Liquid crystal sealant composition and liquid crystal element

Abstract

To provide a liquid crystal seal agent composition that retains liquid crystal resistance while exhibiting improved cleaning properties, and a liquid crystal element including the seal agent composition.SOLUTION: A liquid crystal seal agent composition contains a curable resin (A), a photopolymerization initiator (B), a thermosetting agent (C), and a wet dispersant with an acid value and / or an amine value (D).SELECTED DRAWING: Figure 1

Description

[Technical field]

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

[0002] A liquid crystal dropping method is known as one of the methods for manufacturing liquid crystal panels. In the liquid crystal dropping method, for example, a sealant is applied to a substrate to form a frame, liquid crystal is dropped into the frame, and the opposing substrate is bonded together, and then the sealant is cured to manufacture a liquid crystal panel.

[0003] For example, Patent Document 1 discloses a specific sealant for the liquid crystal dropping method, which has excellent adhesiveness and moisture resistance reliability and contains a curable resin, fillers with different particle sizes, a heat curing agent, and a radical polymerization initiator.

[0004] On the other hand, the sealant is usually applied using an applicator. If the applicator is used with residual sealant attached, problems such as nozzle clogging and broken seal may occur, so after using the applicator, it is necessary to clean the components to which the sealant may adhere (especially the syringe, nozzle, etc.).

[0005] Patent Document 2 discloses a drop sealant composition that contains (A) an epoxy compound and (B) a curing agent obtained by reacting an amine compound with an isocyanate compound, as a sealant resin composition that does not reduce curability, has good liquid stability, and makes it difficult for the sealant remaining in an apparatus to become viscous.

[0006] Furthermore, Patent Document 3 discloses a curable composition that suppresses alignment disorder of liquid crystals and has excellent cleanability, the curable composition containing a curable compound, a photoinitiator, a heat curing agent, and a polymerization inhibitor, in which the heat curing agent is an adduct of an amine compound having a urea structure. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2013-015769 A [Patent Document 2] JP 2013-095795 A [Patent Document 3] JP 2019-182931 A Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a liquid crystal sealant composition having excellent cleanability while maintaining resistance to liquid crystals, and a liquid crystal element using the sealant composition.

[0009] The liquid crystal sealant composition according to the present invention contains a curable resin (A), a photopolymerization initiator (B), a heat curing agent (C), and a wetting and dispersing agent (D) having an acid value and / or an amine value.

[0010] In one embodiment of the liquid crystal sealing material composition, the wetting and dispersing agent (D) has an acid value of 20 to 150 mgKOH / g.

[0011] In one embodiment of the liquid crystal sealing material composition, the wetting dispersant (D) has an amine value of 20 to 100 mgKOH / g.

[0012] In one embodiment of the liquid crystal sealing composition, the wetting dispersant (D) has a weight average molecular weight of 2,000 or more.

[0013] In one embodiment of the liquid crystal sealing composition, the curable resin (A) has heat curing properties and photocuring properties.

[0014] In one embodiment of the liquid crystal sealant composition, the curable resin (A) contains one or more selected from a partially esterified epoxy resin (A1) and a combination of an epoxy resin and an acrylic resin (A2).

[0015] In one embodiment of the liquid crystal sealing composition, the heat curing agent (C) includes an amine-based curing agent.

[0016] In one embodiment of the liquid crystal sealing composition, the heat curing agent (C) contains a powder.

[0017] One embodiment of the liquid crystal sealing composition further contains a filler (E).

[0018] In one embodiment of the liquid crystal sealant composition, the content of the wetting dispersant (D) is 0.1 to 10 mass % based on the total amount of the liquid crystal sealant composition.

[0019] In one embodiment of the liquid crystal sealant composition, the content of the solvent is 5 mass % or less based on the total amount of the liquid crystal sealant composition.

[0020] The liquid crystal element according to the present invention comprises a cured product of the liquid crystal sealant composition. Effect of the Invention

[0021] According to the present invention, it is possible to provide a liquid crystal sealant composition having excellent cleanability while maintaining resistance to liquid crystals, and a liquid crystal element using the sealant composition. [Brief description of the drawings]

[0022] [Figure 1] FIG. 2 is a plan view illustrating an example of a liquid crystal element. [Diagram 2] 1A to 1C are schematic process diagrams showing an example of a method for manufacturing a liquid crystal element. [Figure 3A] 1 is a photograph for explaining a method for evaluating cleaning performance. [Figure 3B] FIG. 2 is a schematic diagram for explaining a method for evaluating cleaning performance. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] The curable composition and laminate according to the present invention will be described in detail below. In the present invention, (meth)acrylic means at least one of acrylic and methacrylic, and (meth)acrylic acid, (meth)acrylate, etc. are equivalent to this. Furthermore, unless otherwise specified, the symbol "~" indicating a numerical range includes the lower limit and the upper limit.

[0024] [Liquid crystal sealant composition] The liquid crystal sealant composition of the present embodiment (hereinafter also referred to as the present sealant composition) contains a curable resin (A), a photopolymerization initiator (B), a heat curing agent (C), and a wetting dispersant (D) having an acid value and / or an amine value. The liquid crystal sealant composition contains a wetting dispersant (D) having an acid value and / or an amine value, and while maintaining liquid crystal resistance, the solubility or dispersibility of each component in the sealant composition in an organic solvent is improved during cleaning, and adhesion to each member in a coating device is suppressed, thereby improving cleanability.

[0025] The liquid crystal sealant composition of the present invention contains at least a curable resin (A), a photopolymerization initiator (B), a heat curing agent (C), and a wetting and dispersing agent (D), and may further contain other components within the scope of the effect of the present invention. Each component that may be contained in the liquid crystal sealant composition of the present invention will be described below.

[0026] <Curable resin (A)> In this embodiment, the curable resin (A) refers to a resin having at least one of thermosetting and photocuring properties, and examples thereof include a thermosetting resin, a photocuring resin, and a resin having both thermosetting and photocuring properties (hereinafter also referred to as a thermo-photocuring resin). The curable resin (A) may be one component alone or a combination of two or more components. In this embodiment, the curable resin (A) is preferably thermosetting and photocuring. Examples of the curable resin (A) having thermosetting and photocuring properties include the above-mentioned thermo-photocuring resin and a combination of the above-mentioned thermosetting resin and the above-mentioned photocuring resin. In order to reduce the amount of solvent used in the present sealant composition, it is preferable that at least one component of the curable resin (A) is liquid at 25°C.

[0027] The thermosetting resin may be a compound having one or more, preferably two or more, thermosetting groups in one molecule. The thermosetting group may be an epoxy group, an oxetanyl group, an isocyanate group, etc., and an epoxy group is preferred. The epoxy group may have an oxirane ring structure, and may be, for example, a glycidyl group, a methylglycidyl group, an epoxycyclohexyl group, etc. The thermosetting resin is preferably an epoxy resin. Specific examples of the epoxy resin 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, glycidyl amine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, and phenol novolac type epoxy resin having a triphenolmethane skeleton. In addition, as the epoxy resin, diglycidyl etherified products of bifunctional phenols, diglycidyl etherified products of bifunctional alcohols, and their halides and hydrogenated products can also be used. In addition, as the epoxy resin, various polyfunctional epoxy resins can also be used, such as trifunctional and tetrafunctional epoxy resins. In addition, the epoxy resins described in JP-A-2012-077202 can also be used suitably.

