with an epoxy equivalent of 200g/epo or more and an aromatic ring weight of less than 0.43; an epoxy equivalent of less than 200g/epo and an aromatic ring weight Epoxy resin above 0.43; or epoxy resin with epoxy equivalent less than 200g/epo and aromatic ring less than 0.43. The oligomer C of a resin having an epoxy group is obtained by adding alkylene carbonate or halohydrin to a compound having one or more phenolic hydroxyl groups as described in JP 2017-214462 A, and further glycidyl etherification Epoxy resin is preferred.

Examples of the oligomer C of the resin having an ethylenically unsaturated group include compounds in which all epoxy groups in the oligomer C of the resin having an epoxy group are modified by (meth)acrylic acid.

Examples of the oligomer C of the resin having an ethylenically unsaturated group and an epoxy group include partial (meth)acrylic modified compounds of epoxy resins other than the raw material epoxy resin.

In addition to the above, the oligomer C is described in WO2014/057871, JP 2017-002204 A, etc., and can be selected appropriately. In addition, oligomer C preferably does not have silicon atoms.

(Photoinitiator) The photopolymerization initiator means a compound that is activated by absorbing the energy of light and generates free radicals. The photopolymerization initiator is not particularly limited, and examples include benzoin, acetophenone, benzophenone, thioxanthone, α-oxime ester, phenyl glyoxylate, and diphenyl ethyl A polymerization initiator for diketones, azo compounds, diphenyl sulfide compounds, phosphine oxide compounds, benzoins, benzoin ethers, and anthraquinones. The photopolymerization initiator preferably has a low solubility to liquid crystals and has a reactive group that does not vaporize the decomposition product when exposed to light. Examples of such suitable polymerization initiators include EY resin KR-2 (manufactured by KSM Corporation). In addition, a radical polymerization initiator, as described in WO2012/077720, is a compound obtained by reacting a compound having at least two epoxy groups with dimethylaminobenzoic acid, and a compound having at least two epoxy groups The polymerization initiator for the mixture of the compound obtained by reacting the compound with hydroxythioxanthone is preferred.

(Thermal hardener) The thermosetting agent is not particularly limited. Examples of the amine curing agent include organic acid dihydrazine compounds, amine adducts, imidazoles and their derivatives, dicyandiamide, aromatic amines, and epoxy-modified polyamines. And polyaminourea, etc., VDH (1,3-bis(hydrazinocarbonylethyl)-5-isopropyl hydantoin), ADH (dihydrazine adipate), UDH (7,11-octadecane) Diene-1,18-dicarbonyl hydrazine) and LDH (octadecane-1,18-dicarboxylic acid dihydrazine) and other organic acid dihydrazides; Adeka Hardener EH5030S from ADEKA, Ajinomoto FineTechno company sells amine adducts under the names of Ajicure PN-23, Ajicure PN-30, Ajicure MY-24, Ajicure MY-H, etc. These hardeners can be used singly or in multiples.

(Additional ingredients) The sealing compound for liquid crystal dropping methods may further contain additional components such as a filler and a coupling agent. The additional components may be singly or in combination of two or more.

The filler is used to control the viscosity of the liquid crystal dropping method sealant, or to increase the strength of the cured product after the liquid crystal dropping method sealant is cured, or to improve the adhesion reliability of the liquid crystal dropping method sealant by suppressing linear expansion. Add for purpose. The filler is not particularly limited, and examples include well-known inorganic fillers and organic fillers used for sealants for liquid crystal dropping methods.

Inorganic fillers include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, titanium oxide, aluminum oxide, zinc oxide, silicon dioxide, kaolin, talc, glass beads, sericite activated clay, bentonite, and nitrogen Aluminum and silicon nitride.

Organic fillers include polymethylmethacrylate, polystyrene, copolymers obtained by copolymerizing monomers constituting these polymers with other monomers, polyester microparticles, polyurethane microparticles, rubber microparticles, and Core-shell particles and the like composed of a shell containing a copolymer having a high glass transition temperature and a core of a copolymer having a low glass transition temperature.

