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] This invention relates to a liquid crystal sealant composition. [Background technology]

[0002] In the manufacturing method of liquid crystal display elements, the drop method is a method that allows for the creation of a panel by directly dropping liquid crystal into a closed loop of sealant, vacuum bonding, and then releasing the vacuum. This drop method offers numerous advantages, such as reducing the amount of liquid crystal used and shortening the time required to inject the liquid crystal into the panel, and has become the mainstream method for manufacturing liquid crystal panels using large substrates. In methods including the drop method, the sealant and liquid crystal are applied, bonded, gaps are created, and the sealant is cured mainly by ultraviolet curing. In addition, the method of manufacturing electrochemical cells by bonding under reduced pressure uses a sealant to seal the electrolyte of the electrochemical cell, and has the advantage of being able to manufacture electrochemical cells without providing an electrolyte inlet.

[0003] In liquid crystal sealants, ion scavengers are used to reduce the amount of water-soluble inorganic ions that dissolve into the liquid crystal. Patent Document 1 describes a liquid crystal sealant for liquid crystal display elements containing a curable resin, a thermal radical polymerization initiator, and an ion scavenger containing antimony and bismuth. Patent Document 2 describes a liquid crystal sealant containing an aromatic epoxy resin having alcoholic hydroxyl groups, a thermosetting agent, a filler, and an ion scavenger containing magnesium and aluminum. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2015-127802 [Patent Document 2] Japanese Patent Publication No. 2004-244515 [Overview of the project] [Problems that the invention aims to solve]

[0005] The sealants containing specific ion scavengers described in Patent Documents 1 and 2 had the problem that they were insufficiently able to reduce ionic impurities and unreacted curable resin compared to sealants without ion scavengers. Therefore, the object of the present invention is to provide a liquid crystal sealant in which the amount of ionic impurities and unreacted curable resin is further reduced. [Means for solving the problem]

[0006] The present invention relates to the following [1] to [3]. [1] A curable resin comprising one or more selected from the group consisting of (A)(A-1) combinations of epoxy resin and acrylic resin, and (A-2) partially (meth)acrylic epoxy resins of bifunctional or higher epoxy resins, (B) Photopolymerization initiator, (C) Thermosetting agent and, (D) Ion scavengers containing Zr, Mg and Al, and / or ion scavengers containing Zr and Bi A liquid crystal sealant composition containing the above. [2] The liquid crystal sealant composition according to [1], further comprising one or more selected from the group consisting of fillers (excluding thixotropic agents), thixotropic agents, and coupling agents. [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). [Effects of the Invention]

[0007] The present invention can provide a liquid crystal sealant in which the amount of ionic impurities and unreacted curable resin is further reduced. [Modes for carrying out the invention]

[0008] Preferred embodiments of the present invention will be described below. In this specification, "(meth)acryloyl group" includes 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) Thermosetting agent", etc.

[0010] [Liquid crystal sealant composition] The liquid crystal sealant composition comprises (A) a curable resin selected from the group consisting of a partially (meth)acrylic epoxy resin of a bifunctional or more functional epoxy resin and a combination of epoxy resin and acrylic resin, (B) a photopolymerization initiator, (C) a thermosetting agent, and (D) an ion scavenger containing Zr, Mg and Al, and / or an ion scavenger containing Zr and Bi.

[0011] The liquid crystal sealant composition can reduce ionic impurities and unreacted curable resin by including an ion scavenger containing a specific element.

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

[0013] Furthermore, in this specification, "ionic impurities" include cations such as sodium ions, potassium ions, and calcium ions, as well as anions such as halogen ions (fluoride ions, chloride ions, bromide ions, etc.), sulfate ions, and nitrate ions. And, "the amount of ionic impurities has been further reduced" means that at least the total amount of sodium ions, potassium ions, chloride ions, and nitrate ions has been reduced.

[0014] Because the liquid crystal sealant composition can reduce the amount of ionic impurities, it can minimize adverse effects on the liquid crystal. Furthermore, because the liquid crystal sealant composition can reduce the amount of unreacted curable resin, the curing rate of epoxy groups and other components is improved during the curing process, which is expected to lead to improvements in other properties as well.

[0015] Since a liquid crystal sealant composition contains both a photopolymerization initiator and a thermosetting agent, it is a composition that cures with at least one of light (energy rays) and heat. Therefore, a liquid crystal sealant composition can be a photocurable composition, a thermosetting composition, or a photo- and thermosetting composition. Preferably, the liquid crystal sealant composition is a photo- and thermosetting composition that cures with both light and heat.