[0028] The photocurable resin may be a compound having one or more photocurable groups in one molecule. Examples of the photocurable resin include groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, or a (meth)acryloyl group, and among these, an acrylic resin having a (meth)acryloyl group is preferred. Specific examples of photocurable resins include styrene, vinyl acetate, maleic anhydride, succinic anhydride, and acrylic resins having one or more groups selected from methacrylic groups and acrylic groups in one molecule, with acrylic resins being preferred. Specific examples of the acrylic resin include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, tert-butyl (meth)acrylate, benzyl (meth)acrylate, hydroxyl group-containing (meth)acrylate, alicyclic (meth)acrylate, and polyfunctional (meth)acrylate having two or more groups selected from methacryl groups and acrylic groups in one molecule.

[0029] Examples of the hydroxy group-containing (meth)acrylate include hydroxyalkyl (meth)acrylates (e.g., 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, etc.), polyol (meth)acrylates (glycerin mono(meth)acrylate, trimethylolpropane mono(meth)acrylate, ditrimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, etc.), alkylene oxide-added polyol (meth)acrylates (e.g., alkylene oxide-added trimethylolpropane di(meth)acrylate, alkylene oxide-added pentaerythritol tri(meth)acrylate, alkylene oxide-added dipentaerythritol penta(meth)acrylate, etc.).

[0030] Examples of the alicyclic (meth)acrylates that can be used include monocyclic (meth)acrylates such as cyclopropyl (meth)acrylate, cyclopentyl (meth)acrylate, and cyclohexyl (meth)acrylate; bicyclic (meth)acrylates such as isobornyl (meth)acrylate and norbornyl (meth)acrylate; and tricyclic (meth)acrylates such as dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and adamantyl (meth)acrylate.

[0031] Examples of the polyfunctional (meth)acrylate include bifunctional (meth)acrylates such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, stearic acid modified pentaerythritol di(meth)acrylate, propylene glycol di(meth)acrylate, glycerol di(meth)acrylate, and triethylene glycol di(meth)acrylate; Examples of the polyfunctional (meth)acrylate include trifunctional or higher polyfunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexa(meth)acrylate, and dipentaerythritol penta(meth)acrylate.

[0032] In the present sealant composition, the combination of the thermosetting resin and the photocurable resin is preferably the combination (A2) of the epoxy resin and the acrylic resin. When the thermosetting resin and the photocurable resin are used in combination, the mixing ratio is not particularly limited, but from the viewpoint of sealing property and liquid crystal resistance, the mass ratio of the thermosetting resin to the photocurable resin is preferably 1:9 to 9:1, and more preferably 2:8 to 8:2.

[0033] The thermosetting resin may be a compound having one or more thermosetting groups and one or more photocurable groups in one molecule. Specific examples of the thermosetting group and the photocurable group are as described above. The thermosetting resin is preferably a compound having one or more epoxy groups and one or more ethylenically unsaturated bonds in one molecule. As the thermosetting resin, for example, a compound represented by the following general formula (1) is preferable in addition to glycidyl (meth)acrylate.

[0034] [ka] In general formula (1), R1 and R 2 each independently represents an alkylene group which may have an ether bond between the carbon-carbon bond, R 11 is a glycidyl group or a methylglycidyl group, R 12 is a group containing a (meth)acryloyl group, Q 1 is a linking group having a valence of m1+m2, m1 is an integer from 1 to 3; m2 is an integer from 1 to 3; R 1 , R 2 , R 11 or R 12 If there are multiple R 1 , R 2 , R 11 or R 12 may be the same or different.

[0035] R 1 and R 2 Examples of the alkylene group include a linear alkylene group having 1 to 6 carbon atoms, a (poly)oxyalkylene group (-(OR 3 ) m3 -; but R 3 is a linear alkylene group having 1 to 6 carbon atoms, and m3 is an integer of 1 to 12. Examples of the (poly)oxyalkylene group include (poly)ethylene oxide and (poly)propylene oxide.

[0036] R 12 From the viewpoint of ease of synthesis, it is preferable that the compound has a hydroxyl group, and more preferable that the compound has a structure represented by the following chemical formula.

[0037] [ka] In the formula, * stands for R 2 It is a combination with.

[0038] Above Q 1is a divalent to hexavalent linking group that links an epoxy group and a (meth)acryloyl group. From the viewpoints of sealing property and resistance to liquid crystals, Q 1 Q preferably has an aryl group, and more preferably has a phenyl group. 1 Specific examples of Q include the structures shown in the following chemical formulas. In the following chemical formulas, * represents a bond to O in each general formula (1), and one ring may have two or more bonds. 1 When is a divalent linking group, it may be a linear alkylene group having 1 to 6 carbon atoms.

[0039] [ka]

[0040] m1 may be an integer of 1 to 3, preferably 1 or 2, and more preferably 1. m2 may be an integer of 1 to 3, preferably 1 or 2, and more preferably 1. Furthermore, m1+m2 is preferably 2 to 4, more preferably 2 to 3, and further preferably 2.

[0041] Among the thermosetting resins, from the viewpoints of sealing properties and liquid crystal resistance, a partially esterified epoxy resin (A1) obtained by subjecting one of the epoxy groups of a compound having two epoxy groups to an esterification reaction with (meth)acrylic acid is preferred.

[0042] The compound having two epoxy groups is preferably a diglycidyl ether, such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, bisphenol diglycidyl ether, biphenol diglycidyl ether, or benzenediol diglycidyl ether.

[0043] The partially esterified epoxy resin (A1) can be synthesized by referring to the synthesis method described in, for example, WO 2012-77720.

[0044] <Photopolymerization initiator (B)> The photopolymerization initiator (B) can be appropriately selected from those that promote the reaction of the photocurable group of the curable resin (A) by irradiation with light, and includes a photoinitiator compound and a photosensitizer compound. Here, the photoinitiator compound refers to a compound that absorbs light such as ultraviolet light or visible light, or receives the energy absorbed by the photosensitizer compound to generate radicals, and the photosensitizer compound refers to a compound that absorbs light and provides the energy obtained to the photoinitiator compound, etc. The photosensitizer compound may be, for example, a visible light sensitizer compound that absorbs light having a wavelength of 380 nm or more.

[0045] The photoinitiating compound may be a self-cleavage type or a hydrogen abstraction type (electron donating type). From the viewpoint of suppressing the generation of outgassing, it is preferable to use a hydrogen abstraction type photoinitiating compound. As the hydrogen abstraction type photoinitiator compound, a compound having a benzoyl group [C6H5-C(=O)-] is preferable in terms of reactivity. The benzoyl group may further have a substituent on the aromatic ring. The substituent is not particularly limited, and examples thereof include an alkyl group, an aryl group, an amino group, a carboxy group, a hydroxyl group, a carboxyalkyl group, an oxyalkyl group, and combinations thereof. Examples of such photoinitiating compounds include benzophenones, acetophenones, benzoin ethers, anthraquinones, and the like, which are known as photoinitiators. As the photoinitiating compound, preferred are benzophenone, 4-chlorobenzophenone, 4-methylbenzophenone, o-benzoylbenzoic acid, 4-hydroxybenzophenone, 4-phenylbenzophenone, acetophenone, alkoxyacetophenone, hydroxyacetophenone, and the like, as well as compounds having a dialkylaminobenzoyl group represented by the general formula (2) described below.

