Liquid crystal sealant composition

Abstract

To provide a liquid crystal sealant in which the amounts of the ionic impurity and the curable resin are reduced.SOLUTION: The invention relates to a liquid crystal sealant composition including: a curable resin (A) containing at least one selected from the group consisting of (A-1) a combination of an epoxy resin and an acrylic resin, and (A-2) a partially (meth)acrylated epoxy resin derived from a difunctional or higher epoxy resin; (B) a photopolymerization initiator; (C) a thermal curing agent; and (D) an ion scavenger containing Zr, Mg, and Al, and / or an ion scavenger containing Zr and Bi.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a liquid crystal sealing composition. [Background technology]

[0002] In the manufacturing method of liquid crystal display elements, the dropping method is a method that can create a panel by directly dropping liquid crystal into a closed loop of a sealant, vacuum lamination, and releasing the vacuum. This dropping method has many advantages such as reducing the amount of liquid crystal used and shortening the time it takes to inject liquid crystal into the panel, and is currently the mainstream method for manufacturing liquid crystal panels using large substrates. In methods including the dropping method, after applying the sealant and liquid crystal and laminating them, gaps are removed, the position is aligned, and the seal is cured mainly by ultraviolet curing. In addition, the method of manufacturing an electrochemical cell by the vacuum lamination method uses a sealant to seal the electrolyte in the electrochemical cell, and has the advantage of being able to manufacture an electrochemical cell without having to provide an electrolyte injection port.

[0003] In liquid crystal sealants, ion trapping agents are used to reduce water-soluble inorganic ions eluted into the liquid crystal. As such liquid crystal sealants, Patent Document 1 describes a sealant for liquid crystal display elements that contains a curable resin, a thermal radical polymerization initiator, and an ion trapping agent containing antimony and bismuth. Patent Document 2 describes a liquid crystal sealant that contains an aromatic epoxy resin having an alcoholic hydroxyl group, a thermal curing agent, a filler, and an ion trapping agent containing magnesium and aluminum. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2015-127802 A [Patent Document 2] JP 2004-244515 A Summary of the Invention [Problem to be solved by the invention]

[0005] The sealants containing the specific ion scavengers described in Patent Documents 1 and 2 have a problem in that the reduction of ionic impurities and the reduction of unreacted curable resin are insufficient compared to sealants not containing ion scavengers. Therefore, an object of the present invention is to provide a liquid crystal sealant in which the amounts of ionic impurities and unreacted curable resin are further reduced. [Means for solving the problem]

[0006] The present invention relates to the following [1] to [3]. [1] (A) (A-1) a combination of an epoxy resin and an acrylic resin, and (A-2) a curable resin containing one or more selected from the group consisting of a partially (meth)acrylated epoxy resin of a difunctional or higher epoxy resin, (B) a photopolymerization initiator; (C) a heat curing agent; (D) an ion scavenger containing Zr, Mg and Al, and / or an ion scavenger containing Zr and Bi; A liquid crystal sealant composition comprising: [2] The liquid crystal sealant composition according to [1], further comprising one or more selected from the group consisting of a filler (excluding a thixotropic agent), a thixotropic agent, and a coupling agent. [3] The liquid crystal sealant composition according to [1] or [2], wherein the content of component (D) is 1.0 part by mass or more and 20 parts by mass or less per 100 parts by mass of component (A). Effect of the Invention

[0007] The present invention can provide a liquid crystal sealant in which the amounts of ionic impurities and unreacted curable resin are further reduced. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] Preferred embodiments of the present invention will now be described. In this specification, the term "(meth)acryloyl group" refers to at least one of an acryloyl group (CH2=CH2-C(=O)-) and a methacryloyl group (CH2=CH(CH3)-C(=O)-).

[0009] In this specification, "(B) photopolymerization initiator" may also be referred to as "component (B)." The same applies to "(C) heat curing agent" and the like.

[0010] [Liquid crystal sealant composition] The liquid crystal sealant composition includes (A) a curable resin containing one or more selected from the group consisting of partially (meth)acrylated epoxy resins of difunctional or higher epoxy resins and combinations of epoxy resins and acrylic resins, (B) a photopolymerization initiator, (C) a heat curing agent, and (D) an ion scavenger containing Zr, Mg, and Al, and / or an ion scavenger containing Zr and Bi.

[0011] The liquid crystal sealing composition contains an ion scavenger containing a specific element, so that the amount of ionic impurities and the amount of unreacted curable resin can be reduced.

[0012] In this specification, "unreacted curable resin" means a resin in which the epoxy group in the component (A) is unreacted, and preferably means a resin in which both the epoxy group and the (meth)acrylic group in the component (A) are unreacted. And, "the amount of unreacted curable resin is further reduced" means that the amount of unreacted curable resin is reduced compared to a liquid crystal sealing composition that does not contain an ion scavenger.

[0013] In this specification, "ionic impurities" include cations such as sodium ions, potassium ions, and calcium ions, and anions such as halogen ions (fluorine ions, chloride ions, bromine ions, and the like), sulfate ions, and nitrate ions. And, "the amount of ionic impurities is further reduced" means that at least the total amount of sodium ions, potassium ions, chloride ions, and nitrate ions is reduced.

[0014] The liquid crystal sealant composition can reduce the amount of ionic impurities, so that the liquid crystal sealant composition can reduce adverse effects on liquid crystal. In addition, the liquid crystal sealant composition can reduce the amount of unreacted curable resin, so that when the liquid crystal sealant composition is cured, the curing rate of epoxy groups and the like is improved, which is thought to lead to improvements in other properties.

[0015] Since the liquid crystal sealant composition contains both a photopolymerization initiator and a heat curing agent, the liquid crystal sealant composition is a composition that is cured by at least one of light (energy rays) and heat. Therefore, the liquid crystal sealant composition may be a photocurable composition, a heat curable composition, or a photo- and heat-curable composition. The liquid crystal sealant composition is preferably a photo- and heat-curable composition that is cured by both light and heat.

[0016] <(A) (A-1) A curable resin containing at least one selected from the group consisting of a combination of an epoxy resin and an acrylic resin, and (A-2) a partially (meth)acrylated epoxy resin of a difunctional or higher epoxy resin> Component (A) is a curable component of the liquid crystal sealant composition. Component (A) includes component (A-1) and / or component (A-2). Component (A-1) is a combination of an epoxy resin and an acrylic resin. Component (A-2) is a partially (meth)acrylated epoxy resin of a bifunctional or higher epoxy resin. By including component (A-1) and / or component (A-2), component (A) can have properties of both an epoxy resin and a (meth)acrylic resin. Here, the term "unsaturated group" refers to an ethylenically unsaturated group and / or an acetylenically unsaturated group.

[0017] <Epoxy resin> The epoxy resin is a curable resin having an epoxy group. The number of epoxy functionalities of the epoxy resin can be appropriately set according to the desired properties of the liquid crystal sealant composition, but is preferably difunctional or more, and more preferably difunctional to tetrafunctional.