[0016] <(A)(A-1) A combination of epoxy resin and acrylic resin, and (A-2) A curable resin comprising one or more selected from the group consisting of bifunctional or more epoxy resins with partial (meth)acrylic properties> Component (A) is a curable component of the liquid crystal sealant composition. Component (A) contains component (A-1) and / or component (A-2). Component (A-1) is a combination of epoxy resin and acrylic resin. Component (A-2) is a partially (meth)acrylic epoxy resin of a bifunctional or more epoxy resin. Because component (A) contains component (A-1) and / or component (A-2), component (A) can possess the properties of both epoxy resin and (meth)acrylic resin. Here, "unsaturated group" means an ethylenically unsaturated group and / or an acetylenely unsaturated group.

[0017] Epoxy resin The epoxy resin is a curable resin having epoxy groups. The number of epoxy functionalities in the epoxy resin can be appropriately set according to the desired properties of the liquid crystal sealant composition, but it is preferably two or more functionalities, and particularly preferably two to four functionalities.

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

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

[0020] (Meth)acrylic resin (Meth)acrylic resin is a curable resin having (meth)acryloyl groups. The number of functionalities of the (meth)acrylic resin can be appropriately set according to the desired properties of the liquid crystal sealant composition, but it is preferably two or more functionalities, and particularly preferably two to four functionalities.

[0021] Examples of (meth)acrylic resins with two or more functionalities include esters of aliphatic polyhydric alcohols and (meth)acrylic acid, and esters of alkylene oxide adducts of aliphatic polyhydric alcohols and (meth)acrylic acid. Specific examples of (meth)acrylic resins with two or more functionalities 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, tricyclodecanedimethanol 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 Toagosei Co., Ltd.), polyethylene glycol di(meth)acrylate (e.g., 4G, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and silicon di(meth)acrylate (e.g., EBECRYL Examples include 350 (manufactured by Daicel Ornex Co., Ltd.). Here, "EO" means ethylene oxide and "PO" means propylene oxide.

[0022] Examples of (meth)acrylic resins with three or more functions include 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] Furthermore, as (meth)acrylic resins, modified resins are obtained in which all of the epoxy groups of a bifunctional or more functional epoxy resin are modified with (meth)acrylic acid and / or acrylic anhydride. Here, the bifunctional or more functional epoxy resins are as described above, including preferred ones.

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

[0025] <Partially (meth)acrylic epoxy resins with bifunctional or higher properties> A partially (meth)acrylic epoxy resin of a bifunctional or more functional epoxy resin is a modified resin obtained by modifying some of the epoxy groups of a bifunctional or more functional epoxy resin with (meth)acrylic acid or (meth)acrylic anhydride. That is, a partially (meth)acrylic epoxy resin of a bifunctional or more functional epoxy resin has both epoxy groups and (meth)acryloyl groups in the resin. Here, the bifunctional or more functional epoxy resin is as described above, including preferred ones.

[0026] Partially (meth)acrylicated epoxy resins of bifunctional or more epoxy resins are preferably modified resins in which a portion of the epoxy groups of a bifunctional epoxy resin are modified with (meth)acrylic acid or (meth)acrylic anhydride.

[0027] Partially (meth)acrylic epoxy resins of bifunctional or more functional epoxy resins may consist of one component or a combination of two or more components.

[0028] ≪Desired form 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 with 6 to 20 carbon atoms - alkylene with 1 to 4 carbon atoms - arylene group with 6 to 20 carbon atoms", only the alkylene group with 1 to 4 carbon atoms may be substituted, or all of the two arylene groups with 6 to 20 carbon atoms and the alkylene group with 1 to 4 carbon atoms may be substituted.

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

[0030] [wherein, X is -O- or an alkylene group having 1 to 4 carbon atoms, Y is, independently of each other, an arylene group having 6 to 20 carbon atoms, an alkylene-arylene group having 1 to 4 carbon atoms and 6 to 20 carbon atoms, an alkylene-arylene-alkylene group having 1 to 4 carbon atoms, 6 to 20 carbon atoms and 1 to 4 carbon atoms, an arylene-alkylene-arylene group having 6 to 20 carbon atoms and 1 to 4 carbon atoms, or the group: -R 5 , 21 , 13 , 1 , 12 , , 6 , 4 , 1 , 12 , 13 -(O-R 11 ) n1 -(wherein, R 11 ​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​Each of these is independently either a hydrogen atom or a methyl group.

[0031] [ka]

[0032] [During the ceremony, Y and R 21 As stated above, A 1 These are aryl-O- with 6 to 20 carbon atoms, and aryl-(OR) with 6 to 20 carbon atoms. 14 ) n2 -O-(wherein, R 14 (where n2 is an alkylene group with 1 to 6 carbon atoms, and n2 is an integer from 1 to 10), or a heteroaryl group with a total of 5 to 30 atoms. R 7 and R 8 Each of these is independently a glycidyl group, a methylglycidyl group, or a group:-CH2CR 12 (OR 13 )CH2O-Z 1 And R 12 , R 13 and Z 1 This is as stated above.