[0046] The photosensitizing compound is preferably a compound having a photosensitizing moiety such as xanthone, thioxanthone, anthraquinone, coumarin, etc. as a substituent, and from the standpoint of reactivity, thioxanthones having thioxanthone are preferred. Specific examples of thioxanthones include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, and the like, as well as a compound represented by the general formula (2) described below and having a 9-oxo-9H-thioxanthenyl group.

[0047] In the present embodiment, as the photopolymerization initiator (B), it is preferable to use a compound having an alkylene oxide, and it is more preferable to use a compound represented by the following general formula (2). In the case where the substituent in the general formula (2) has a 9-oxo-9H-thioxanthenyl group, the photoinitiator acts as the photosensitizing compound. In the case where the substituent in the general formula (2) has a dialkylaminobenzoyl group, the photoinitiator acts as the photoinitiating compound.

[0048] [ka] In general formula (2), Q 2 represents an alkylene group which may have a substituent and which may have an oxygen atom in the carbon chain; R 21 , R 22 , R 23 , and R 24 each independently represents a 9-oxo-9H-thioxanthenyl group, a dialkylaminobenzoyl group, a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an aralkyl group, an acyl group, a silyl group, an acetal group, or -CO-NH-Z 1 and Z 1 is an alkyl group, an aryl group, or a heteroaryl group; R 21 , R 22 , R 23 , and R 24 , and Q 2At least one of the substituents contained in is a 9-oxo-9H-thioxanthen-yl group or a dialkylaminobenzoyl group.

[0049] Q 2 The alkylene group in the formula (I) is a linear or branched alkylene group having 1 to 20 carbon atoms, preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and examples thereof include linear alkylene groups such as methylene, ethylene, propylene, and butylene groups; and branched alkylene groups such as methylethylene, methylpropylene, methylhexylene, and ethylbutylene groups. The alkylene group may have a hydrogen atom substituted therein. Substituents for the hydrogen atom may include halogen atoms, hydroxyl groups, 9-oxo-9H-thioxanthenyl groups, and dialkylaminobenzoyl groups. Also, Q 2 The alkylene group in may have an oxygen atom in the carbon chain, and may be an oxyalkylene group or an alkylene oxide group. 2 is [-Q 3 -(OQ 3 ) p In the substituent, p is an integer of 1 to 50, preferably 2 to 42, and more preferably 4 to 24. In the substituent, Q 3 is preferably an alkylene group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. 3 Q may further have a substituent. 3 Examples of the substituent in the above formula include an alkyl group having 1 to 4 carbon atoms and a group represented by the following general formula (2a) or (2b).

[0050] [ka] In the general formulas (2a) and (2b), R 25 , R 26 , R 27 , and R 28each independently represents a 9-oxo-9H-thioxanthenyl group, a dialkylaminobenzoyl group, a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an aralkyl group, an acyl group, a silyl group, an acetal group, or -CO-NH-Z 1 and Z 1 is an alkyl group, an aryl group, or a heteroaryl group.

[0051] R 21 ~R 28 The alkyl group is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an isopropyl group, a t-butyl group, etc. The alkyl group may have a halogen atom or a hydroxyl group as a substituent.

[0052] R 21 ~R 28 The aryl group in the above may be a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms, such as a phenyl group, a naphthyl group, an anthracenyl group, or a biphenyl group. The aryl group may have, as a substituent, an amino group, an alkylamino group, a cyano group, an alkoxy group, an alkyl group, an acyl group, a nitro group, an alkoxycarbonyl group, or a silyl group. The alkyl chain of the alkyl group, alkoxy group, acyl group, and alkoxycarbonyl group as the substituent may be any of the R 21 ~R 28 The alkyl group may be the same as that of the alkyl group described above.

[0053] R 21 ~R 28The heteroaryl group is a monocyclic or polycyclic heterocycle having 5 to 20 atoms containing one or more heteroatoms selected from an oxygen atom, a sulfur atom, and a nitrogen atom, and examples thereof include 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, a pyridazinyl group, an indolizinyl group, an isoindolyl group, an in ... Examples of the heteroaryl group include a doryl 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. The heteroaryl group may have the same substituent as the aryl group.

[0054] R 21 ~R 28 The aralkyl group has a structure in which an aryl group is substituted on an alkyl group, and the alkyl group and the aryl group can be the same as the alkyl group and the aryl group described above. Specific examples of the alkyl group include a benzyl group and a phenylethyl group.

[0055] R 21 ~R 28 The acyl group of Z 2 -C(=O)-(where Z 2 Z is an alkyl group, an aryl group, or a heteroaryl group. 2 The alkyl group, aryl group, and heteroaryl group in R 21 ~R 28 Specific examples of the acyl group include an acetyl group, a propionyl group, and a benzoyl group.

[0056] R 21 ~R 28 The silyl group is -Si(Z 3 )3(where Z3 are each independently an alkyl group, an alkoxy group, an aryl group, or a heteroaryl group. 3 The alkyl group, alkoxy group, aryl group, and heteroaryl group in R 21 ~R 28 Specific examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, a monomethyldimethoxysilyl group, a diethylmonoethoxysilyl group, and a monomethyldiethoxysilyl group.

[0057] R 21 ~R 28 The acetal group of -C(Z 4 )(Z 5 )(OZ 6 )(where Z 4 and Z 5 are each independently a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group; Z 6 Z is an alkyl group, an aryl group, or a heteroaryl group. 4 ~Z 6 The alkyl, aryl and heteroaryl groups of R 21 ~R 28 Specific examples of the acetal group include -CH2OCH3, -CH(CH3)OCH3, -CH(CH3)OC2H5, and the like.

[0058] R 21 ~R 28 The substituent -CO-NH-Z 1 (In the formula, Z 1 is an alkyl group, an aryl group, or a heteroaryl group; 1 The alkyl, aryl or heteroaryl group of R 21 ~R 28 Specific examples of the substituent include a phenylaminocarbonyl group, a methylaminocarbonyl group, and an ethylaminocarbonyl group.

[0059] R 21 ~R28 The dialkylaminobenzoyl group is a benzoyl group substituted with a dialkylamino group. The two alkyl groups in the dialkylamino group can each independently be the same alkyl group as the alkyl group. Specific examples of the dialkylaminobenzoyl group include 2-dialkylaminobenzoyl, 3-dialkylaminobenzoyl, and 4-dialkylaminobenzoyl groups as dialkylaminobenzoyl groups. Examples of the dialkylaminobenzoyl group include dimethylaminobenzoyl, diethylaminobenzoyl, dipropylaminobenzoyl, dibutylaminobenzoyl, dihexylaminobenzoyl, dioctylaminobenzoyl, methylethylaminobenzoyl, methylpropylaminobenzoyl, methylbutylaminobenzoyl, methylhexylaminobenzoyl, ethylpropylaminobenzoyl, ethylbutylaminobenzoyl, ethylhexylaminobenzoyl, butyloctylaminobenzoyl, and hexyloctylaminobenzoyl groups. From the viewpoint of photocurability, the dimethylaminobenzoyl group is preferred, and the 4-dimethylaminobenzoyl group is more preferred.

[0060] Also, R 21 ~R 28 Specific examples of the 9-oxo-9H-thioxanthene-yl group include, as the 9-oxo-9H-thioxanthene-yl group, a 9-oxo-9H-thioxanthene-1-yl group, a 9-oxo-9H-thioxanthene-2-yl group, a 9-oxo-9H-thioxanthene-3-yl group, and a 9-oxo-9H-thioxanthene-4-yl group.