Commercially available fillers can be used. Commercially available inorganic fillers include glass fillers ("CF0023-05C" manufactured by Japan Frit), amorphous silica ("SEAHOSTAR KE-P250" manufactured by Nippon Shokubai Co., Ltd.), fuming silica (shake Denaturing agent) ("TG-308F" manufactured by Cabot Specialty Chemicals), spherical silica ("CF0018-WB15C" manufactured by Japan Frit). Silicon dioxide particles (SEAHOSTAR KE series (KE-C50, etc.)), etc. In addition, commercially available organic fillers include core-shell particles ZEFIAC series (F-351, etc., manufactured by AICA Industry Co., Ltd.). The fillers may be one type or a combination of two or more types.

The coupling agent is added for the purpose of improving the adhesiveness of the liquid crystal display substrate. The coupling agent is not particularly limited, and examples include γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-isocyanatepropyltrimethoxysilane, and 3-glycidoxypropylmethyl Diethoxy silane and 3-glycidoxy propyl trimethoxy silane, etc. The silane coupling agent may be one type or a combination of two or more types.

The additional components other than the filler and the coupling agent are additives added to the sealing compound for liquid crystal dropping methods, and known components or commercially available products can be mentioned.

(composition) The content of oligomer A is preferably 1 to 99 parts by weight, preferably 10 to 95 parts by weight, and particularly preferably 40 to 90 parts by weight relative to 100 parts by weight of the total of oligomer A and oligomer B.

The content of suitable oligomer A is preferably 1-100 parts by weight, preferably 50-99 parts by weight, and particularly preferably 90-95 parts by weight, relative to 100 parts by weight of the total of oligomer A.

The content of suitable oligomer B is preferably from 1 to 100 parts by weight, preferably from 50 to 99 parts by weight, and particularly preferably from 90 to 95 parts by weight, relative to 100 parts by weight of the total of oligomer B.

The total of the content of the oligomer A and the content of the oligomer B is preferably 50-100 parts by weight, particularly preferably 70-100 parts by weight, relative to the total weight of 100 parts of the curable resin. In addition, in the curable resin, components other than oligomer A and oligomer B are oligomer C.

The content of the photopolymerization initiator is preferably 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the curable resin in total.

The content of the thermosetting agent is preferably 1 to 50 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of the curable resin in total.

The content of the filler is preferably 1-50 parts by weight, preferably 5-30 parts by weight, relative to 100 parts by weight of the curable resin in total.

The content of the coupling agent is preferably 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the curable resin in total.

When the total amount of the sealing compound for the liquid crystal dropping method is 100 parts by weight, the content of the curable resin is preferably 40 parts by weight or more and less than 100 parts by weight, and preferably 60 parts by weight or more and less than 100 parts by weight.

(use) The cured product of the sealing compound for the liquid crystal dropping method is used for sealing the liquid crystal display. The liquid crystal display body is not specifically limited, The liquid crystal display body applied to the sealing compound for conventional liquid crystal dropping methods can be used. The sealant for the liquid crystal dropping method is cured by irradiating energy rays such as ultraviolet rays, heating, or heating before, after or simultaneously irradiating energy rays such as ultraviolet rays. [Example]

The following examples further illustrate the specific aspects of the present invention in detail, but the present invention is not limited by these examples.

(Use products) The components used in Examples and Comparative Examples are as follows. The sealing compound for liquid crystal dropping methods of an Example and a comparative example was prepared by mixing the following components to the composition described in the table. In addition, the values in the table are parts by weight.

化合物1可藉由以下的方法來獲得。1. Oligo A (1) Compound 1

Compound 1 can be obtained by the following method.

(Production of Compound 1) 166 g of phenyl glycidyl ether (EX-141, manufactured by Nagasechemtex), 200 g of RESITOP BPF-SG (bisphenol F) (manufactured by Gunei Chemical Industry Co., Ltd.), and benzyltrimethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 g and 600 g of toluene (manufactured by Kanto Chemical Co., Ltd.) were put in a flask equipped with a thermometer and a stirrer, and stirred at 120°C for 8 hours. After the reaction, the mixture was cooled to room temperature, and washed with 2000 g of 1% sodium hydroxide aqueous solution once and washed with 2000 mL of water twice. The solvent of the obtained organic phase was distilled off under reduced pressure to obtain 336 g of a yellow transparent viscous ring-opened body (EX-141-bisphenol F ring-opened body).