[0018] Examples of epoxy resins having two or more functionalities include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, bisphenol F novolac type epoxy resins, alicyclic epoxy resins, aliphatic chain epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, hydantoin type epoxy resins, isocyanurate type epoxy resins, and phenol novolac type epoxy resins having a triphenolmethane skeleton. In addition, glycidyl ethers of phenols having two or more functionalities, glycidyl ethers of alcohols having two or more functionalities, and halides and hydrogenated products thereof can also be used.

[0019] The epoxy resin may be a single component or a combination of two or more components.

[0020] <(Meth)acrylic resin> The (meth)acrylic resin is a curable resin having a (meth)acryloyl group. The functionality of the (meth)acrylic resin can be appropriately set depending on the desired properties of the liquid crystal sealing composition, but is preferably bifunctional or more, and more preferably bifunctional to tetrafunctional.

[0021] Examples of the di- or higher functional (meth)acrylic resin include an ester of an aliphatic polyhydric alcohol and (meth)acrylic acid, and an ester of an alkylene oxide adduct of an aliphatic polyhydric alcohol and (meth)acrylic acid. Specific examples of bifunctional or higher (meth)acrylic resins include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, dimethylol dicyclopentane di(meth)acrylate, EO-modified 1,6-hexanediol di(meth)acrylate, EO-modified bisphenol A di(meth)acrylate, PO-modified bisphenol A di(meth)acrylate, polyester di(meth)acrylate (e.g., ARONIX M-6100, manufactured by Toa Gosei Co., Ltd.), polyethylene glycol di(meth)acrylate (e.g., 4G, manufactured by Shin-Nakamura Chemical Co., Ltd.), and silicon di(meth)acrylate (e.g., EBECRYL 350, manufactured by Daicel Allnex Corporation), etc. Here, "EO" means ethylene oxide, and "PO" means propylene oxide.

[0022] The tri- or higher functional (meth)acrylic resin may be one or more resins selected from EO-modified glycerol tri(meth)acrylate (trifunctional), PO-modified glycerol tri(meth)acrylate (trifunctional), pentaerythritol tri(meth)acrylate (trifunctional), dipentaerythritol hexa(meth)acrylate (hexafunctional), and pentaerythritol tetra(meth)acrylate (tetrafunctional).

[0023] Further, the (meth)acrylic resin may be a modified resin in which all of the epoxy groups of a difunctional or higher epoxy resin are modified with (meth)acrylic acid and / or acrylic anhydride. Here, the difunctional or higher epoxy resin, including the preferred ones, is as described above.

[0024] The (meth)acrylic resin may be a single component or a combination of two or more components.

[0025] <Partially (meth)acrylated epoxy resins of bifunctional or higher epoxy resins> The partially (meth)acrylated epoxy resin of a bifunctional or higher epoxy resin is a modified resin in which a part of the epoxy groups of a bifunctional or higher epoxy resin is modified with (meth)acrylic acid or (meth)acrylic anhydride. That is, the partially (meth)acrylated epoxy resin of a bifunctional or higher epoxy resin has both an epoxy group and a (meth)acryloyl group in the resin. Here, the bifunctional or higher epoxy resin, including the preferred ones, is as described above.

[0026] The partially (meth)acrylated epoxy resin of a di- or higher functional epoxy resin is preferably a modified resin in which a portion of the epoxy groups of a difunctional epoxy resin is modified with (meth)acrylic acid or (meth)acrylic anhydride.

[0027] The partially (meth)acrylated epoxy resin of di- or higher functional epoxy resin may be one type of component or a combination of two or more types of components.

[0028] <Preferred embodiment of component (A)> Component (A) preferably contains one or more resins selected from the group consisting of resins represented by the following general formulas (1) to (4). Here, each group may be unsubstituted or substituted. For example, in "arylene having 6 to 20 carbon atoms-alkylene having 1 to 4 carbon atoms-arylene group having 6 to 20 carbon atoms", only the alkylene group having 1 to 4 carbon atoms may be substituted, or both of the two arylene groups having 6 to 20 carbon atoms and the alkylene group having 1 to 4 carbon atoms may be substituted.

[0029] [ka] [ka] [ka]

[0030] [During the ceremony, X is -O- or an alkylene group having 1 to 4 carbon atoms; Y's each independently represent 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, an alkylene group having 1 to 4 carbon atoms-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-an alkylene group having 1 to 4 carbon atoms-an arylene group having 6 to 20 carbon atoms, or a group: -R 11 -(OR 11 ) n1 -(In the formula, R 11 is an alkylene group having 1 to 6 carbon atoms, and n1 is 0 or an integer of 1 to 10; R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently a hydrogen atom, a glycidyl group, a methylglycidyl group, or the group: -CHCR 12 (OR 13 )CH2O-Z 1 However, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 At least two of the groups are glycidyl groups, methylglycidyl groups, or the group: -CHCR 12 (OR 13 )CH2O-Z 1 and R 12 is a hydrogen atom or a methyl group, R 13 is a hydrogen atom or a (meth)acryloyl group, Z 1 is a (meth)acryloyl group, R 21are each independently a hydrogen atom or a methyl group.

[0031] [ka]

[0032] [During the ceremony, Y and R 21 is as described above, A 1 is aryl-O- having 6 to 20 carbon atoms, aryl-(OR 14 ) n2 -O-(wherein, R 14 is an alkylene group having 1 to 6 carbon atoms, and n2 is an integer of 1 to 10), or a heteroaryl group having a total of 5 to 30 atoms, R 7 and R 8 are each independently a glycidyl group, a methylglycidyl group, or the group: -CHCR 12 (OR 13 )CH2O-Z 1 and R 12 , R 13 and Z 1 is as described above.

[0033] In the general formulae (1) to (4), each group can be appropriately set according to the number of carbon atoms from the following.

[0034] In this specification, alone or in combination with other terms, an "alkyl group" is a monovalent group that is linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 4. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, and an n-dodecyl group.

[0035] The alkyl group may be unsubstituted or substituted with a substituent. The substituent of the alkyl group is not particularly limited, and examples thereof include an aryl group having 6 to 20 carbon atoms (particularly, a phenyl group) and a halogen atom.

[0036] In this specification, either alone or in combination with other terms, an "alkylene group" is a linear or branched divalent group. The alkylene group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, a propylene group (propane-1,2-diyl group), a propylidene group (propane-1,1-diyl group), an isopropylidene group (propane-2,2-diyl group), a tetramethylene group, a butylidene group (butane-1,1-diyl group), an isobutylidene group (2-methylpropane-1,1-diyl group), a pentamethylene group, a 2-methylpentane-1,5-diyl group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, and a dodecamethylene group.

[0037] The alkylene group may be unsubstituted or substituted with a substituent, such as a halogen atom, an aryl group (particularly a phenyl group), or the like.

[0038] In this specification, either alone or in combination with other terms, an "aryl group" is a monovalent group having a monocyclic or polycyclic aromatic ring. The number of carbon atoms in the aryl group is preferably 6 to 20. Examples of the aryl group include a phenyl group, a biphenylyl group, a naphthyl group, a terphenylyl group, an anthracenyl group, and a fluorenyl group, and the phenyl group and the biphenylyl group are preferable.