[0061] The compound represented by the general formula (2) has one or more dialkylaminobenzoyl groups or 9-oxo-9H-thioxanthenyl groups in the molecule. When the compound has two or more in the molecule, the compound may have both a dialkylaminobenzoyl group and a 9-oxo-9H-thioxanthenyl group, but it is preferable to have only one of them.

[0062] Among the compounds represented by the general formula (2), R 21and R 23 are identical and are a 9-oxo-9H-thioxanthenyl group or a dialkylaminobenzoyl group, R 22 and R 24 each independently represents a 9-oxo-9H-thioxanthenyl group, a dialkylaminobenzoyl group, a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an aralkyl group, an acyl group, a silyl group, an acetal group, or -CO-NH-Z 1 And Q 2 But -Q 3 -(OQ 3 ) p It is particularly preferred that

[0063] The method for producing the compound represented by general formula (2) is not particularly limited, but the compound can be produced by referring to, for example, JP-A-2014-227344.

[0064] The photopolymerization initiator (B) may be used alone or in combination of two or more. In particular, in the present embodiment, it is preferable to use the above-mentioned photoinitiator compound in combination with the above-mentioned photosensitizer compound in terms of curability and the like.

[0065] When a photoinitiator compound and a visible light sensitizing compound are used in combination as the photopolymerization initiator (B), the molar ratio (photoinitiator compound / visible light sensitizing compound) is preferably 1 / 5 to 5 / 1, more preferably 1 / 3 to 3 / 1, and even more preferably 1 / 2 to 2 / 1, from the viewpoint of supplying stable and sufficient radicals.

[0066] In the present sealant composition, the content of the photopolymerization initiator (B) is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the curable resin (A) from the viewpoints of sealing properties, liquid crystal resistance, and the like.

[0067] <Thermal hardener (C)> The thermosetting agent (C) can be appropriately selected according to the thermosetting group of the curable resin (A). For example, when the curable resin (A) has an epoxy group, the curing agent may be an amine compound, an imidazole compound, an acid anhydride compound, an organic phosphinic acid compound, a phenolic compound, a hydrazide compound, a carbazide compound; a compound obtained by adducting an imidazole to an epoxy resin; a compound obtained by adducting a polyamine compound to at least one compound selected from the group consisting of an epoxy resin, an isocyanate compound, and an urea; a mixed crystal of two or more hydrazide compounds; a mixed crystal of one or more polyamine compounds and one or more hydrazide compounds, a mixed crystal of one or more imidazole compounds and one or more hydrazide compounds, a mixed product of a carboxylic acid compound and an amine compound, etc.

[0068] Examples of the amine compounds include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines. Examples of the aliphatic amines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, and dodecamethylenediamine. Examples of polyetheramines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis(propylamine), polyoxypropylene diamine, and polyoxypropylene triamines. Examples of the alicyclic amines include isophoronediamine, bis(aminomethyl)cyclohexane, etc. Examples of the aromatic amines include phenylenediamine, xylylenediamine, diaminodiphenylmethane, m-aminophenol, etc.

[0069] The amines may be amine adducts, such as those obtained by adducting imidazoles or amines with epoxy resins, those obtained by adducting amines or hydrazine with isocyanates, and those obtained by adducting amines with urea.

[0070] Examples of imidazole compounds include 2-phenylimidazole, 1-benzyl-2-methylimidazole, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, and 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine. Examples of the acid anhydride compound include phthalic anhydride, trimellitic anhydride, and pyromellitic anhydride. Examples of the organic phosphinic acid compound include triphenylphosphine, tributylphosphine, methyldiphenylphosphine, and diphenylphosphine. Examples of phenol-based curing agents include bisphenol A, bisphenol F, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, and phenol novolak.

[0071] Examples of hydrazide compounds include VDH, VDH-J [1,3-bis(hydrazinocarboethyl)-5-isopropylhydantoin], MDH (malonic acid dihydrazide), ADH (adipic acid dihydrazide), UDH, UDH-J (7,11-octadecadiene-1,18-dicarbohydrazide), and LDH (octadecane-1,18-dicarboxylic acid dihydrazide).

[0072] The mixture product of the carboxylic acid compound and the amine compound includes a mixture product of a carboxylic acid compound represented by the following formula (I) and at least one selected from the group consisting of amine compounds represented by the following formulas (II), (III) and (IV) and compounds having an azole ring structure. R 41 -[COOH]x (I) In formula (I), x is 1 or 2; R 41 represents a C1 to C24 linear or branched saturated or unsaturated aliphatic hydrocarbon group (the branched chain may be substituted with a hydroxyl group).

[0073] R42 -[NH2]2(II) In formula (II), R 42 is a C1-C24 linear or branched alkylene group, a C2-C12 linear or branched alkylene group discontinuously interrupted by one or more NH groups (the H atoms bonded to the N atoms may be substituted with amino groups or C1-C12 alkylamino groups), a C6-C14 arylene group, a C1-C4 linear or branched alkylene group-C6-C14 arylene group, or a C1-C4 linear or branched alkylene group-C6-C14 arylene group-C1-C4 linear or branched alkylene group.

[0074] [ka] In formula (III), R 43 are each independently a single bond, or 42 is the same as:

[0075] [ka] In formula (IV), R 42 and R 43 is the same as in the above formula (II) and formula (III).

[0076] In the present embodiment, the heat curing agent (C) is preferably the above-mentioned amine adduct, and among them, the compound represented by the following general formula (3) is preferable.

[0077] [ka] In general formula (3), R 31 is a single bond, or a linear alkylene group, a cycloalkylene group, an arylene group, or a combination thereof, which may have a substituent and may have an imino group (-NH-) or an oxygen atom in the carbon chain. A is an organic group having a valence of n11, where n11 is an integer of 1 to 4. When n11 is 2 or more, there are multiple R 31 may be the same or different from each other.

[0078] R 31 The linear alkylene group in is preferably an alkylene group having 1 to 12 carbon atoms, such as a methylene group, an ethylene group, a propylene group, or a butylene group. The cycloalkylene group is preferably a cycloalkylene group having 3 to 12 carbon atoms, such as a cyclopentylene group, or a cyclohexylene group. The arylene group is preferably an arylene group having 6 to 14 carbon atoms, such as a phenylene group, or a naphthylene group. These combinations include, for example, a structure in which a straight-chain alkylene group-cycloalkylene group-straight-chain alkylene group is linked, or a straight-chain alkylene group-arylene group-straight-chain alkylene group is linked, etc. R 31 The substituents that may be included in the above include an alkyl group, a cycloalkyl group, an aryl group, a halogen atom, and a hydroxyl group, and the alkyl group, cycloalkyl group, and aryl group may have an oxygen atom in the carbon chain. The alkyl group is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an isopropyl group, and a t-butyl group. The cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group. The aryl group is preferably a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms, and examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and a biphenyl group. The alkyl group, cycloalkyl group, and aryl group may further have a halogen atom or a hydroxyl group as a substituent.

[0079] When n11 is 1, A is a monovalent organic group, and the monovalent organic group is preferably an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonylalkylene group, or a (meth)acryloyloxyalkyl group, which may have a substituent. The alkyl group, the cycloalkyl group, and the aryl group are preferably the same as those described above in R 31 The substituents which these may have include those listed above.31 The substituents may be the same as those exemplified above. The alkyl group of the alkyloxycarbonylalkylene group and the (meth)acryloyloxyalkyl group is preferably a straight-chain or branched alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an isopropyl group, and a t-butyl group. The alkyl group may have a halogen atom or a hydroxyl group as a substituent. The alkylene group of the alkyloxycarbonylalkylene group is preferably an alkylene group having 1 to 12 carbon atoms, such as a methylene group, an ethylene group, a propylene group, and a butylene group.