330 g of EX-141-bisphenol F ring-opened body, 1742 g of epichlorohydrin (manufactured by Wako Pure Chemical Industries, Ltd.), and 35 g of benzyltrimethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a thermometer, condenser, and Dean. -A 2L three-necked round bottom flask with a Stark separator, dropping funnel, and agitator. Next, while stirring the mixture under a reduced pressure of 50 torr, it was heated to about 50° C., and 282 g of a 48% sodium hydroxide aqueous solution (manufactured by Kanto Chemical Co., Ltd.) was dropped over 3 hours. The epichlorohydrin in the azeotropically distilled water/epichlorohydrin mixture is returned to the reaction system while continuing to stir. After the addition, stirring was continued for 3 hours. Next, the reaction mixture was cooled to room temperature, 900 g of toluene and 300 g of methyl isobutyl ketone were added, and the mixture was washed with 1500 mL of water 4 times. The solvent of the obtained organic phase was distilled off under reduced pressure to obtain 395 g of glycidyl ether body (compound 1a, raw material epoxy resin) as a yellow transparent viscous substance.

200 g of compound 1a, 35 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 212 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) as a catalyst, and 50 mg of BHT (dibutylhydroxytoluene, manufactured by Kanto Chemical Co., Ltd.) were added to the thermometer. , The flask of the stirrer, stir at 100 ℃ for 8 hours. After the completion of the reaction, a part of the methacrylated epoxy compound (Compound 1) was obtained.

化合物2是依據日本特開2017-002246號公報之第106段落～第111段落所記載的方法來獲得。(2) Compound 2

Compound 2 was obtained according to the method described in paragraph 106 to paragraph 111 of JP 2017-002246 A.

化合物3是藉由以下的方法來獲得。(3) Compound 3

Compound 3 was obtained by the following method.

(Production of Compound 3) 50 g of phenyl glycidyl ether (EX-141, manufactured by Nagasechemtex), 116 g of BisP-AP (manufactured by Honshu Chemical Industry Co., Ltd.), 3.1 g of benzyltrimethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), and toluene (Kanto Chemical Co., Ltd.) (Company) 200g was put into a flask equipped with a thermometer and a stirrer, and stirred at 120°C for 8 hours. After the reaction, the mixture was cooled to room temperature, 200 g of methyl isobutyl ketone (manufactured by Kanto Chemical Co., Ltd.) was added, and the mixture was washed 4 times with 500 g of a 1% sodium hydroxide aqueous solution and 4 times with 500 mL of water. The solvent of the obtained organic phase was distilled off under reduced pressure to obtain 124 g of a yellow transparent viscous ring-opened body (EX-141-BisP-AP ring-opened body).

100g of EX-141-BisP～AP ring-opening body, 421g of epichlorohydrin (manufactured by Wako Pure Chemical Industries, Ltd.), and 8.4g of benzyltrimethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) An-Stark separator, dropping funnel, 1L three-necked round bottom flask with stirrer. Next, while stirring the mixture under reduced pressure of 50 torr, it was heated to about 50°C, and 68 g of 48% sodium hydroxide aqueous solution (manufactured by Kanto Chemical Co., Ltd.) was dropped over 3 hours. The epichlorohydrin in the azeotropically distilled water/epichlorohydrin mixture is returned to the reaction system while continuing to stir. After the addition, stirring was continued for 3 hours. Next, the reaction mixture was cooled to room temperature, 250 g of toluene and 250 g of methyl isobutyl ketone were added, and the mixture was washed with 500 mL of water 4 times. The solvent of the obtained organic phase was distilled off under reduced pressure to obtain 120 g of a yellow transparent viscous glycidyl ether body (compound 3a, raw material epoxy resin).