[0039] The aryl group may be unsubstituted or substituted with a substituent, such as an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkylmercapto group, a cycloalkyl group, or a halogen atom.

[0040] In this specification, either alone or in combination with other terms, an "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 to 20. Examples of the arylene group include a phenylene group, a naphthylene group, an anthranylene group, and a phenanthranylene group, and the phenylene group is preferable.

[0041] The arylene group may be unsubstituted or substituted with a substituent, such as an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkylmercapto group, a cycloalkyl group, or a halogen atom.

[0042] In this specification, the term "cycloalkyl group", alone or in combination with other terms, refers to a monovalent group having a monocyclic or polycyclic alicyclic group having 3 to 20 carbon atoms. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a cyclododecyl group, and an adamantyl group.

[0043] The cycloalkyl group can be unsubstituted or substituted with a substituent, such as an alkyl group or a halogen atom.

[0044] In this specification, either alone or in combination with other terms, "a cycloalkylene group is a divalent group having a monocyclic or polycyclic alicyclic group having 3 to 20 carbon atoms. Examples of the cycloalkyl group include a cycloalkyl group from which one hydrogen atom has been removed. The cycloalkylene group can be unsubstituted or substituted with a substituent. Examples of the substituent of the cycloalkyl group include an alkyl group, a halogen atom, and the like. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cycloundecylene, and a cyclododecylene group.

[0045] In this specification, either alone or in combination with other terms, the term "heteroaryl group having a total of 5 to 30 atoms" refers to a monocyclic or polycyclic heterocyclic group containing, in addition to carbon atoms, at least one heteroatom selected from the group consisting of oxygen atoms, sulfur atoms, and nitrogen atoms, and is preferably a phthalimidyl group, an imidazolyl group, a xanthenyl group, a thioxanthenyl group, a thienyl group, a dibenzofuryl group, a chromenyl group, an isothiochromenyl group, a phenoxathiinyl group, a pyrrolyl group, a pyrazolyl group, a pyrazinyl group, a pyrimidinyl group, Examples of such an alkyl group include a pyridazinyl group, an indolizinyl group, an isoindolyl group, an indolyl group, an indazolyl group, a purinyl group, a quinolidinyl group, an isoquinolyl group, a quinolyl group, a phthalazinyl group, a naphthyridinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, a pteridinyl group, a carbazolyl group, a β-carbolinyl group, a phenanthridinyl group, an acridinyl group, a perimidinyl group, a phenanthrolinyl group, a phenazinyl group, an isothiazolyl group, a phenothiazinyl group, an isoxazolyl group, and a furazanyl group.

[0046] The heteroaryl group having a total of 5 to 30 atoms may be unsubstituted or substituted with a substituent. Examples of the substituent in the heteroaryl group having a total of 5 to 30 atoms include an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkylmercapto group, a cycloalkyl group, and a halogen atom.

[0047] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogen atom as a substituent is preferably a fluorine atom or a chlorine atom, and more preferably a fluorine atom.

[0048] Examples of the alkyl moiety in the alkoxy group include the above-mentioned alkyl group examples. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an i-butoxy group, a sec-butoxy group, and a tert-butoxy group.

[0049] Examples of the alkyl group in the alkylcarbonyl group and the alkylmercapto group include the above-mentioned alkyl group examples. Examples of the alkylcarbonyl group include an acetyl group, a propanoyl group, a 2-methylpropanoyl group, and a butanoyl group. Examples of the alkylmercapto group include a methylmercapto group, an ethylmercapto group, a propylmercapto group, an i-propylmercapto group, a butylmercapto group, an i-butylmercapto group, a sec-butylmercapto group, and a tert-butylmercapto group.

[0050] Examples of the alkylene group having 1 to 4 carbon atoms and 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 are as described above. As the alkylene group having 1 to 4 carbon atoms-arylene group having 6 to 20 carbon atoms, a methylene-1,4-phenylene group and an ethylene-1,4-phenylene group are preferred. The order of bonding to each group in the alkylene group having 1 to 4 carbon atoms-arylene group having 6 to 20 carbon atoms may be any order, but A 1 The oxygen atom having a group containing the following is preferably bonded to an 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.

[0051] Examples of the alkylene group having 1 to 4 carbon atoms and 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-alkylene group having 1 to 4 carbon atoms are as described above. As the alkylene group having 1 to 4 carbon atoms-arylene group having 6 to 20 carbon atoms-alkylene group having 1 to 4 carbon atoms, a 1,3-phenylenebismethylene group (m-xylylene group) and a 1,4-phenylenebismethylene group (p-xylylene group) are preferred.

[0052] Examples of the alkylene group having 1 to 4 carbon atoms and the arylene group having 6 to 20 carbon atoms in 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 as described above. Examples of 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 include the following groups: [ka] (In the formula, R 31 and R 32 are each independently a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group or a phenyl group, [ka] It is particularly preferred that:

[0053] General formulas (1) to (4) are R 1 ~R 8 can be used for component (A-1) and component (A-2) by selecting as follows:

[0054] General formula (1) and general formula (2) In the general formula (1) and the general formula (2), R 1 , R 2 , R 4 and R 5 is a hydrogen atom, a glycidyl group, or a methylglycidyl group, and R 1 , R 2 , R 4 and R 5 When at least two of the above are glycidyl groups or methylglycidyl groups, the resins represented by general formulas (1) and (2) can be used as the epoxy resin in component (A-1).

[0055] In the general formula (1) and the general formula (2), R 1 , R 2 , R 4 and R 5is a hydrogen atom or a group: -CH2CR 12 (OR 13 )CH2O-Z 1 and R 1 , R 2 , R 4 and R 5 At least two of the groups: -CH2CR 12 (OR 13 )CH2O-Z 1 In this case, the resins represented by general formula (1) and general formula (2) can be used as the (meth)acrylic resin in component (A-1).

[0056] In the general formula (1) and the general formula (2), R 1 , R 2 , R 4 and R 5 At least one of R is a glycidyl group or a methylglycidyl group, 1 , R 2 , R 4 and R 5 At least one of the groups: -CH2CR 12 (OR 13 )CH2O-Z 1 and optionally containing a hydrogen atom, the resins represented by general formula (1) and general formula (2) can be used as the partially (meth)acrylated epoxy resin of the difunctional or higher epoxy resin in component (A-2). 12 (OR 13 )CH2O-Z 1 The ratio of these is preferably 10:90 to 90:10.

[0057] ·General formula (3) In the general formula (3), R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is a hydrogen atom, a glycidyl group, or a methylglycidyl group, and R 1 , R 2 , R 3 , R 4 , R5 and R 6 When at least two of the above are glycidyl groups or methylglycidyl groups, the resin represented by general formula (3) can be used as the epoxy resin in component (A-1).