[0080] When n11 is 2, A is a divalent organic group, and the divalent organic group is preferably an alkylene group, a cycloalkylene group, or an arylene group which may have a substituent. The alkylene group is as described above. The alkylene group, the cycloalkylene group, and the arylene group, as well as the substituents which they may have, are as described above in R 31 The same as that exemplified in the above can be used.

[0081] When n11 is 3, A is a trivalent organic group and preferably has a structure represented by any one of the following general formulas (4) to (6).

[0082] [ka] In general formula (4), R 32 each independently represents a linear or branched alkylene group which may have a substituent.

[0083] [ka] In general formula (5), R 33 each independently represents a linear or branched alkylene group which may have a substituent.

[0084] [ka] In general formula (6), R 34 each independently represents a linear or branched alkylene group which may have a substituent; R 35 is a CH≡ group (methine group).

[0085] Above R 32 ~R 34 The straight chain alkylene group in R 31 In addition, R 32 ~R 34 The branched alkylene group in the formula (I) may have a structure in which the linear alkylene group is substituted with an alkyl group having 1 to 5 carbon atoms, and may have an oxygen atom in the carbon chain. Other substituents that may be present include the above-mentioned R 31 The same as that exemplified in the above can be used.

[0086] When n is 4, A is a tetravalent organic group and preferably has a structure represented by the following general formula (7).

[0087] [ka] In general formula (7), X 11 is a tetravalent residue derived from a cycloalkyl-alkylene-cycloalkyl group, an aryl-alkylene-aryl group, or a Si (silicon) atom.

[0088] X 11 The cycloalkyl-alkylene-cycloalkyl group in the above formula is a composite group in which two cycloalkyl groups are connected by an alkylene group, and may further have a substituent and may have an oxygen atom in the carbon chain. The two cycloalkyl groups may be the same or different. Specific examples of each of the cycloalkyl groups, alkylene groups, and optional substituents are shown in the above formula R. 11 It can be the same as that exemplified in . Also, X 11The aryl-alkylene-aryl group in the above formula is a composite group in which two aryl groups are connected by an alkylene group, and may further have a substituent and may have an oxygen atom in the carbon chain. The two aryl groups may be the same or different. Specific examples of each of the cycloalkyl group, alkylene group, and the substituent that may be possessed are shown in the above-mentioned R 11 It can be the same as that exemplified in .

[0089] Specific examples of the compound represented by the general formula (3) include 1,1'-[methylenebis(cyclohexane-1,4-diyl)]bis[3-(12-aminododecyl)urea], 1,1'-[methylenebis(cyclohexane-1,4-diyl)]bis[3-(2-aminoethyl)urea], 1,1'-[methylenebis(cyclohexane-1,4-diyl)]bis[3-(6-aminohexyl)urea], 1,1'-(hexa N,N'-hexamethylene[carbonylbis(azanediyl)-2-aminoethyl]-[carbonylbis(azanediyl)-6-aminohexyl] and the like.

[0090] The synthesis method of the amine compound represented by the general formula (3) is not particularly limited, but for example, it can be obtained by reacting a compound having two or more amino groups with an isocyanate compound. For example, it is preferable that the amine compound having a urea structure is obtained by reacting at least one isocyanate compound selected from the group consisting of the monoisocyanate compound, the diisocyanate compound, the triisocyanate compound, and the tetraisocyanate compound with hydrazine or a polyamine compound. The amine compound having a urea structure is preferably obtained by reacting the isocyanate compound with the hydrazine or a polyamine compound in an organic solvent or neat (solvent-free) at a controlled temperature of preferably -10°C to 120°C, more preferably -5°C to 100°C, even more preferably 0°C to 50°C, and especially preferably 5 to 30°C, so that the amount of the hydrazine or a polyamine compound is preferably 0.01 mol to 50 mol, more preferably 0.1 mol to 50 mol, still more preferably 0.1 mol to 30 mol, and particularly preferably 0.1 mol to 20 mol per mol of the isocyanate compound.

[0091] The isocyanate compound is not particularly limited as long as it is a compound having at least one isocyanate group in the molecule, and a monoisocyanate having one isocyanate group in the molecule or a polyisocyanate having two or more isocyanate groups in the molecule can be used.

[0092] As the arbitrary combination, one type of monoisocyanate may be used alone, two or more types of monoisocyanates may be used in combination, one type of polyisocyanate may be used alone, two or more types of polyisocyanates may be used in combination, or a monoisocyanate and a polyisocyanate may be used in combination.

[0093] Monoisocyanates include ethyl isocyanate, butyl isocyanate, propyl isocyanate, isopropyl isocyanate, tert-butyl isocyanate, dodecyl isocyanate, cyclohexyl isocyanate, octadecyl isocyanate, (R)-(+)-α-methylbenzyl isocyanate, (S)-(-)-α-methylbenzyl isocyanate, (R)-(-)-1-(1-naphthyl)ethyl isocyanate, ethyl isocyanatoacetate, and butyl isocyanatoacetate.

[0043] Preferably, the isocyanate compound is at least one selected from the group consisting of 2-isocyanatoethyl methacrylate, 3-(triethoxysilyl)propyl isocyanate, 6,7-methylenedioxy-(4-isocyanatomethylcoumarin), benzyl isocyanate, 3-isopropenyl-α,α-dimethylbenzyl isocyanate, (S)-(-)-methyl 2-isocyanatopropionate, (S)-2-isocyanato-3-methylpropionate, 2-isocyanatoethyl methacrylate, 3-(triethoxysilyl)propyl isocyanate, and 6,7-methylenedioxy-(4-isocyanatomethylcoumarin).

[0094] Specific examples of diisocyanates include propane-1,2-diisocyanate, 2,3-dimethylbutane-2,3-diisocyanate, 2-methylpentane-2,4-diisocyanate, octane-3,6-diisocyanate, 3,3-dinitropentane-1,5-diisocyanate, octane-1,6-diisocyanate, 1,6-hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate. It is preferable that the heat curing agent is at least one isocyanate compound selected from the group consisting of 1,3- or 1,4-bis(isocyanatemethyl)cyclohexane, diphenylmethane-4,4'-diisocyanate, hydrogenated tolylene diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate. The heat curing agent may be used alone or in combination of two or more.

[0095] The amine adduct may be synthesized or a commercially available product may be used. Specific examples of the amine adduct include ADEKA Hardener EH series (e.g., EH-5015S, EH-5030S, EH-4357S, EH-5057P, etc.) manufactured by ADEKA CORPORATION, and Fujicure series (e.g., FXR-1020, FXR-1030, etc.) manufactured by Fuji Chemical Industry Co., Ltd.

[0096] The heat curing agent (C) can be used alone or in combination of two or more kinds. The heat curing agent (C) may be liquid or powder. When the heat curing agent (C) is powder, the median diameter of the heat curing agent (C) is preferably 0.1 to 6 μm, more preferably 0.5 to 4 μm. Within this range, the sealant composition has excellent cleaning properties when combined with the wetting dispersant (D) described below.

[0097] In the present sealant composition, the content of the heat curing agent (C) is preferably 1 to 40 parts by mass, and more preferably 2 to 35 parts by mass, per 100 parts by mass of the curable resin (A) from the viewpoint of sealability and the like.