Add 50 g of compound 3a, 7.2 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 22 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 11 mg of BHT (dibutylhydroxytoluene, manufactured by Kanto Chemical Co., Ltd.) as a catalyst. The flask of a thermometer and a stirrer was stirred at 100°C for 8 hours. After the completion of the reaction, a part of the methacrylated epoxy compound (Compound 3) was obtained.

化合物4是藉由以下的方法來獲得。(4) Compound 4

Compound 4 was obtained by the following method.

(Production of compound 4) 75 g of biphenyl type monofunctional epoxy resin (OPP-G, manufactured by Sanko Co., Ltd.), 2,2-bis(4-hydroxyphenyl) propane (bisphenol A) (manufactured by Kanto Chemical Co., Ltd.) 91 g, and benzyl three 3.1 g of methyl ammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 200 g of toluene (manufactured by Kanto Chemical Co., Ltd.) were placed in a flask equipped with a thermometer and a stirrer, and stirred at 120°C for 8 hours. After the reaction, the mixture was cooled to room temperature, 200 g of methyl isobutyl ketone (manufactured by Kanto Chemical Co., Ltd.) was added, and the mixture was washed twice with 1000 g of 1% sodium hydroxide aqueous solution and twice with 1000 mL of water. The solvent of the obtained organic phase was distilled off under reduced pressure to obtain 135 g of a yellow transparent viscous ring-opened body (OPP-G-bisphenol A ring-opened body).

100g of OPP-G-bisphenol A ring opener, 406g of epichlorohydrin (manufactured by Wako Pure Chemical Industries, Ltd.), and 8.2g of benzyltrimethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) An-Stark separator, dropping funnel, 1L three-necked round bottom flask with stirrer. Next, while stirring the mixture under a reduced pressure of 50 torr, it was heated to about 50° C., and 66 g of a 48% sodium hydroxide aqueous solution (manufactured by Kanto Chemical Co., Ltd.) was dropped over 3 hours. The epichlorohydrin in the azeotropically distilled water/epichlorohydrin mixture is returned to the reaction system while continuing to stir. After the addition, stirring was continued for 3 hours. Next, the reaction mixture was cooled to room temperature, 250 g of toluene and 250 g of methyl isobutyl ketone were added, and the mixture was washed with 500 mL of water 4 times. The solvent of the obtained organic phase was distilled off under reduced pressure to obtain 113 g of a yellow transparent viscous glycidyl ether body (compound 4a, raw material epoxy resin).

Add 50 g of compound 4a, 7.0 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 21 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 11 mg of BHT (dibutylhydroxytoluene, manufactured by Kanto Chemical Co., Ltd.) as a catalyst. The flask of a thermometer and a stirrer was stirred at 100°C for 8 hours. After the completion of the reaction, a part of the methacrylated epoxy compound (Compound 4) was obtained.

化合物5是藉由以下的方法來獲得。2. Oligo B (1) Compound 5

Compound 5 was obtained by the following method.

(Production of compound 5) 200 g of bisphenol F epoxy resin (EXA-830CRP, manufactured by DIC Corporation), 54 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 328 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) as a catalyst, BHT (dibutyl) 50 mg of hydroxytoluene (manufactured by Kanto Chemical Co., Ltd.) was added to a flask equipped with a thermometer and a stirrer, and stirred at 100°C for 8 hours. After the completion of the reaction, a part of the methacrylated epoxy compound (Compound 5) was obtained.

化合物6是依據WO2014/057871的第92段落所記載的方法來獲得。(2) Compound 6

Compound 6 was obtained according to the method described in paragraph 92 of WO2014/057871.

化合物7是依據日本特開2017-214462號公報的第131段落～第135段落所記載的方法來獲得。3. Oligo C (1) Compound 7

Compound 7 was obtained according to the method described in paragraphs 131 to 135 of JP 2017-214462 A.

光起始劑1是依據WO2012/077720之第58段落所記載的方法來獲得。4. Photoinitiator (1) Photoinitiator 1

Photoinitiator 1 was obtained according to the method described in paragraph 58 of WO2012/077720.

光起始劑2是依據WO2012/077720的第60段落所記載的方法來獲得。(2) Photoinitiator 2

Photoinitiator 2 was obtained according to the method described in paragraph 60 of WO2012/077720.