[0058] In the general formula (3), R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is a hydrogen atom or a group: -CH2CR 12 (OR 13 )CH2O-Z 1 and R 1 , R 2 , R 3 , R 4 , R 5 and R 6 At least two of the groups: -CH2CR 12 (OR 13 )CH2O-Z 1 In this case, the resin represented by general formula (3) can be used as the (meth)acrylic resin in component (A-1).

[0059] In the general formula (3), R 1 , R 2 , R 3 , R 4 , R 5 and R 6 At least one of R is a glycidyl group or a methylglycidyl group, 1 , R 2 , R 3 , R 4 , R 5 and R 6 At least one of the groups: -CH2CR 12 (OR 13 )CH2O-Z 1 and optionally containing a hydrogen atom, the resin represented by general formula (3) can be used as a partially (meth)acrylated epoxy resin of a difunctional or higher epoxy resin in component (A-2). 12 (OR13 )CH2O-Z 1 The ratio of these is preferably 10:90 to 90:10.

[0060] ·General formula (4) In the general formula (4), R 7 and R 8 When is a glycidyl group or a methylglycidyl group, the resin represented by general formula (4) can be used as the epoxy resin in component (A-1).

[0061] In the general formula (4), R 7 and R 8 But the group: -CH2CR 12 (OR 13 )CH2O-Z 1 In this case, the resin represented by general formula (4) can be used as the (meth)acrylic resin in component (A-1).

[0062] In the general formula (4), R 7 and R 8 one of which is a glycidyl group or a methylglycidyl group, and the other is a group: -CHCR 12 (OR 13 )CH2O-Z 1 In this case, the resin represented by the general formula (4) can be used as a partially (meth)acrylated epoxy resin of the difunctional or higher epoxy resin in the component (A-2). 12 (OR 13 )CH2O-Z 1 The ratio of these is preferably 10:90 to 90:10.

[0063] In the general formulas (1) to (4), from the viewpoint of ease of synthesis, R 21 is preferably a hydrogen atom.

[0064] In the general formula (4), A 1is a phenoxy group, a 4-tert-butyl-phenoxy group, a biphenyl-2-yloxy group, a phthalimidyl group, a phenyl-(OCH2CH2) n1a It is preferably a -O- group (wherein n1a represents an integer of 2 to 10), and more preferably a phenoxy group.

[0065] Other examples of component (A) include the resins described in JP-A-2012-077202, JP-A-2022-165527, WO2020 / 230789, and JP-A-2012-077202.

[0066] Other hardening resins The component (A) may contain other curable resins in addition to the component (A-1) and / or the component (A-2).

[0067] When component (A) includes a combination of (A-1) an epoxy resin and an acrylic resin, other curable resins include a resin having an unsaturated group and / or an epoxy group, which is used as a base resin for the liquid crystal sealant composition, and a resin having neither an unsaturated group nor an epoxy group.

[0068] When component (A) contains (A-2) a partially (meth)acrylated epoxy resin of a difunctional or higher epoxy resin, the other curable resin may contain, in addition to the above-mentioned components, an epoxy resin and a (meth)acrylic resin, where the epoxy resin and the (meth)acrylic resin are as described above for component (A-1).

[0069] Examples of resins having an unsaturated group include diene-based polymers (for example, polybutadiene polymers, polyisoprene polymers, etc.).

[0070] Examples of resins having neither an unsaturated group nor an epoxy group include modified epoxy resins in which all of the epoxy groups of an epoxy resin have been modified with a modifying compound having no unsaturated groups, and urethane resins formed from a hydroxyl group-containing compound and an isocyanate group-containing compound.

[0071] Component (A) may be one component or a combination of two or more components. The component (A) is preferably a combination of one or more components selected from the group consisting of curable resins represented by general formulas (1) to (4) as component (A-2) and one or more epoxy resins selected from the group consisting of curable resins represented by general formulas (1) to (4). Incidentally, the component (A) is preferably a curable resin that does not contain silicon atoms.

[0072] <(B) Photopolymerization initiator> (B) Photopolymerization initiator is a component that can make the liquid crystal sealing material composition a photopolymerizable and curable composition. Examples of the photopolymerization initiator include a radical polymerization initiator, an anionic polymerization initiator, and / or a cationic polymerization initiator.

[0073] Examples of the radical polymerization initiator include benzoins, acetophenones, benzophenones, thioxanthones, α-acyloxime esters, phenylglyoxylates, benzyls, azo compounds, diphenyl sulfide compounds, acylphosphine oxide compounds, benzoin ethers, anthraquinones, and organic peroxides. The radical polymerization initiator is preferably one that has low solubility in liquid crystals and has a reactive group that does not gasify the decomposition product when irradiated with light. In addition, the radical polymerization initiator is preferably a polymerization initiator that is a mixture of a compound obtained by reacting a compound having at least two epoxy groups with dimethylaminobenzoic acid and a compound obtained by reacting a compound having at least two epoxy groups with hydroxythioxanthone, as described in WO2012 / 077720.

[0074] Examples of the anionic polymerization initiator include imidazoles, amines, phosphines, organic metal salts, metal chlorides, and organic peroxides.

[0075] Examples of the cationic polymerization initiator include onium salts, iron allene complexes, titanocene complexes, arylsilanol aluminum complexes, Lewis acid compounds, Bronsted acid compounds, benzylsulfonium salts, thiophenium salts, thioranium salts, benzylammonium, pyridinium salts, hydrazinium salts, carboxylate esters, sulfonate esters, amine imides, sulfone compounds, sulfonate esters, sulfonimides, disulfonyldiazomethanes, and amines.

[0076] The photopolymerization initiators are commercially available or can be prepared according to known methods. Component (B) may be one component or a combination of two or more components.

[0077] <(C) Heat curing agent> (C) The heat curing agent is a component that can make the liquid crystal sealant composition a heat curable composition. Examples of the heat curing agent include amine-based heat curing agents. Examples of the amine-based heat curing agent include organic acid dihydrazide compounds, amine adducts (adducts of polyamine compounds and epoxy resins, compounds in which imidazole compounds are adducted to epoxy resins, etc.), imidazole compounds, derivatives of imidazole compounds, dicyandiamide, and other heat curing agents. Here, the polyamine compound is a compound having at least two primary amino groups, and examples thereof include a diamine compound having two primary amino groups and a triamine compound having three primary amino groups.

[0078] Examples of organic acid dihydrazides include VDH (1,3-bis(hydrazinocarboethyl)-5-isopropylhydantoin), ADH (adipic acid dihydrazide), UDH (7,11-octadecadiene-1,18-dicarbohydrazide), and LDH (octadecane-1,18-dicarboxylic acid dihydrazide).

[0079] Commercially available adducts of polyamine compounds and epoxy resins include EH-5001P, EH-4370S, EH-5015S, EH-4375S, EH-5030S, EH-5057P, and EH-4358S (all manufactured by ADEKA CORPORATION), FXR-1020, FXR-1030, and FXR-1081 (all manufactured by T&K TOKA CORPORATION).

[0080] Commercially available products of a compound in which an imidazole compound is adducted with an epoxy resin include EH-5011S (manufactured by ADEKA Corporation) and FXR-1121 (manufactured by T&K TOKA Corporation).