[0098] <Wetting and dispersing agent (D)> This sealant composition contains a wetting dispersant (D) having an acid value and / or an amine value. By containing the wetting dispersant (D), this sealant composition has excellent liquid crystal resistance and improved washability. Although the reason why the use of the wetting dispersant (D) improves washability is partially unclear, it is presumed that the wetting dispersant (D) suppresses the aggregation of powdered thermosetting agents and fillers in this sealant composition, and that the wetting dispersant (D) adsorbs to the surface of the member of the coating device and prevents the viscous sealant from sticking to the member. In addition, no washability effect was observed with a nonionic dispersant that does not have an acid value or an amine value.

[0099] The present wetting and dispersing agent (D) is required to have at least one of an acid value or an amine value, and may have both an acid value and an amine value. When the wetting dispersant (D) has an acid value, the wetting dispersant (D) has an acidic group. Examples of the acidic group include a carboxyl group (-COOH), a sulfo group (-SO3H), and a phosphate group (-OP(=O)(OH)2), and each hydrogen atom may be dissociated or may be substituted with an alkali metal ion or the like to form a salt. In addition, some OH of the phosphate group may be esterified to form a phosphate ester. As the acidic group, a carboxyl group or a phosphate group containing a phosphate ester is preferred, and a phosphate group is more preferred. When the wetting and dispersing agent (D) has an acid value, the acid value is preferably from 20 to 150 mgKOH / g, more preferably from 30 to 140 mgKOH / g, from the viewpoint of cleaning properties. The acid value is a value determined by potentiometric titration in accordance with JIS K 0070.

[0100] When the wetting and dispersing agent (D) has an amine value, the wetting and dispersing agent (D) has an amino group or an ammonium salt. When the wetting and dispersing agent (D) has an amine value, the acid value is preferably 20 to 100 mgKOH / g, more preferably 30 to 90 mgKOH / g, from the viewpoint of cleaning properties. The amine value refers to the amount of potassium hydroxide (mg) equivalent to the amount of perchloric acid required to neutralize the amine component contained in 1 g of sample, and is a value measured by the method defined in JIS-K7237.

[0101] From the viewpoint of further improving the cleaning property, it is more preferable that the wetting and dispersing agent (D) has both an acid value and an amine value. It is preferable that the acid value and the amine value of the wetting and dispersing agent (D) having an acid value and an amine value each satisfy the above range.

[0102] The wetting and dispersing agent (D) may be, for example, an anionic surfactant such as fatty acid sodium salt, monoalkyl sulfate salt, or monoalkyl phosphate salt; a cationic surfactant such as alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, or alkyl benzyl dimethyl ammonium salt; or an amphoteric surfactant such as alkyl carboxy betaine or imidazoline derivative. On the other hand, from the viewpoint of further improving liquid crystal resistance and washability, a wetting and dispersing agent having a weight average molecular weight of 2000 or more is preferred, and a wetting and dispersing agent having a weight average molecular weight of 2000 or more and 200,000 or less is more preferred.

[0103] Examples of the main chain skeleton of the wetting and dispersing agent include polyether, polyester, polyamine, polyurethane, polyacrylate, polyamide, polyethyleneimine, etc. It is preferable that the acidic group or amino group is arranged in a side chain or at an end of the main chain skeleton.

[0104] The wetting and dispersing agent (D) may be synthesized or may be a commercially available product. Examples of commercially available products include DISPERBYK-102, -106, -111, -140, -145, -180 manufactured by BYK-Chemie; BYK-2096, -2155, -9076, -9077 manufactured by Kao Corporation, and Homogenol L-95 manufactured by Kao Corporation.

[0105] The content of the wetting dispersant (D) is preferably 0.1 to 10 mass% based on the total amount of the liquid crystal sealant composition from the viewpoint of achieving both liquid crystal resistance and washability. From the viewpoint of washability, the content of the wetting dispersant (D) is preferably 0.1 mass% or more, more preferably 0.15 mass% or more, and particularly preferably 0.3 mass% or more. From the viewpoint of liquid crystal resistance, the content of the wetting dispersant (D) is preferably 10 mass% or less, more preferably 8 mass% or less, and more preferably 5 mass% or less.

[0106] <Optional ingredients> The liquid crystal sealing composition may further contain other components within the range in which the effects of the present invention are exhibited, such as fillers, polymerization inhibitors, silane coupling agents, light-shielding materials, thixotropic agents, elastomers, reactive diluents, chain transfer agents, curing accelerators, ion trapping agents, ion exchange agents, leveling agents, pigments, dyes, plasticizers, and defoamers.

[0107] (Filler (E)) The sealant composition may contain a filler (E) from the viewpoints of adjusting the viscosity of the sealant, improving the strength after curing, suppressing linear expansion, etc. The filler (E) can be appropriately selected from known inorganic fillers and organic fillers used in liquid crystal sealant applications. Examples of inorganic fillers include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, titanium oxide, alumina, zinc oxide, silicon dioxide, kaolin, talc, glass beads, sericite activated clay, bentonite, aluminum nitride, and silicon nitride. Examples of organic fillers include polymethyl methacrylate, polystyrene, copolymers obtained by copolymerizing monomers constituting these with other monomers, polyester fine particles, polyurethane fine particles, rubber fine particles, and core-shell particles composed of a shell containing a copolymer having a high glass transition temperature and a core of a copolymer having a low glass transition temperature. The fillers may be used alone or in combination of two or more, and it is preferable to use an inorganic filler and an organic filler in combination. The content of the filler is preferably from 2 to 40 parts by mass, and more preferably from 5 to 30 parts by mass, relative to 100 parts by mass of the curable resin (A).

[0108] (Polymerization inhibitor) The present sealant composition may contain a polymerization inhibitor in order to improve storage stability and cleaning properties. The polymerization inhibitor can be appropriately selected from those that suppress the curing reaction of the curable resin (A). Examples of the polymerization inhibitor include hindered amine-based, hindered phenol-based, quinone-based, phenothiazine-based, and nitrosamine-based polymerization inhibitors, and among these, hindered phenol-based compounds are preferred. Hindered phenol compounds are compounds having bulky structures at the 2- and 6-positions of phenol, and examples thereof include 2,6-t-butylphenol, 2,6-t-butyl-4-methylphenol, and 2,4,6-t-butylphenol. The polymerization inhibitors can be used alone or in combination of two or more. When a polymerization inhibitor is used in the present sealant composition, the content ratio thereof is preferably 0.0001 to 0.5 parts by mass, more preferably 0.0005 to 0.3 parts by mass, relative to 100 parts by mass of the curable resin (A), from the viewpoint of achieving both storage stability and curability during use.

[0109] (Silane coupling agent) The present sealant composition may contain a silane coupling agent in order to further improve adhesion to the substrate. Examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-isocyanatepropyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane. These silane coupling agents may be used alone or in combination of two or more. When a silane coupling agent is used, the content thereof is preferably from 0.1 to 10 parts by mass, and more preferably from 0.5 to 3 parts by mass, relative to 100 parts by mass of the curable resin (A).

[0110] (Light blocking material) The present sealant composition may contain a light-shielding material to prevent light leakage near the seal of the liquid crystal element and to improve contrast. Here, light-shielding means that the cured product of the present sealant composition containing the light-shielding material has an OD (optical density) value of 3 to 5. It is preferable to use a light-shielding material that has little staining properties against liquid crystal. Examples of the light-shielding material include carbon black and titanium black. The light-shielding material can be used in an amount of 50 parts by mass or less, preferably 5 to 40 parts by mass, and more preferably 10 to 30 parts by mass, based on 100 parts by mass of the curable resin (A).