5. Thermal hardener Polyamine compound (EH-5030S, manufactured by ADEKA, active hydrogen equivalent 105g/eq)

6. Other ingredients (1) Packing ・Organic filler; core-shell particles (ZEFIAC F-351, manufactured by AICA Industry Co., Ltd.) ・Inorganic filler; silica particles (SEAHOSTAR KE-C50, manufactured by Nippon Shokubai Co., Ltd.) ・Inorganic filler; fuming silica (thixotropy imparting agent) (TG-308F, manufactured by Cabot Specialty Chemicals) (2) Coupling agent ・Silane coupling agent; 3-glycidoxypropylmethyl diethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)

(Determination of epoxy equivalent) The epoxy equivalent of the epoxy resin (raw material epoxy resin) before methacrylic acid modification of Compounds 1-7 is measured by JISK7236:2001.

(Aromatic ring amount) The amount of aromatic rings of the epoxy resin before methacrylic acid modification of Compounds 1 to 7 is calculated based on the structural formula of the corresponding raw epoxy resin.

(Adhesion strength) On the dried ITO substrate (403005XG-10SQ1500A, manufactured by GEOMATEC) after washing with pure water, use a pneumatic dispenser to drop a polyimide-based alignment liquid (SUNEVER SE-7492, manufactured by Nissan Chemical Industry Co., Ltd.) (0.4MPa) , 5.0 seconds) After that, use a spin coater to reach 5000 rpm for 10 seconds and then maintain the uniform coating for 20 seconds. After uniform coating, it was pre-baked on a hot plate at 85°C (1 minute) and post-baked in an oven at 230°C (60 minutes) to produce a polyimide alignment film substrate.

The sealant for the liquid crystal dropping method was spot-coated on the ITO substrate sprinkled with 6μm spacers and the substrate (30mm×30mm×0.5mmt) on the substrate (30mm×30mm×0.5mmt) with 6μm spacers, and made The diameter of the sealing compound for liquid crystal dropping methods after bonding is in the range of 1.5 to 2.5 mmφ. Then, the same kind of substrates (23mm×23mm×0.5mmt) were bonded together, and irradiated with ultraviolet rays (irradiation device: UVX-01224S1, manufactured by Ushio Electric Co., Ltd.) ^{with a cumulative amount of light of 3,000mJ/cm 2 to be cured, and heated in an oven at 120°C.} Harden for 1 hour to produce a test piece. Using a universal testing machine (TG-2kN, manufactured by MINEBEA), the test piece was fixed and punched at the position of 15mm×25mm on the substrate at a speed of 5mm/min to measure ITO substrates (ITO/ITO) and polyimide substrates. Bond strength to each other (PI/PI(TN)).

(Moisture permeability) The liquid crystal dropping method is sandwiched by a 100mm×100mm PET film with a thickness of 0.1mm with a sealant to have a diameter of 3.6mm～3.8mm, a thickness of 0.28mm～0.32mm, and irradiate both sides ^{with 100mW/cm 2 ultraviolet light.} Each was irradiated with light energy of 1,500 mJ/cm ² and thermally cured in a hot-air oven at 120° C. for 1 hour to prepare samples for moisture permeability measurement. The moisture permeability measurement is based on JISK0208:1976, using a 65°C/95% constant temperature and humidity bath, and calculating the moisture permeability from the weight change measured by the moisture permeable cup method. The unit of moisture permeability is g/(m ² ･24h).

(Test for leaks in the liquid crystal test tank) On an ITO glass substrate (0.7mm thickness) with an alignment film (SE-5662, manufactured by Nissan Chemical Industry Co., Ltd.), using a seal dispenser, each at 25mm×25mm The frame-shaped pattern dispensing coating liquid crystal dropping method uses sealant. Then, liquid crystal (MLC-6609, manufactured by Merck Co., Ltd.) was dropped on the substrate by the liquid crystal dropping method, the upper and lower substrates were bonded together, and ultraviolet rays were irradiated (UV irradiation device: UVX-01224S1, manufactured by Ushio Electric Co., Ltd.) after 3 minutes. Cumulative light quantity: 3,000mJ/cm ² ), light-cured, and then heat-cured in a hot-air oven at 120°C for 60 minutes to create a test tank. Regarding the produced liquid crystal test cell, the case where there was a leak in the seal was rated as ×, and the case where no leak in the seal was observed was rated as ○.