[0081] Other amine adducts include Amicure PN-23, Amicure PN-30, Amicure MY-24, and Amicure MY-H (manufactured by Ajinomoto Fine-Techno Co., Ltd.).

[0082] The other heat curing agent may be a compound having a urea structure in the molecule and having at least one primary amino group. The other heat curing agent may be one described in WO2014 / 010446. The other heat curing agent is preferably a carbazide compound; or a compound obtained by adducting a polyamine compound with at least one compound selected from the group consisting of an epoxy resin, an isocyanate compound, and urea. The other heat curing agent is more preferably a compound represented by the following general formula (5).

[0083] [ka] [During the ceremony, B 1 are each independently a single bond, an alkylene group having 1 to 12 carbon atoms, a group: -R 15 -(OR 15 ) n3 -(In the formula, R 15 is an alkylene group having 1 to 6 carbon atoms, and n3 is an integer of 0 or 1 to 10), a cycloalkylene group having 3 to 20 carbon atoms, an alkylene-C3-C412 a cycloalkylene group, an alkylene having 1 to 12 carbon atoms-a cycloalkylene having 3 to 20 carbon atoms-an alkylene group having 1 to 12 carbon atoms, a cycloalkylene having 3 to 20 carbon atoms-an alkylene having 1 to 12 carbon atoms-a cycloalkylene group having 3 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkylene having 1 to 4 carbon atoms-an arylene group having 6 to 20 carbon atoms, an alkylene having 1 to 4 carbon atoms-an arylene group having 6 to 20 carbon atoms-an alkylene group having 1 to 4 carbon atoms, or an arylene having 6 to 20 carbon atoms-an alkylene having 1 to 4 carbon atoms-an arylene group having 6 to 20 carbon atoms; B 2 is an alkylene group having 1 to 12 carbon atoms, the group: -R 16 -(OR 16 ) n4 -(In the formula, R 16 is an alkylene group having 1 to 6 carbon atoms, and n4 is 0 or an integer of 1 to 10), alkylene-oxycarbonyl-alkylene group having 1 to 12 carbon atoms, cycloalkylene group having 3 to 20 carbon atoms, alkylene-cycloalkylene group having 3 to 20 carbon atoms, alkylene-cycloalkylene group having 3 to 20 carbon atoms-alkylene group having 1 to 12 carbon atoms, carbon a cycloalkylene having 3 to 20 atoms-alkylene having 1 to 12 carbon atoms-cycloalkylene group having 3 to 20 carbon atoms, a dicycloalkanediyl group having 3 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkylene having 1 to 4 carbon atoms-arylene having 6 to 20 carbon atoms-alkylene having 1 to 4 carbon atoms, or an arylene having 6 to 20 carbon atoms-alkylene having 1 to 4 carbon atoms-arylene group having 6 to 20 carbon atoms.

[0084] In the compound represented by the following general formula (5), the alkylene group, cycloalkylene group, and arylene group can be appropriately selected from the above groups depending on the number of carbon atoms. The above groups may be unsubstituted or substituted. The above groups can be used as the substituent.

[0085] In the compound represented by the following general formula (5), examples of the "alkylene-oxycarbonyl-alkylene group having 1 to 12 carbon atoms" include methoxycarbonylmethylene, ethoxycarbonylmethylene, n-propoxycarbonylmethylene, n-butoxycarbonylmethylene, n-pentyloxycarbonylmethylene, n-hexyloxycarbonylmethylene, n-heptyloxycarbonylmethylene, n-octyloxycarbonylmethylene, n-nonyloxycarbonylmethylene, Examples of such carbonylmethylene include straight-chain carbonylmethylene, n-decyloxycarbonylmethylene, n-undecyloxycarbonylmethylene, and n-dodecyloxycarbonylmethylene, and branched-chain carbonylmethylene, such as isopropoxycarbonylmethylene, isobutoxycarbonylmethylene, sec-butoxycarbonylmethylene, t-butoxycarbonylmethylene, 2-methylbutoxycarbonylmethylene, isooctyloxycarbonylmethylene, t-octyloxycarbonylmethylene, and 2-ethylhexyloxycarbonylmethylene.

[0086] The (C) heat curing agent is preferably in a granular form. The average particle size of the (C) heat curing agent is not particularly limited, but is preferably 0.1 to 20.0 μm, and particularly preferably 0.2 to 10.0 μm. The average particle size of the (C) component can be measured by a laser diffraction particle size distribution measuring device. Specifically, the average particle size is the volume average value D 50 (D 50 is the particle size when the cumulative volume is 50%, i.e., the median size). Component (C) having a granular form can be obtained by pulverizing component (C).

[0087] In the compound represented by the general formula (5), B 1 When is a single bond, it is also called a semicarbazide compound. In addition, for the compound represented by general formula (5), WO2014 / 010446, WO2019 / 107070, etc. can be referred to.

[0088] Component (C) may be one type of component or a combination of two or more types of components. Component (C) is preferably a combination of an adduct of a polyamine compound and an epoxy resin, and a compound having a urea structure in the molecule and at least one primary amino group.

[0089] <(D) Ion scavenger containing Zr, Mg and Al, and / or ion scavenger containing Zr and Bi> (D) The ion scavenger containing Zr, Mg and Al, and / or the ion scavenger containing Zr and Bi is a component that can reduce adverse effects on the liquid crystal by capturing water-soluble ions in the liquid crystal sealing material composition.

[0090] The ion trapping agents containing Zr, Mg and Al, and the ion trapping agents containing Zr and Bi function as both ion trapping agents capable of trapping positive ions and negative ions.

[0091] The ion trapping agent containing Zr, Mg and Al may be composed of, for example, a zirconium-based compound, a magnesium-based compound and an aluminum-based compound, and the ion trapping agent containing Zr and Bi may be composed of, for example, a zirconium-based compound and a bismuth-based compound. Examples of the zirconium-based compound include zirconium hydroxide, zirconium phosphate, zirconium molybdate, zirconium tungstate, and hydrates thereof. Examples of the bismuth-based compound include bismuth hydroxide, bismuth nitrate, and hydrates thereof. Examples of the aluminum-based compound include aluminum oxide and its hydrates. The magnesium-based compounds include magnesium oxide and its hydrates.

[0092] The average particle size of component (D) is not particularly limited, but is preferably 0.01 μm to 10 μm, and particularly preferably 0.1 μm to 1.0 μm. The average particle size of component (D) can be measured with a laser diffraction particle size distribution analyzer.

[0093] Examples of the ion scavenger containing Zr, Mg, and Al include IXEPLAS-A1 and IXEPLAS-A2 (both manufactured by Toagosei Co., Ltd.). An example of an ion scavenger containing Zr and Bi is IXEPLAS-B1 (manufactured by Toagosei Co., Ltd.).

[0094] Component (D) may be one component or a combination of two or more components.