[0111] (thixotropic agent) The present sealant composition may contain a thixotropic agent for the purpose of improving coatability, etc. Examples of the thixotropic agent include fine silica particles such as fumed silica, fine alumina particles, and non-spherical particles such as aliphatic amides. The amount of the thixotropic agent is preferably 10 parts by mass or less relative to 100 parts by mass of the curable resin (A) in order to suppress unevenness at the sealant interface after lamination, and is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass in order to improve coatability.

[0112] <Applications of liquid crystal sealant composition> Since the present sealant composition has excellent resistance to liquid crystals, it can be suitably used as a sealant that comes into contact with liquid crystals, and in particular, it can be suitably used as a sealant for a liquid crystal dropping method that comes into contact with liquid crystals in an uncured state.

[0113] [Liquid crystal element] The liquid crystal element according to the present invention is characterized by comprising a cured product of the present liquid crystal sealant composition. The present liquid crystal element has excellent resistance to liquid crystals, and disturbance of the liquid crystal is suppressed.

[0114] An example of the present liquid crystal element will be described with reference to Fig. 1. Fig. 1 is a plan view showing an example of the present liquid crystal element 100. As shown in FIG. 1, the liquid crystal element 100 comprises two substrates (a first substrate 10 and a second substrate 40) arranged opposite each other, a sealing member 22 arranged in a frame shape between the two substrates, and a liquid crystal 30 filled in the space formed by the two substrates and the sealing member 22. The present liquid crystal element has excellent resistance to liquid crystals since the sealing member 22 is a cured product of the present liquid crystal sealant composition.

[0115] The first substrate 10 and the second substrate 40 may be any substrate that is generally transparent to visible light, and may be appropriately selected from transparent substrates used in general liquid crystal elements. Specific examples of the substrate include rigid materials that are not flexible, such as quartz glass, non-alkali glass, and synthetic quartz plate; and flexible materials that are flexible, such as transparent resin film and flexible glass. The thickness of the substrate is not particularly limited, but may be, for example, about 50 μm to 1 mm. The surface of the substrate that comes into contact with the liquid crystal may have an alignment film for aligning the liquid crystal according to the driving method of the liquid crystal element. When the alignment film is provided, the alignment film may be any of a rubbed alignment film, a photo-aligned film, and a shaped alignment film. The substrate may further include any known configuration used in liquid crystal devices, such as a transparent electrode layer and a color filter. The liquid crystal 30 is not particularly limited, and may be appropriately selected from known liquid crystals used in liquid crystal elements according to the liquid crystal drive method and the like.

[0116] <Method of manufacturing liquid crystal element> A method for manufacturing a liquid crystal element will be described with reference to Fig. 2. Fig. 2 is a schematic process diagram showing an example of a method for manufacturing a liquid crystal element 100, and (a) to (e) of Fig. 2 are cross-sectional views of the liquid crystal element 100 in each of the processes (a) to (e) described below. (e) of Fig. 2 corresponds to the cross-sectional view taken along the cutting line IIE-IIE of Fig. 1. As shown in the example of FIG. 2, the method includes a step (a) of applying the liquid crystal sealant composition 20 in a frame-shaped pattern on a first substrate 10, a step (b) of dropping a liquid crystal 30 into the frame, a step (c) of bonding a second substrate 40 to the side of the first substrate 10 on which the frame of the liquid crystal sealant composition 20 is formed, a step (d) of irradiating the liquid crystal sealant composition 20 with light, and a step (e) of heating the liquid crystal sealant composition 20.

[0117] The method of applying the liquid crystal sealant composition 20 in the step (a) is not particularly limited, and may be appropriately selected from known printing methods and application methods. In the example of Fig. 1, the liquid crystal sealant composition 20 is applied to the edge of the first substrate 10, but depending on the application, it may be formed on the inside of the first substrate 10, or the first substrate may be cut after forming a plurality of frame-shaped patterns.

[0118] The method of dropping the liquid crystal 30 in the step (b) is not particularly limited and may be appropriately selected from known methods. The uncured liquid crystal sealant composition 20 contacts the liquid crystal 30, but when the present liquid crystal sealant composition is used, the liquid crystal sealant composition is prevented from eluting into the liquid crystal, etc., and the alignment disorder of the liquid crystal is prevented.

[0119] Next, in the step (c), the first substrate 10 and the second substrate 40 are bonded together via a liquid crystal sealant composition, and the liquid crystal 30 is sealed in. Thereafter, in step (d), light irradiation is carried out to cure the uncured liquid crystal sealant composition 20, and a photocured product 21 is obtained. Thereafter, in step (e), heating is performed to further cure the sealant composition that has become the photocured product 21, and a sealing member 22 is obtained. The curing conditions in steps (d) and (e) may be appropriately adjusted depending on the composition of the sealant composition. For example, ultraviolet light is 1,000 mJ / cm 2 The liquid crystal sealant composition 20 is irradiated with light and then heated at about 100 to 120° C. for about 1 hour, whereby a sealing member 22, which is a cured product of the liquid crystal sealant composition 20, is formed. In the liquid crystal element of the present invention, the sealing member 22 is a cured product of the liquid crystal sealant composition of the present invention, and therefore, the alignment disorder of the liquid crystal is suppressed.

[0120] The first base material 10 and the second base material 40 may be any base material that is generally transparent to visible light, and may be appropriately selected from transparent substrates used in general liquid crystal panels. Specific examples of such base materials include rigid materials with no flexibility, such as quartz glass, non-alkali glass, and synthetic quartz plate; and flexible materials having flexibility, such as transparent resin film and flexible glass. The thickness of the substrate is not particularly limited, but may be, for example, about 50 μm to 1 mm. The surface of the substrate that contacts the liquid crystal generally has an alignment film for aligning the liquid crystal. In the present invention, the alignment film is not particularly limited, and may be any of a rubbed alignment film, a photo-aligned film, and a shaped alignment film. The substrate may further include any known configuration used in liquid crystal devices, such as a transparent electrode layer and a color filter. The liquid crystal 30 is not particularly limited, and may be appropriately selected from known liquid crystals used in liquid crystal elements according to the liquid crystal drive method and the like. EXAMPLES

[0121] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0122] [Raw materials] <Curable resin (A)> [ka]

[0123] <Photopolymerization initiator (B)> [ka]

[0124] <Thermal hardener (C)> [ka]

[0125] <Wetting and dispersing agent (D)> (d1) DISPERBYK-145: Polyether-based polymer dispersant with phosphate and amino groups, acid value 76 mg / KOH, amine value 71 mg / KOH (d2) BYK-9076: Polyether-based polymer dispersant having a phosphate group and an alkyl ammonium salt, acid value 38 mg / KOH, amine value 44 mg / KOH, weight average molecular weight 10,000 (d3) DISPERBYK-111: polyester polymer dispersant with phosphate group, acid value 129 mg / KOH, weight average molecular weight 2,200 (d4) BYK-9077: Urethane polymer dispersant with amino groups, amine value 48 mg / KOH (d5) DISPERBYK-192: Nonionic acrylic dispersant containing styrene

[0126] <Filler (E)> (e1) KE-C50HG: Silica filler, manufactured by Nippon Shokubai Co., Ltd. (e2) F-351: Core-shell type acrylic resin filler, manufactured by Aica Kogyo Co., Ltd.