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

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

[0035] Alkyl groups can be unsubstituted or substituted with substituents. The substituents on the alkyl group are not particularly limited and include aryl groups (especially phenyl groups) having 6 to 20 carbon atoms, halogen atoms, and the like.

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

[0037] Alkylene groups can be unsubstituted or substituted with substituents. Examples of substituents on alkylene groups include halogen atoms and aryl groups (particularly phenyl groups).

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

[0039] The aryl group may be unsubstituted or substituted with substituents. Examples of substituents on the aryl group include alkyl groups, alkoxy groups, alkylcarbonyl groups, alkylmercapto groups, cycloalkyl groups, and halogen atoms.

[0040] In this specification, "arylene group," either alone or in combination with other terms, is a divalent group having a monocyclic or polycyclic aromatic ring. The number of carbon atoms in the arylene group is preferably 6 to 20. Examples of arylene groups include phenylene group, naphthylene group, anthranylene group, phenanthrane group, etc., with phenylene group being preferred.

[0041] The arylene group may be unsubstituted or substituted with substituents. Examples of substituents on the arylene group include alkyl groups, alkoxy groups, alkylcarbonyl groups, alkylmercapto groups, cycloalkyl groups, halogen atoms, and the like.

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

[0043] Cycloalkyl groups can be unsubstituted or substituted with substituents. Examples of substituents on cycloalkyl groups include alkyl groups and halogen atoms.

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

[0045] In this specification, either alone or in combination with other terms, "heteroaryl group having a total of 5 to 30 atoms" is a monocyclic or polycyclic heterocyclic group containing, in addition to carbon atoms, one or more heteroatoms selected from the group consisting of at least oxygen atoms, sulfur atoms, and nitrogen atoms, including phthalimidyl group, imidazolyl group, xanthenyl group, thioxanthenyl group, thienyl group, dibenzofuryl group, clomenyl group, isothioclomenyl group, phenoxathiinyl group, pyrrolyl group, pyrazolyl group, pyrazinyl group, pyrimidinyl group, Examples include pyridadinyl group, indolidinyl group, isoindolyl group, indolyl group, indazolyl group, prinyl group, quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthylidinyl group, quinoxalinyl group, quinazolinyl group, synnolinyl group, pteridinyl group, carbazolyl group, β-carbolinyl group, phenantridinyl group, acridinyl group, perimidinyl group, phenanthrolinyl group, phenadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, and fluzanyl group.

[0046] Heteroaryl groups with a total of 5 to 30 atoms can be unsubstituted or substituted with substituents. Examples of substituents for heteroaryl groups with a total of 5 to 30 atoms include alkyl groups, alkoxy groups, alkylcarbonyl groups, alkylmercapto groups, cycloalkyl groups, halogen atoms, and the like.

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

[0048] Examples of alkyl groups in alkoxy groups include the alkyl groups mentioned above. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, i-butoxy, sec-butoxy, and tert-butoxy groups.

[0049] Examples of alkyl groups in alkylcarbonyl groups and alkylmercapto groups include the examples of alkyl groups mentioned above. Examples of alkylcarbonyl groups include acetyl group, propanoyl group, 2-methylpropanoyl group, and butanoyl group. Examples of alkylmercapto groups include methyl mercapto group, ethyl mercapto group, propyl mercapto group, i-propyl mercapto group, butyl mercapto group, i-butyl mercapto group, sec-butyl mercapto group, and tert-butyl mercapto group.

[0050] Examples of the alkylene group with 1 to 4 carbon atoms and the arylene group with 6 to 20 carbon atoms in the alkylene-arylene group with 1 to 4 carbon atoms are as described above. Methylene-1,4-phenylene and ethylene-1,4-phenylene are preferred as the alkylene-arylene group with 1 to 4 carbon atoms and the arylene group with 6 to 20 carbon atoms. The order of bonding to each group in the alkylene-arylene group with 1 to 4 carbon atoms and the arylene group with 6 to 20 carbon atoms may be any order, but A 1 Preferably, the oxygen atom to which the group containing the group is bonded is bonded to an arylene group having 6 to 20 carbon atoms, in the case of an alkylene group having 1 to 4 carbon atoms and an 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-arylene-arylene-alkylene group having 6 to 20 carbon atoms are as described above. Preferred examples of the alkylene group having 1 to 4 carbon atoms are the 1,3-phenylenebismethylene group (m-xylylene group) and the 1,4-phenylenebismethylene group (p-xylylene group).

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

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

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

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

[0056] In the general formula (1) and the general formula (2), at least one of R 1 、R 2 、R 4 and R 5 is a glycidyl group or a methyl glycidyl group, and at least one of R 1 、R 2 、R 4 and R 5 is the group: -CH2CR 12 (OR 13 )CH2O-Z 1 and optionally contains a hydrogen atom, in this case, the resins represented by the general formula (1) and the general formula (2) can be used as the partially (meth)acrylated epoxy resin of the bifunctional or higher-functional epoxy resin in the component (A-2). Here, the ratio of the glycidyl group and the methyl glycidyl group to the group: -CH2CR 12 (OR 13 )CH2O-Z 1 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 are a hydrogen atom, a glycidyl group or a methyl glycidyl group, and R 1 、R 2 、R 3 、R 4 、R5 and R 6 When at least two of them are glycidyl groups or methyl glycidyl groups, the resin represented by the general formula (3) can be used as the epoxy resin in the component (A-1).