[0095] <Other ingredients (E)> The liquid crystal sealant composition may contain other components (E) depending on the purpose, as long as the effects of the present invention are not impaired. Examples of the components (E) include fillers (excluding thixotropy-imparting agents), thixotropy-imparting agents, coupling agents, polymerization inhibitors, solvents, photosensitizers, bulking agents, reinforcing materials, colorants, stabilizers, extenders, viscosity regulators, tackifiers, flame retardants, UV absorbers, antioxidants, discoloration inhibitors, antibacterial agents, antifungal agents, antiaging agents, antistatic agents, plasticizers, lubricants, smoothing agents, foaming agents, and mold release agents. The other components are not the above-mentioned components (A) to (D).

[0096] <Fillers (excluding thixotropic agents)> Fillers (excluding thixotropy-imparting agents) are added for the purpose of controlling the viscosity of the liquid crystal sealant composition, improving the strength of a cured product obtained by curing the liquid crystal sealant composition, or suppressing linear expansion to improve the adhesive reliability of the liquid crystal sealant composition, etc. Examples of fillers (excluding thixotropy-imparting agents) include inorganic fillers and organic fillers.

[0097] Examples of inorganic fillers include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, titania, alumina, zinc oxide, silica (excluding fumed silica), kaolin, talc, glass beads, sericite activated clay, bentonite, aluminum nitride, and silicon nitride. The inorganic filler is preferably silica.

[0098] Examples of the organic filler include acrylic particles, polymethyl methacrylate, polystyrene (polystyrene beads), copolymers obtained by copolymerizing the monomers constituting these (i.e., methyl methacrylate or styrene) with other monomers, polyethylene particles, polysiloxane resin particles, polyamide particles, polyester fine particles, polyurethane fine particles, and rubber fine particles (acrylic rubber particles, isoprene rubber particles). The organic filler may be a core-shell type particle.

[0099] The average particle size of the filler is not particularly limited, but is preferably 0.01 μm to 10 μm, and particularly preferably 1 μm to 5 μm. The average particle size of the filler can be measured by a laser diffraction particle size distribution measuring device.

[0100] The filler may be a commercially available product. Examples of commercially available inorganic fillers include Seahoster KE-C50 (manufactured by Nippon Shokubai Co., Ltd.). Examples of commercially available organic fillers include Zefiac F-351 (manufactured by Aica Kogyo Co., Ltd.).

[0101] The filler may be one component or a combination of two or more components.

[0102] <Thixotropic agent> The thixotropic agent is added for the purpose of imparting thixotropy to the liquid crystal sealing material composition, etc. Examples of the thixotropic agent include powder thixotropic agents and liquid thixotropic agents.

[0103] Examples of the powder thixotropy-imparting agent include inorganic or organic powder thixotropy-imparting agents. The powder thixotropy-imparting agent may be dissolved or dispersed in a solvent. Here, examples of the inorganic powder thixotropy-imparting agent include fumed silica. Examples of the organic powder thixotropy-imparting agent include amide-based (polyhydroxycarboxylic acid amide-based), castor oil-based, polyethylene oxide-based, polyhydroxycarboxylic acid ester-based, and other powder thixotropy-imparting agents.

[0104] Commercially available powder thixotropy-imparting agents can be used. Commercially available fumed silica products include TG-308F (manufactured by Cabot Japan Co., Ltd.) and RY200 (manufactured by Nippon Aerosil Co., Ltd.). Commercially available powder thixotropy-imparting agents other than fumed silica include Disparlon 305, Disparlon 4300, Disparlon 6650, Disparlon 6500, Disparlon 6700, and Disparlon F9050 (manufactured by Kusumoto Chemicals Co., Ltd.).

[0105] Examples of the liquid thixotropic agent include ester-based, amide-based, and polyvalent carboxylic acid-based liquid thixotropic agents.

[0106] The ester-based liquid thixotropic agent may be a phosphate liquid thixotropic agent or a fatty acid ester liquid thixotropic agent. The phosphate ester is preferably a polyether-based phosphate ester. The polyether-based phosphate ester may be a polyoxyethylene alkyl ether phosphate ester, a polyoxyethylene alkyl phenyl ether phosphate ester, or a higher alcohol phosphate ester.

[0107] Commercially available liquid thixotropic agents include Disparlon 3500, Disparlon 3600N, Disparlon 3900EF (manufactured by Kusumoto Chemical Co., Ltd.), RCM-100 (manufactured by Kyoeisha Chemical Co., Ltd.), BYK-R606, BYK-405, BYK-R605, etc. (manufactured by BYK-Chemie Japan KK).

[0108] The thixotropy-imparting agent is preferably a powder thixotropy-imparting agent, more preferably an inorganic powder thixotropy-imparting agent, and particularly preferably fumed silica. In addition, when the liquid crystal sealant composition contains a resin having a (meth)acryloyloxy group (i.e., the (meth)acrylic resin contained in component (A-1) and component (A-2)), the powder thixotropy-imparting agent has high compatibility with the resin having a (meth)acryloyloxy group, and is likely to efficiently exhibit the effect of improving the thixotropy of the liquid crystal sealant composition.

[0109] The thixotropic agent may be one component or a combination of two or more components.

[0110] <Coupling Agent> Examples of the coupling agent include a silane-based coupling agent, a titanate-based coupling agent, etc. The coupling agent is preferably a silane-based coupling agent.

[0111] Examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane.

[0112] Commercially available silane coupling agents include KBM-403, KBE-403, KBE-9007N, KBE-1003, KBE-503, KBE-846, X-12-1308ES, KBE-903, X-12-1056ES, and X-12-1200EP (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0113] Examples of titanate coupling agents include phosphorous acid type titanate coupling agents, alkylbenzenesulfonic acid type titanate coupling agents, pyrophosphoric acid type titanate coupling agents, carboxylic acid type titanate coupling agents, and amine type titanate coupling agents.

[0114] Commercially available titanate coupling agents include PLENACT 46B, PLENACT 55, PLENACT 41B, PLENACT 9SA, PLENACT 38S, PLENACT 138S, PLENACT 238S, PLENACT 338X, PLENACT 44, and PLENACT TTS (all manufactured by Ajinomoto Fine-Techno Co., Ltd.).

[0115] The coupling agent may be one component or a combination of two or more components.

[0116] <Antioxidants> Examples of the antioxidant include phenol-based antioxidants such as 2,6-di-t-butyl-4-cresol, n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate, 2,2'-methylenebis(4-methyl-6-t-butylphenol), and tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane; sulfur-based antioxidants such as dilauryl thiodipropionate, lauryl stearyl thiodipropionate, and pentaerythritol tetrakis(3-lauryl thiopropionate); and phosphorus-based antioxidants such as tris(nonylphenyl)phosphite and tris(2,4-di-t-butylphenyl)phosphite.

[0117] The antioxidant may be one component or a combination of two or more components.

[0118] <Other Ingredients (E)> The component (E) other than the above-mentioned components can be appropriately selected from known components used in liquid crystal sealants. Each of the components (E) may be one component or a combination of two or more components.