[0127] (f1) Thixotropic agent: TG-308F, amorphous silica, manufactured by Cabot Japan Co., Ltd. (f2) Polymerization inhibitor: dibutylhydroxytoluene (BHT)

[0128] [Example 1: Production of liquid crystal sealant composition] A sealant composition was obtained by blending 100 parts by mass of a curable resin (a1), 2 parts by mass of a photopolymerization initiator (b1), 2 parts by mass of a photopolymerization initiator (b2), 10 parts by mass of a heat curing agent (c1), 1.3 parts by mass of a wetting dispersant (d1), 10 parts by mass of a filler (e1), 7.5 parts by mass of a filler (e2), 1 part by mass of a thixotropic agent (f1), and 0.15 parts by mass of a polymerization inhibitor (f2) and thoroughly kneading the mixture.

[0129] [Examples 2 to 6: Production of liquid crystal sealant compositions] Liquid crystal sealant compositions of Examples 2 to 6 were obtained in the same manner as in Example 1, except that the components and the blending amounts in Example 1 were changed as shown in Table 1.

[0130] [Comparative Examples 1-2: Production of Liquid Crystal Sealant Composition] Liquid crystal sealant compositions of Comparative Examples 1 and 2 were obtained in the same manner as in Example 1, except that the components in Example 1 were changed as shown in Table 1.

[0131] [evaluation] <Cleaning performance evaluation> The cleaning performance evaluation will be described with reference to Figs. 3A and 3B. As shown in Fig. 3A, 0.2 mL of liquid crystal sealant composition 51 was filled into syringe head 52. Syringe head 52 was immersed in acetone 53 in container 55 with the top surface facing up. Container 55 was placed in tank 54 of an ultrasonic cleaner (IUC-4811N, manufactured by Tokyo Ultrasonic Engineering Co., Ltd.). Thereafter, the time from when ultrasonic waves were applied under conditions of an output of 700 W and a frequency of 28 kHz until the sealant was completely removed was measured. The results are shown in Table 1. (Cleaning Evaluation Criteria) Excellent: Completely removed within 20 minutes. ◯ (Good): Completely removed within 20 to 40 minutes. △(Fair): A small amount of residue was observed after 40 minutes. × (Fail): The syringe head was still clogged with sealant even after 40 minutes had passed.

[0132] <Evaluation of liquid crystal resistance> First, the following two samples (sample 1 and sample 2) were prepared. Sample 1: 0.1g of liquid crystal sealant composition was placed in an ampoule, and 1g of liquid crystal (MLC-6609, Merck) was added. The bottle was placed in a 120°C oven for 1 hour, and then left to stand at room temperature until it returned to room temperature (25°C). The liquid crystal portion was removed and filtered through a 0.2μm filter to prepare a sample for evaluation. Sample 2: First, the liquid crystal sealant composition was poured into a mold with a diameter of 5 mm and a thickness of 0.5 mm, and then irradiated with ultraviolet light (UV irradiation device: UVX-01224S1, manufactured by Ushio Inc., cumulative light amount 3000 mJ / cm 2 ) was then carried out. Next, 0.1 g of the liquid crystal sealant composition after UV irradiation was placed in an ampoule, and 1 g of liquid crystal (MLC-6609, Merck) was added. The bottle was placed in a 120°C oven for 1 hour, and then left to stand at room temperature until it returned to room temperature (25°C), after which the liquid crystal portion was removed and filtered through a 0.2 μm filter to prepare a sample for evaluation. The following NI point (Nematic-Isotropic transition temperature) measurement and specific resistance measurement were carried out for the liquid crystals of Sample 1 and Sample 2. The results are shown in Table 1.

[0133] (NI point measurement) The NI point was measured using a differential scanning calorimeter (DSC, PerkinElmer, Pyris6) by filling a measurement cell with liquid crystal and measuring at a temperature rise rate of 5°C / min in the range of 60 to 110°C. The NI point of a liquid crystal (MLC-6609, Merck) to which no liquid crystal sealant composition was added was 93.8°C, and the closer it is to this point, the more excellent the liquid crystal resistance of the liquid crystal sealant composition can be evaluated.

[0134] (Resistivity measurement) The resistivity was measured using a liquid crystal resistivity measurement system SR-6517 (manufactured by Toyo Corporation) by filling the measurement cell with liquid crystal and measuring it at room temperature (25°C), with an applied voltage of 10 V, for 120 seconds. The higher the resistivity, the better the liquid crystal resistance.

[0135] [Table 1]

[0136] As shown in Table 1, the liquid crystal sealant composition of Comparative Example 1, which did not contain the wetting dispersant (D), had good liquid crystal resistance but poor cleanability. The liquid crystal sealant composition of Comparative Example 2, which used a nonionic dispersant, did not improve cleanability. It was shown that the liquid crystal sealant compositions of Examples 1 to 6, which contained a wetting dispersant (D) having an acid value and / or an amine value, maintained liquid crystal resistance while exhibiting significantly improved cleanability. As described above, according to the present invention, a liquid crystal sealant composition having excellent washability while maintaining resistance to liquid crystals, and a liquid crystal device having excellent display performance can be obtained by using the sealant composition. [Explanation of symbols]

[0137] 10: first substrate, 20: sealant composition, 21: photocured product, 22: sealing member; 30: liquid crystal; 40: second base material; 51: sealing agent composition, 52: syringe head, 53: acetone, 54: Tank, 55: Container, 56: Water, 100: Liquid crystal element

Claims

1. The composition contains a curable resin (A), a photopolymerization initiator (B), a heat curing agent (C), and a wetting and dispersing agent (D) having an acid value, The liquid crystal sealing composition, wherein the wetting and dispersing agent (D) has an acid value of 20 to 150 mgKOH / g.

2. The composition contains a curable resin (A), a photopolymerization initiator (B), a heat curing agent (C), and a wetting and dispersing agent (D) having an amine value, The liquid crystal sealing composition, wherein the wetting and dispersing agent (D) has an amine value of 20 to 100 mgKOH / g.

3. The liquid crystal sealant composition according to claim 1 or 2, wherein the wetting and dispersing agent (D) has a weight average molecular weight of 2,000 or more.

4. The liquid crystal sealant composition according to any one of claims 1 to 3, wherein the curable resin (A) has heat curing properties and photocuring properties.

5. The liquid crystal sealant composition according to any one of claims 1 to 4, wherein the curable resin (A) comprises at least one selected from a partially esterified epoxy resin (A1) and a combination of an epoxy resin and an acrylic resin (A2).

6. The liquid crystal sealant composition according to any one of claims 1 to 5, wherein the heat curing agent (C) includes an amine-based curing agent.

7. The liquid crystal sealant composition according to any one of claims 1 to 6, wherein the heat curing agent (C) comprises a powder.

8. The liquid crystal sealing composition according to any one of claims 1 to 7, further comprising a filler (E).

9. The liquid crystal sealant composition according to any one of claims 1 to 8, wherein the content of the wetting dispersant (D) is 0.1 to 10 mass% based on the total amount of the liquid crystal sealant composition.

10. The liquid crystal sealant composition according to any one of claims 1 to 9, wherein the content of the solvent is 5 mass % or less based on the total amount of the liquid crystal sealant composition.

11. A liquid crystal element comprising a cured product of the liquid crystal sealant composition according to any one of claims 1 to 10.

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