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

[0059] In the general formula (3), R 1 , R 2 , R 3 , R<0000​​​​​​​​​​​​​​​​​​​​​​​​​13 )CH2O-Z 1 The ratio is preferably 10:90 to 90:10.

[0060] ·General formula (4) In general formula (4), R 7 and R 8 However, if it 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 general formula (4), R 7 and R 8 However, base:-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 general formula (4), R 7 and R 8 One of them is a glycidyl group or a methylglycidyl group, and the other is a group: -CH2CR 12 (OR 13 )CH2O-Z 1 In this case, the resin represented by general formula (4) can be used as a partially (meth)acrylic epoxy resin of a bifunctional or more epoxy resin in component (A-2). Here, a glycidyl group and a methylglycidyl group, and a group: -CH2CR 12 (OR 13 )CH2O-Z 1 The ratio is preferably 10:90 to 90:10.

[0063] In general formulas (1) to (4), R 21 It is preferable that it be a hydrogen atom.

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

[0065] In addition, as component (A), examples include the resins described in Japanese Patent Publication No. 2012-077202, Japanese Patent Publication No. 2022-165527, WO2020 / 230789, and Japanese Patent Publication No. 2012-077202.

[0066] <<Other curable resins>> Component (A) may contain other curable resins in addition to component (A-1) and / or component (A-2).

[0067] If component (A) includes a combination of (A-1) epoxy resin and acrylic resin, other curable resins include resins having unsaturated groups and / or epoxy groups, and resins having neither unsaturated groups nor epoxy groups, which are used as the main component of liquid crystal sealant compositions.

[0068] Furthermore, if component (A) contains (A-2) a partially (meth)acrylic epoxy resin of a bifunctional or more functional epoxy resin, the other curable resins may include epoxy resin and (meth)acrylic resin in addition to the components mentioned above. Here, the epoxy resin and (meth)acrylic resin are as described above in component (A-1).

[0069] Examples of resins containing unsaturated groups include diene polymers (e.g., polybutadiene polymer, polyisoprene polymer, etc.).

[0070] Examples of resins that do not contain either unsaturated groups or epoxy groups include modified epoxy resins in which all of the epoxy groups of an epoxy resin are modified with a modified compound that does not contain 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. Component (A) is preferably a combination of one or more curable resins represented by general formulas (1) to (4), which are component (A-2), and one or more curable resins represented by general formulas (1) to (4), which are epoxy resins. Furthermore, component (A) is preferably a curable resin that does not contain silicon atoms.

[0072] <(B) Photopolymerization initiator> (B) Photopolymerization initiators are components that can make the liquid crystal sealant composition a photopolymerizable and curable composition. Examples of photopolymerization initiators include radical polymerization initiators, anionic polymerization initiators, and / or cationic polymerization initiators.

[0073] Examples of radical polymerization initiators include benzoins, acetophenones, thioxanthones, α-acyloxime esters, phenylglyoxylates, benzyls, azo compounds, diphenyl sulfide compounds, acylphosphine oxide compounds, benzoin ethers, anthraquinones, and organic peroxides. Radical polymerization initiators are preferably those with low solubility in liquid crystals and reactive groups that do not produce gaseous decomposition products upon light irradiation. Furthermore, a polymerization initiator that is a mixture of a compound obtained by reacting a compound having at least two epoxy groups with dimethylaminobenzoic acid, as described in WO2012 / 077720, and a compound obtained by reacting a compound having at least two epoxy groups with hydroxythioxanthone is preferred as a radical polymerization initiator.

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

[0075] Examples of cationic polymerization initiators include onium salts, iron allene complexes, titanocene complexes, arylsilanolaluminum complexes, Lewis acid compounds, Brønsted acid compounds, benzylsulfonium salts, thiophenium salts, thiolanium salts, benzylammonium, pyridinium salts, hydrazinium salts, carboxylic acid esters, sulfonic acid esters, amineimides, sulfone compounds, sulfonic acid esters, sulfonimides, disulfonyldiazomethanes, and amines.

[0076] 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) Thermosetting agent> (C) The thermosetting agent is a component that can make the liquid crystal sealant composition a thermosetting composition. Examples of thermosetting agents include amine-based thermosetting agents. Examples of amine-based thermosetting agents include organic acid dihydrazide compounds, amine adducts (adducts of polyhydric amine compounds and epoxy resins, compounds obtained by adducting imidazole compounds to epoxy resins, etc.), imidazole compounds, derivatives of imidazole compounds, dicyandiamides, and other thermosetting agents. Here, the polyhydric amine compound is a compound having at least two primary amino groups, and examples include diamine compounds having two primary amino groups and triamine compounds having three primary amino groups.