[0119] <Content of each ingredient> The content of the component (A) is preferably 45 to 90 parts by mass, particularly preferably 55 to 85 parts by mass, based on 100 parts by mass of the liquid crystal sealing composition. The total content of components (A-1) and (A-2) is preferably 30 to 100 parts by mass, more preferably 40 to 100 parts by mass, and particularly preferably 50 to 100 parts by mass, per 100 parts by mass of component (A). The content of component (B) is preferably from 0.1 to 7 parts by mass, and particularly preferably from 1 to 5 parts by mass, per 100 parts by mass of component (A). The content of component (C) is preferably 5.0 to 50 parts by mass, and particularly preferably 10 to 40 parts by mass, per 100 parts by mass of component (A). The content of component (D) is preferably 1.0 to 20 parts by mass, and may be 5.0 to 20 parts by mass, per 100 parts by mass of component (A). In component (E), the content of the filler (excluding the thixotropic agent) is preferably 5 to 50 parts by mass, and particularly preferably 10 to 40 parts by mass, per 100 parts by mass of component (A). In component (E), the content of the thixotropic agent is preferably from 0.1 to 10 parts by mass, and particularly preferably from 0.2 to 5 parts by mass, per 100 parts by mass of component (A). In component (E), the content of the coupling agent is preferably from 0.1 to 20 parts by mass, and particularly preferably from 0.5 to 5 parts by mass, per 100 parts by mass of component (A). In addition to the above, the total content of component (E) is preferably 2 to 50 parts by mass, and particularly preferably 5 to 40 parts by mass, per 100 parts by mass of component (A).

[0120] <Method for preparing liquid crystal sealant composition> The liquid crystal sealing composition can be produced by mixing the respective components.

[0121] <Curing method> The liquid crystal sealing composition can be cured by irradiation with energy rays such as ultraviolet rays and by application of heat, or by application of heat before, after, or simultaneously with irradiation with energy rays such as ultraviolet rays.

[0122] <Application> The liquid crystal sealant composition can be used to seal (encapsulate) the liquid crystal, which is the object. Specifically, the liquid crystal sealant composition can be used in liquid crystal displays or liquid crystal display elements including module displays, three-dimensional displays, head-mounted displays, projection displays, etc.; light amount adjusting liquid crystal elements such as light control filters, light control shutters, anti-glare mirrors, and spatial light amount modulators; focus variable liquid crystal elements such as liquid crystal lenses; and light modulation liquid crystal elements such as optical deflectors, optical splitters, phase controls, polarization controls, holograms, diffraction gratings, wavelength filters, and frequency filters; and the like.

[0123] Examples of methods for manufacturing a liquid crystal display using a liquid crystal sealant include a process that includes the steps of applying the sealant to one of two transparent substrates with electrodes using a dispenser to form a pattern of the sealant, dropping liquid crystal onto the entire surface within the frame of the transparent substrate and immediately laminating the other transparent substrate, and curing the sealant by irradiating the seal pattern portion with ultraviolet light or the like, heating the sealant, or applying heat before, after, or simultaneously with irradiating the seal pattern portion with ultraviolet light or the like. EXAMPLES

[0124] Next, specific embodiments of the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0125] [Ingredients used] 1.Curing resin (1) Curable resin 1: Partially (meth)acrylated epoxy resin Curable resin 1 was obtained according to the method for producing "compound 1" described in paragraphs 0070 to 0073 of WO2020 / 230789. Curable resin 1 was a compound represented by the following formula: [ka]

[0126] It is a partially methacrylated epoxy resin represented by the formula:

[0127] (2) Curable resin 2: Partially (meth)acrylated epoxy resin

[0128] According to the method described in paragraph 0060 (Comparative Synthesis Example 1) of JP 2022-165527 A, a curable resin 2 was obtained. The curable resin 2 is a partially methacrylated bisphenol A type epoxy resin.

[0129] (3) Curable resin 3: Epoxy resin Curable resin 3 was obtained according to the method for producing "compound 1b" described in paragraphs 0089 to 0090 of JP 2012-077202 A. Curable resin 3 was a compound represented by the following formula: [ka]

[0130] and R 1 , R 2 , R 4 and R 5 Of these, 3.8 are glycidyl groups and the rest are hydrogen atoms, making it an epoxy resin.

[0131] (4) Curable resin 4: Epoxy resin Curable resin 4 was obtained according to the method for producing "compound 2b" described in paragraphs 0092 to 009 of JP 2012-077202 A. Curable resin 4 was a compound represented by the following formula: [ka]

[0132] where Y is a methylene-phenylene group and R 1 , R 2 , R 4 and R 5 Of these, 3.6 are glycidyl groups and the rest are hydrogen atoms, making it an epoxy resin.

[0133] 2-1. Photopolymerization initiator (1) Photopolymerization initiator 1 Diethylene glycol diglycidyl ether (Denacol EX-850L, Nagase Chemtex Corporation) 14.5g (0.1 epoxy equivalent), 4-dimethylaminobenzoic acid 16.5g (1.0 equivalent), benzyltrimethylammonium chloride 3.71g (0.2 equivalent), and MIBK (methyl isobutyl ketone) 50g were placed in a flask and stirred at 110°C for 24 hours. The reaction mixture was cooled to room temperature (25°C, the same applies below), dissolved in 50g of chloroform, and washed six times with 100ml of water. The solvent in the organic phase was distilled off under reduced pressure to obtain 23.3g of photopolymerization initiator 1.

[0134] (2) Photopolymerization initiator 2 Diethylene glycol diglycidyl ether (Denacol EX-850L, Nagase Chemtex Corporation) 14.5g (0.1 epoxy equivalent), 2-hydroxy-9H-thioxanthen-9-one 22.8g (1.0 equivalent), benzyltrimethylammonium chloride 3.71g (0.2 equivalent), and MIBK 50g were placed in a flask and stirred at 110°C for 24 hours. The reaction mixture was cooled to room temperature, dissolved in 50g of chloroform, and washed six times with 100ml of water. The solvent in the organic phase was distilled off under reduced pressure to obtain 27.8g of photopolymerization initiator 2.

[0135] 2-2.Heat curing agent (1) Polyamine compound (EH-5057P, manufactured by ADEKA Corporation) (2) Polyamine compound (EH-5030S, manufactured by ADEKA Corporation)

[0136] (3) Heat curing agent 1: 4,4'-hexamethylenebis(semicarbazide) represented by the following formula [ka] Heat curing agent 1 is a carbazide compound having an average particle size of 2.1 μm, obtained according to the method described in paragraphs 0121 to 0122 (Example 2) of WO2014 / 010446.

[0137] (4) Heat curing agent 2: 1,1'-(hexane-1,6-diyl)bis[3-(2-aminoethyl)urea] represented by the following formula: [ka] Heat curing agent 2 is an amine compound having an average particle size of 2.2 μm, obtained according to the method described in paragraphs 0137 to 0138 (Example 11) of WO2014 / 010446.

[0138] 3-1. Filler (excluding thixotropic agents) (1) Silica filler (Sea Hoster KE-C50, manufactured by Nippon Shokubai Co., Ltd.) (2) Core-shell type acrylic resin filler (Zefiac F-351, manufactured by Aica Kogyo Co., Ltd.)