The results are consolidated in Table 1 and Table 2.

The sealing compound for the liquid crystal dropping method of the example produced a cured product having excellent adhesion to the alignment film and excellent low moisture permeability. In addition, in the sealing compound for the liquid crystal dropping method of the example, in the sealing leak test, no sealing leak was observed, and the liquid crystal sealing was completed. From the comparison of Examples 1 and 2, it can be seen that when the oligomer B has a bisphenol F type structure, it is excellent in low moisture permeability. From the comparison of Examples 1 and 3, it can be seen that when the oligomer A has a bisphenol F type structure, it is excellent in low moisture permeability. From the comparison of Examples 1 and 4, it can be seen that when the content of oligomer A is reduced relative to 100 parts by weight of the total of oligomer A and oligomer B, low moisture permeability is excellent. From the comparison of Examples 4 to 6, it can be seen that when the epoxy equivalent and aromatic ring weight of the raw material epoxy resin of the oligomer A are in a preferable range, the low moisture permeability is excellent. In particular, from the comparison of Examples 5 and 6, it can be seen that when the epoxy equivalent of the raw material epoxy resin of the oligomer A increases, the low moisture permeability is superior.

On the other hand, since the sealing compound for liquid crystal dropping methods of Comparative Example 1 contains only the oligomer A, the cured product obtained using the sealing compound for liquid crystal dropping methods of Comparative Example 1 has high moisture permeability. The sealing compound for liquid crystal dropping method of Comparative Example 2 contains only oligomer B. Therefore, the sealing compound for liquid crystal dropping method of Comparative Example 2 has poor adhesion to the alignment film. Therefore, the sealing compound for liquid crystal dropping method of Comparative Example 2 is used. The resulting cured product has high moisture permeability. The sealing compound for the liquid crystal dropping method of Comparative Example 3 contains two types of oligomer B. In addition, the sealing compound for the liquid crystal dropping method of Comparative Example 3 contains Compound 5 having an "oligomer with an epoxy equivalent of less than 200 g/epo and an aromatic ring content of 0.43 or more" instead of the oligomer A. Therefore, the sealing compound of Comparative Example 3 The sealing compound for the liquid crystal dropping method has poor adhesion to the alignment film, and the cured product obtained by using the sealing compound for the liquid crystal dropping method of Comparative Example 3 has high moisture permeability. The sealing compound for the liquid crystal dropping method of Comparative Example 4 contains compound 7 having an "oligomer with an epoxy equivalent of 200 g/epo or more and an aromatic ring content of less than 0.43" instead of oligomer A. Therefore, the liquid crystal of Comparative Example 4 is used The cured product obtained from the sealant for the drip method has high moisture permeability.

Claims (4)

A sealing compound for liquid crystal dropping method, which is a sealing compound for liquid crystal dropping method containing a curable resin, a photoinitiator, and a thermosetting agent, and The curable resin contains oligomer A and oligomer B, The oligomer A is a compound that modifies the (meth)acrylic resin part of the epoxy resin having an epoxy equivalent of 200 g/epo or more and an aromatic ring weight of 0.43 or more, The oligomer B is a compound selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, and bisphenol A type epoxy resin partially modified by (meth)acrylic acid. One or more of the group consisting of the compound which modified the bisphenol F type epoxy resin part (meth)acrylic acid and the compound which modified the bisphenol AD type epoxy resin part (meth)acrylic acid. The sealing compound for liquid crystal dropping method according to claim 1, wherein the oligomer A has 3 or more benzene rings in one molecule. The sealing compound for liquid crystal dropping methods of claim 1 or 2, wherein the oligomer A has a bisphenol F type structure. The sealing compound for liquid crystal dropping method according to any one of claims 1 to 3, wherein the oligomer B is a compound that partially modifies (meth)acrylic acid of bisphenol F type epoxy resin or bisphenol F type epoxy resin .