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

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

[0080] Commercially available compounds in which imidazole compounds are adducted to 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] Other thermosetting agents include compounds having a urea structure in the molecule and having at least one primary amino group. Other thermosetting agents include those described in WO2014 / 010446. Preferably, other thermosetting agents are carbazide compounds; and compounds obtained by adducting a polyhydric amine compound to at least one compound selected from the group consisting of epoxy resins, isocyanate compounds, and urea. More preferably, other thermosetting agents are compounds represented by the following general formula (5).

[0083] [ka] [During the ceremony, B 1 These are, independently of each other, single bonds, alkylene groups with 1 to 12 carbon atoms, group: -R 15 -(OR 15 ) n3 -(In the formula, R 15 (where n3 is an alkylene group with 1 to 6 carbon atoms, and n3 is an integer from 0 to 10), a cycloalkylene group with 3 to 20 carbon atoms, or an alkylene-C3-C3 group with 1 to 12 carbon atoms.12 A cycloalkylene group, an alkylene with 1 to 12 carbon atoms - a cycloalkylene with 3 to 20 carbon atoms - an alkylene group with 1 to 12 carbon atoms, a cycloalkylene with 3 to 20 carbon atoms - an alkylene with 1 to 12 carbon atoms - a cycloalkylene group with 3 to 20 carbon atoms, an arylene group with 6 to 20 carbon atoms, an alkylene with 1 to 4 carbon atoms - an arylene group with 6 to 20 carbon atoms - an alkylene group with 1 to 4 carbon atoms, or an arylene with 6 to 20 carbon atoms - an alkylene with 1 to 4 carbon atoms - an arylene group with 6 to 20 carbon atoms, B 2 This refers to an alkylene group with 1 to 12 carbon atoms, group: -R 16 -(OR 16 ) n4 -(In the formula, R 16 (where n4 is an alkylene group having 1 to 6 carbon atoms, and n4 is an integer from 0 to 10), alkylene-oxycarbonyl-alkylene group having 1 to 12 carbon atoms, cycloalkylene group having 3 to 20 carbon atoms, alkylene-cycloalkylene group having 1 to 12 carbon atoms, alkylene-cycloalkylene group having 3 to 20 carbon atoms, alkylene group having 1 to 12 carbon atoms, cycloalkylene group having 1 to 12 carbon atoms, carbon [These are cycloalkylene groups with 3 to 20 atoms, alkylene groups with 1 to 12 carbon atoms, cycloalkylene groups with 3 to 20 carbon atoms, cycloalkanediyl groups with 3 to 20 carbon atoms, arylene groups with 6 to 20 carbon atoms, alkylene groups with 1 to 4 carbon atoms, arylene groups with 6 to 20 carbon atoms, or arylene groups with 6 to 20 carbon atoms, alkylene groups with 1 to 4 carbon atoms, and arylene groups with 6 to 20 carbon atoms.]

[0084] In the compound represented by the general formula (5) below, the alkylene group, cycloalkylene group, and arylene group can be appropriately selected from the aforementioned groups according to the number of carbon atoms. Furthermore, the aforementioned groups may be unsubstituted or substituted. Examples of substituents include the aforementioned groups.

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

[0086] (C) The thermosetting agent is preferably in granular form. (C) The average particle size of the thermosetting agent is not particularly limited, but is preferably 0.1 to 20.0 μm, and particularly preferably 0.2 to 10.0 μm. (C) The average particle size of component can be measured with a laser diffraction particle size distribution analyzer. Specifically, the average particle size is the volume average value D in particle size distribution measurement by laser diffraction and scattering method. 50 (D 50 This value is measured as the particle diameter (i.e., median diameter) when the cumulative volume reaches 50%. Component (C), which has a granular morphology, can be obtained by grinding component (C).

[0087] In a compound represented by general formula (5), B 1 However, when it is a single bond, it is also called a semicarbazide compound. For other compounds represented by general formula (5), refer to WO2014 / 010446, WO2019 / 107070, etc.

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

[0089] <(D) Ion scavengers containing Zr, Mg, and Al, and / or ion scavengers containing Zr and Bi> (D) Ion scavengers containing Zr, Mg, and Al, and / or ion scavengers containing Zr and Bi, are components that can reduce adverse effects on liquid crystals by capturing water-soluble ions in liquid crystal sealant compositions.

[0090] Ion scavengers containing Zr, Mg, and Al, and ion scavengers containing Zr and Bi, function as dual ion scavengers capable of capturing both cations and anions.