[0139] 4-1. Thixotropic agents (1) Hydrophobic fumed silica (TG-308F, manufactured by Cabot Japan Co., Ltd.) 4-2. Coupling agents (1) 3-Glycidoxypropyltrimethoxysilane (KBM-403, Shin-Etsu Chemical Co., Ltd.) 4-3. Polymerization inhibitors (1) 2,6-di-t-butyl-4-cresol (BHT, manufactured by Kanto Chemical Co., Ltd.)

[0140] 5-1. Ion trapping agents (1) Zr, Mg, Al-based ion scavenger (IXEPLAS-A1, average particle size 0.5 μm, manufactured by Toagosei Co., Ltd.) (2) Zr, Bi-based ion scavenger (IXEPLAS-B1, average particle size 0.4 μm, manufactured by Toagosei Co., Ltd.) (3) Mg, Al-based ion trap (hydrotalcite, average particle size 0.2 μm, manufactured by Toda Kogyo Co., Ltd.) (4) Sb, Bi-based ion scavenger (IXE-600, average particle size 1.0 μm, manufactured by Toagosei Co., Ltd.)

[0141] [Examples 1 to 7 and Comparative Examples 1 to 5] The components shown in Table 1 were mixed in the amounts (parts by mass) shown in Tables 1 to 3, and then thoroughly kneaded using a three-roll mill (C-4 3 / 4×10, manufactured by Inoue Seisakusho Co., Ltd.) to prepare liquid crystal sealant compositions of the examples and comparative examples.

[0142] The liquid crystal sealing compositions of the examples and comparative examples were evaluated by the following tests.

[0143] (1) Curing rate The sealant composition was sandwiched between a 25 mm × 25 mm, 0.7 mm thick LCD glass on one side and a 25 mm × 25 mm, 0.1 mm thick PET film on the other side so that the thickness of the curable resin composition was 0.5 mm, and the sealant composition was irradiated with an ultraviolet ray irradiation device (UVX-01224S1, manufactured by Ushio Inc.) at 100 mW / cm 2 UV irradiation intensity of 3000mJ / cm 2 After that, the sample was heated in an oven at 120°C for 1 hour to prepare a sample for measurement.

[0144] The curing rate was measured using FT-IR (SpectrumOne, manufactured by PerkinElmer Japan Co., Ltd.), and the reaction rate (conversion rate) of the (meth)acrylic group and the epoxy group was calculated from the peak area of ​​the (meth)acrylic group or the epoxy group in the obtained IR spectrum. -1 (or 945cm -1 ) or the absorption peak area of ​​the epoxy group at 915 cm -1 The decrease in the absorption peak area at 1500 cm of the double bond of the benzene ring -1 The absorption peak area was calculated based on the absorption peak area shown in

[0145] (2) Conductivity, pH, and ion concentration The liquid sealant composition was applied to a 170 mm × 170 mm, 0.1 mm thick PET film, sandwiched between two PET films to a thickness of 50 μm, and irradiated with ultraviolet light at 100 mW / cm using an ultraviolet irradiator (UVX-01224S1, manufactured by Ushio Inc.). 2 UV irradiation intensity of 3000mJ / cm 2The sealant was irradiated with light energy of 10 ...

[0146] (3) Seal pass test The liquid crystal sealant composition was dispensed and applied in a frame-shaped pattern of 25 mm × 25 mm on an ITO glass substrate (thickness: 0.7 mm) with an alignment film (SE-5662, manufactured by Nissan Chemical Industries, Ltd.) using a seal dispenser. Then, liquid crystal (MLC-6609, manufactured by Merck Ltd.) was dropped onto the substrate by the liquid crystal dropping method, and the upper and lower substrates were bonded together. After 3 minutes, ultraviolet light (UV irradiation device: UVX-01224S1, manufactured by Ushio Inc., accumulated light amount: 3,000 mJ / cm) was applied. 2 ) to cure the film, and then heat cure for 60 minutes in a hot air oven at 120°C to prepare a test cell. The liquid crystal test cells thus prepared were rated as × if they had a seal path, and ◯ if they had no seal path.

[0147] The results are shown in Table 1 below.

[0148] [Table 1]

[0149] From Table 1, the sealant composition of the examples was able to reduce the electrical conductivity of the extracted water and the total amount of ions to be detected (particularly the total of sodium ions, potassium ions, chloride ions and nitrate ions). Furthermore, the sealant composition of the examples had a superior epoxy curing rate compared to the corresponding sealant composition of the comparative example that did not contain an ion scavenger. Thus, the liquid crystal sealant composition of the examples can reduce ionic impurities and unreacted components, thereby reducing adverse effects on liquid crystals. Furthermore, the liquid crystal sealant composition of the examples can be used as a liquid crystal sealant, since no seal pass was observed in the seal pass test. Comparison of Examples 1 to 3 showed that when component (D) was an ion scavenger containing Zr and Bi, the epoxy curing rate was superior, and when component (D) was an ion scavenger containing Zr, Mg, and Al, the (meth)acrylic curing rate was superior. Comparing Examples 2, 4 and 5, when the content of component (D) was increased, the epoxy curing rate was better. In addition, comparisons between Example 1 and Comparative Example 1, Example 7 and Comparative Example 5, and Example 4 and Comparative Example 1 showed that, regardless of which cured resin of the Example was used, both the epoxy curing rate and the (meth)acrylic curing rate were excellent by using component (D). Comparing Examples 1 and 2 with Comparative Examples 2 and 3, it was found that the epoxy curing rate was excellent by using the component (D).

[0150] On the other hand, the compositions of Comparative Examples 1 to 5 do not contain component (D). The composition of Comparative Example 2 contains an ion scavenger containing Mg and Al instead of component (D). The composition of Comparative Example 3 contains an ion scavenger containing Sb and Bi instead of component (D). As can be seen from the table, the compositions of Comparative Examples 1 to 5 were inferior in epoxy curing rate. Furthermore, the compositions of Comparative Examples 1 to 5 had higher electrical conductivity and ion concentrations (sodium, potassium, calcium, halogen, sulfuric acid, nitric acid) of the extracted water compared to the corresponding Examples.

Claims

1. (A) a curable resin containing at least one selected from the group consisting of (A-1) a combination of an epoxy resin and an acrylic resin, and (A-2) a partially (meth)acrylated epoxy resin of a difunctional or higher epoxy resin; (B) a photopolymerization initiator; (C) a heat curing agent; (D) an ion trapping agent containing Zr, Mg and Al, and / or an ion trapping agent containing Zr and Bi; A liquid crystal sealant composition comprising:

2. The liquid crystal sealing composition according to claim 1, further comprising at least one selected from the group consisting of a filler (excluding a thixotropic agent), a thixotropic agent, and a coupling agent.

3. The liquid crystal sealant composition according to claim 1 or 2, wherein the content of the component (D) is 1.0 part by mass or more and 20 parts by mass or less based on 100 parts by mass of the component (A).

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