[0091] The ion scavenger containing Zr, Mg, and Al may be composed of, for example, zirconium-based compounds, magnesium-based compounds, and aluminum-based compounds. Furthermore, the ion scavenger containing Zr and Bi may be composed of, for example, zirconium-based compounds and bismuth-based compounds. Examples of zirconium-based compounds include zirconium hydroxide, zirconium phosphate, zirconium molybdate, zirconium tungstate, and their hydrates. Examples of bismuth-based compounds include bismuth hydroxide, bismuth nitrate, and their hydrates. Examples of aluminum-based compounds include aluminum oxide and its hydrate. Examples of magnesium-based compounds include magnesium oxide and its hydrate.

[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 using a laser diffraction particle size distribution analyzer.

[0093] Examples of ion scavengers containing Zr, Mg, and Al include IXEPLAS-A1 and IXEPLAS-A2 (both manufactured by Toagosei Co., Ltd.). Examples of ion scavengers containing Zr and Bi include 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) as long as they do not impair the effects of the present invention, depending on the purpose. Examples of components (E) include fillers (excluding thixotropic agents), thixotropic agents, coupling agents, polymerization inhibitors, solvents, photosensitizers, fillers, reinforcing agents, colorants, stabilizers, bulking agents, viscosity modifiers, tackifiers, flame retardants, ultraviolet absorbers, antioxidants, discoloration inhibitors, antibacterial agents, antifungal agents, anti-aging agents, antistatic agents, plasticizers, lubricants, smoothing agents, foaming agents, and release agents. Note that the other components are not components (A) to (D) described above.

[0096] ≪Fillers (excluding thixotropic agents)≫ Fillers (excluding thixotropes) are added for purposes such as controlling the viscosity of the liquid crystal sealant composition, improving the strength of the cured product obtained by curing the liquid crystal sealant composition, or improving the adhesive reliability of the liquid crystal sealant composition by suppressing linear expansion. Examples of fillers (excluding thixotropes) 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. Silica is preferred as the inorganic filler.

[0098] Examples of organic fillers include acrylic particles, polymethyl methacrylate, polystyrene (polystyrene beads), copolymers obtained by copolymerizing the monomers constituting these (i.e., methyl methacrylate or styrene) with other monomers, polyethylene particles, polysiloxane resin particles, polyamide particles, polyester fine particles, polyurethane fine particles, and rubber fine particles (acrylic rubber particles, isoprene rubber particles). The organic filler may also 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 using a laser diffraction particle size distribution analyzer.

[0100] Commercially available fillers can be used. Examples of commercially available inorganic fillers include Seahostar KE-C50 (manufactured by Nippon Shokubai Co., Ltd.). Examples of commercially available organic fillers include Zephyrac F-351 (manufactured by Aica Kogyo Co., Ltd.).

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

[0102] ≪Thixotropic agents≫ Thixotropic agents are added to liquid crystal sealant compositions for purposes such as imparting thixotropy. Examples of thixotropic agents include powdered thixotropic agents and liquid thixotropic agents.

[0103] Powdered thixotropic agents include inorganic and organic powdered thixotropic agents. The powdered thixotropic agent may be dissolved or dispersed in a solvent. Examples of inorganic powdered thixotropic agents include fumed silica. Examples of organic powdered thixotropic agents include amide-based (polyhydroxycarboxylic acid amide-based), castor oil-based, oxidized polyethylene-based, and polyhydroxycarboxylic acid ester-based powdered thixotropic agents.

[0104] Commercially available powdered thixotropic agents can be used. Examples of commercially available fumed silica include TG-308F (manufactured by Cabot Japan Co., Ltd.) and RY200 (manufactured by Nippon Aerosil Co., Ltd.). Examples of commercially available powdered thixotropic agents other than fumed silica include Disparon 305, Disparon 4300, Disparon 6650, Disparon 6500, Disparon 6700, and Disparon F9050 (manufactured by Kusumoto Kasei Co., Ltd.).

[0105] Examples of liquid thixotropic agents include ester-based, amide-based, and polycarboxylic acid-based liquid thixotropic agents.

[0106] Examples of ester-based liquid thixotropic agents include liquid thixotropic agents of phosphate esters or liquid thixotropic agents of fatty acid esters. Polyether-based phosphate esters are preferred as the phosphate ester. Examples of polyether-based phosphate esters include esters of polyoxyethylene alkyl ether phosphate, esters of polyoxyethylene alkylphenyl ether phosphate, or esters of higher alcohol phosphates.

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

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

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

[0110] Coupling agents Examples of coupling agents include silane-based coupling agents and titanate-based coupling agents. A silane-based coupling agent is preferred.

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

[0112] Examples of 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 phosphite-type titanate coupling agents, alkylbenzene sulfonic acid-type titanate coupling agents, pyrophosphate-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 consist of one component or a combination of two or more components.

[0116] Antioxidants Examples of antioxidants include phenolic 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 dilaurylthiodipropionate, laurylstearylthiodipropionate, and pentaerythritoltetrakis(3-laurylthiopropionate); and phosphorus-based antioxidants such as tris(nonylphenyl)phosphite and tris(2,4-di-t-butylphenyl)phosphite.

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

[0118] ≪Other ingredients (E)≫ Other components (E) can be appropriately selected from known components used in liquid crystal sealants. Each component (E) may be a single component or a combination of two or more components.

[0119] <Content of each ingredient> The content of component (A) is preferably 45 to 90 parts by mass, and particularly preferably 55 to 85 parts by mass, per 100 parts by mass of the liquid crystal sealant composition. The total content of component (A-1) and component (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, based on 100 parts by mass of component (A). The content of component (B) is preferably 0.1 to 7 parts by mass, and particularly preferably 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 fillers (excluding thixotropic agents) 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 0.1 to 10 parts by mass, and particularly preferably 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 0.1 to 20 parts by mass, and particularly preferably 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 a liquid crystal sealant composition> Liquid crystal sealant compositions can be manufactured by mixing the various components.

[0121] <Curing method> The liquid crystal sealant composition can be cured by applying heat through irradiation with energy rays such as ultraviolet light, or by applying heat before, after, or simultaneously with irradiation with energy rays such as ultraviolet light.

[0122] <Application> Liquid crystal sealant compositions can be used to seal (encapsulate) liquid crystal objects. Specifically, liquid crystal sealant compositions can be used in liquid crystal displays or liquid crystal display elements, including modular displays, three-dimensional displays, head-mounted displays, projection displays, etc.; light intensity adjustment liquid crystal elements such as dimming filters, dimming shutters, anti-glare mirrors, and spatial light intensity modulators; variable focus liquid crystal elements such as liquid crystal lenses; and optical modulation liquid crystal elements such as optical deflectors, optical demultiplexers, phase control, polarization control, holograms, diffraction gratings, wavelength filters, and frequency filters.

[0123] A method for manufacturing a liquid crystal display using a liquid crystal sealant includes the steps of: applying the sealant to one of two transparent substrates with electrodes using a dispenser to form a sealant pattern; dropping liquid crystal onto the entire surface within the frame of the transparent substrate and immediately bonding the other transparent substrate to it; and curing the sealant by irradiating the sealant pattern with light such as ultraviolet light, heating the sealant, or applying heat to the sealant pattern before, after, or simultaneously with irradiation with energy rays such as ultraviolet light. [Examples]

[0124] The specific embodiments of the present invention will now 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)acrylic epoxy resin A 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 is given by the following formula: [ka]

[0126] It is a partially methacrylated epoxy resin, as shown by [the formula].

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

[0128] A curable resin 2 was obtained according to the method described in paragraph 0060 (Comparative Synthesis Example 1) of Japanese Patent Publication No. 2022-165527. The curable resin 2 is a partially methacrylated bisphenol A type epoxy resin.

[0129] (3) Curable resin 3: Epoxy resin A curable resin 3 was obtained according to the method for producing "compound 1b" described in paragraphs 0089 to 0090 of Japanese Patent Application Publication No. 2012-077202. The curable resin 3 is given by the following formula: [ka]

[0130] As shown in R 1 , R 2 , R 4 and R 5 Of these, 3.8 are glycidyl groups, and the rest are hydrogen atoms; this is an epoxy resin.

[0131] (4) Curable resin 4: Epoxy resin A curable resin 4 was obtained according to the method for producing "compound 2b" described in paragraphs 0092 to 009 of Japanese Patent Application Publication No. 2012-077202. The curable resin 4 is given by the following formula: [ka]

[0132] This is shown, 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; this is an epoxy resin.

[0133] 2-1. Photopolymerization Initiators (1) Photopolymerization initiator 1 14.5 g (0.1 epoxy equivalent) of diethylene glycol diglycidyl ether (Denacol EX-850L, manufactured by Nagase ChemteX Corporation), 16.5 g (1.0 equivalent) of 4-dimethylaminobenzoic acid, 3.71 g (0.2 equivalent) of benzyltrimethylammonium chloride, and 50 g of MIBK (methyl isobutyl ketone) 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 50 g of chloroform, and washed six times with 100 ml of water. The solvent of the organic phase was removed by vacuum distillation to obtain 23.3 g of photopolymerization initiator 1.

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

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

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

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

[0138] 3-1. Fillers (excluding thixotropic agents) (1) Silica filler (Seahostar KE-C50, manufactured by Nippon Shokubai Co., Ltd.) (2) Core-shell type acrylic resin filler (Zephyr 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, manufactured by 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 scavenger (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 scavenger (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 1-7 and Comparative Examples 1-5] 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 the liquid crystal sealant compositions of the examples and comparative examples.

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

[0143] (1) Curing rate The sealant composition is sandwiched between two pieces of LCD glass (25mm x 25mm, 0.7mm thick) and a PET film (25mm x 25mm, 0.1mm thick) so that the thickness of the curable resin composition is 0.5mm. The mixture is then exposed to ultraviolet light at 100mW / cm² using a UVX-01224S1 (manufactured by Ushio Inc.). 2 UV irradiation intensity of 3000 mJ / cm 2 The samples were irradiated with light energy and then heated in an oven at 120°C for 1 hour to prepare them for measurement.

[0144] The curing rate was measured using FT-IR (SpectrumOne, PerkinElmer Japan Co., Ltd.), and the reaction rate (conversion rate) of the (meth)acrylic group and epoxy group was calculated from the peak area of ​​the (meth)acrylic group or epoxy group in the obtained IR spectrum. The reaction rate was calculated using the 1630 cm⁻¹ peak area of ​​the (meth)acrylic group. -1 (or 945cm) -1 A decrease in the absorption peak area, or absorption of epoxy groups, is observed at 915 cm². -1 The decrease in absorption peak area that appears is due to the double bond of the benzene ring at 1500 cm². -1 The calculation was based on the absorption peak area that appears.

[0145] (2) Conductivity, pH, and ion concentration The sealant composition liquid was applied to a 170mm x 170mm 0.1mm thick PET film, sandwiched between two PET films to a thickness of 50μm, and exposed to ultraviolet light at 100mW / cm² using a UVX-01224S1 (manufactured by Ushio Inc.). 2 UV irradiation intensity of 3000 mJ / cm 2The sealant was cured by irradiating it with light energy and then heating it in an oven at 120°C for 1 hour. The cured sealant was then crushed using an electric mill, and 0.5 g was placed in a Teflon® cup. 50 ml of pure water was added to the Teflon® cup, which was then sealed and left at PCT 121°C for 20 hours. After cooling to room temperature, the ionic conductivity of the extracted water in the cup was measured using a conductivity meter (manufactured by Toa DKK Co., Ltd.), the pH was measured using a pH meter (manufactured by Toa DKK Co., Ltd.), and the ion concentration was measured using ion chromatography (manufactured by Thermo Fisher Scientific Co., Ltd.). In the table, "na" indicates that the value is below the detection limit.

[0146] (3) Seal Pass Test On an ITO glass substrate (0.7 mm thick) with an alignment film (SE-5662, manufactured by Nissan Chemical Industries, Ltd.), a liquid crystal sealant composition was dispensed using a seal dispenser into 25 mm x 25 mm frame-shaped patterns. Then, liquid crystal (MLC-6609, manufactured by Merck KGaA) was dropped onto the substrate using a liquid crystal drop method to bond the upper and lower substrates together. After 3 minutes, ultraviolet light (UV irradiation device: UVX-01224S1, manufactured by Ushio Inc., integrated light intensity: 3,000 mJ / cm²) was applied. 2 Test cells were fabricated by photocuring with irradiator, followed by heat curing in a 120°C hot air oven for 60 minutes. For the fabricated liquid crystal test cells, those with a seal path were marked with ×, and those without a seal path were marked with ○.

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

[0148] [Table 1]

[0149] Table 1 shows that the sealant compositions of the examples were able to reduce the conductivity of the extracted water and the total amount of ions to be detected (especially the total of sodium ions, potassium ions, chloride ions, and nitrate ions). Furthermore, the sealant compositions of the examples had a superior epoxy curing rate compared to the corresponding comparative sealant compositions that did not contain ion scavenging agents. Therefore, the liquid crystal sealant compositions of the examples can reduce ionic impurities and unreacted components, thereby minimizing adverse effects on the liquid crystal. In addition, since no seal pass was observed in the seal pass test, the liquid crystal sealant compositions of the examples can be used as liquid crystal sealants. A comparison of Examples 1-3 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. A comparison of Examples 2, 4-5 showed that the epoxy curing rate was better when the content of component (D) increased. Furthermore, 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 curing resin was used in the examples, the use of component (D) resulted in superior epoxy curing rates and (meth)acrylic curing rates. A comparison of Examples 1-2 and Comparative Examples 2-3 showed that using component (D) resulted in superior epoxy curing rates.

[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 shown in the table, the compositions of Comparative Examples 1 to 5 had inferior epoxy curing rates. In addition, the compositions of Comparative Examples 1 to 5 had higher 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-2) A curable resin comprising a partially (meth)acrylic epoxy resin and an epoxy resin, and optionally further comprising a (meth)acrylic resin, (B) Photopolymerization initiator, (C) Thermosetting agent and (D) Ion scavengers containing Zr, Mg and Al, and / or ion scavengers containing Zr and Bi Includes, A liquid crystal sealant composition in which 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).

2. Furthermore, the liquid crystal sealant composition according to claim 1 further comprises one or more selected from the group consisting of fillers (excluding thixotropic agents), thixotropic agents, and coupling agents.

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