Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1339—Gaskets; Spacers; Sealing of cells

Definitions

• the present invention relates to a photocurable resin composition, a display element sealant, a liquid crystal display element sealant, a liquid crystal display panel, and a method for producing the same.
• a liquid crystal display panel includes two transparent substrates with electrodes provided on the surface, a frame-shaped sealing member sandwiched between them, and liquid crystal sealed in a region surrounded by the sealing member.
• the liquid crystal display panel can be manufactured by a liquid crystal dropping method, for example.
• the liquid crystal display panel is manufactured by the liquid crystal dropping method.
• a liquid crystal display element sealant is applied to the inner edge of a transparent substrate to form a frame for filling the liquid crystal, and (2) liquid crystal is dropped into the frame.
• the two substrates are superposed under high vacuum while the liquid crystal display element sealant is in an uncured state, (4) the liquid crystal display element sealant is cured.
• liquid crystal dropping method photocuring or thermosetting is performed in a state where the uncured liquid crystal display element sealant and the liquid crystal are in contact with each other. Therefore, the liquid crystal display element sealing agent is required not only to have high curability but also to reduce liquid crystal contamination.
• a photocurable resin composition containing a compound having a (meth) acryloyl group in a molecule and an anthraquinone derivative as a photopolymerization initiator has been proposed (for example, a patent) Reference 1).
• a photocurable resin composition comprising a photopolymerizable oligomer and a compound B obtained by reacting hydroxythioxanthone as a photopolymerization initiator with a compound having two or more epoxy groups in the molecule has been proposed ( For example, Patent Document 2).
• a sealing agent for liquid crystal display elements including a curable resin, a specific thioxanthone polymerization initiator, and an amine sensitizer has been proposed (for example, Patent Document 3).
• the present invention has been made in view of the above problems.
• the present invention when used as a display element sealant, particularly a liquid crystal display element sealant, the present invention has sufficient curability for visible light, and the liquid crystal It aims at providing the photocurable resin composition which can suppress contamination highly.
• a photocurable resin composition comprising a curable compound A having an ethylenically unsaturated double bond in the molecule and a compound B represented by the following general formula (1).
• At least one of R 1 to R 8 is —S—X (X is an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted alkenyl group having 1 to 8 carbon atoms, or An optionally substituted aryl group),
• the remaining R 1 to R 8 are each a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted alkenyl group having 1 to 8 carbon atoms, or a substituted group.
• R 1 to R 8 is a C 1-8 alkyl group, hydroxyl group or hydroxyl group substituted with a hydroxyl group, a hydroxyl group or a hydroxyl group-containing group
• X represents an alkyl group having 1 to 8 carbon atoms substituted with a hydroxyl group or a hydroxyl group-containing group, an alkenyl group having 1 to 8 carbon atoms substituted with a hydroxyl group or a hydroxyl group-containing group, or an aryl substituted with a hydroxyl group or a hydroxyl group-containing group Base
• X represents an alkyl group having 1 to 8 carbon atoms substituted with a hydroxyl group or a hydroxyl group-containing group, an alkenyl group having 1 to 8 carbon atoms substituted with a hydroxyl group or a hydroxyl group-containing group, or an aryl substituted with a hydroxyl group or a hydroxyl group-containing group Base
• [4] The photocurable resin composition according to any one of [1] to [3], further comprising an amine sensitizer C.
• thermosetting compound D having an epoxy group in the molecule (provided that the thermosetting compound D is different from the curable compound A) and a thermosetting agent E; [1] The photocurable resin composition according to any one of [6].
• thermosetting agent E is selected from the group consisting of a dihydrazide thermal latent curing agent, an imidazole thermal latent curing agent, an amine adduct thermal latent curing agent, and a polyamine thermal latent curing agent.
• a display element sealing agent comprising the photocurable resin composition according to any one of [1] to [9].
• a liquid crystal display element sealing agent comprising the photocurable resin composition according to any one of [1] to [9].
• a step of forming a seal pattern on one substrate using the liquid crystal display element sealant according to [11], and the seal pattern in an uncured state, or in the region of the seal pattern, or the one A step of dropping liquid crystal on the other substrate paired with the substrate, a step of superimposing the one substrate and the other substrate through the seal pattern, and a step of curing the seal pattern And manufacturing method of liquid crystal display panel.
• the light applied to the seal pattern includes light in a visible light region.
• a resin composition when used as a display element sealant, particularly a liquid crystal display element sealant, it has sufficient curability for visible light and can highly suppress contamination of liquid crystal.
• a resin composition can be provided.
• Photocurable resin composition The photocurable resin composition of the present invention comprises a curable compound A and a compound B, and if necessary, an amine-based sensitizer C, a thermosetting compound D, and a thermosetting agent. And E.
• the photocurable resin composition of the present invention may further contain other components as necessary.
• Curable compound A The curable compound A contained in the photocurable resin composition of the present invention is a compound having an ethylenically unsaturated double bond in the molecule.
• the compound having an ethylenically unsaturated double bond in the molecule is preferably a compound having a (meth) acryloyl group in the molecule.
• the number of (meth) acryloyl groups per molecule is 1 or 2 or more.
• the compound having a (meth) acryloyl group in the molecule may be a monomer, an oligomer or a polymer.
• (Meth) acryloyl group means acryloyl group or methacryloyl group
• (meth) acrylate means acrylate or methacrylate.
• Examples of compounds having one (meth) acryloyl group in one molecule include (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic acid 2-hydroxyethyl ester. Alkyl esters are included.
• Examples of compounds having two or more (meth) acryloyl groups in one molecule include di (meth) acrylates such as polyethylene glycol, propylene glycol, and polypropylene glycol; di (meth) tris (2-hydroxyethyl) isocyanurate Acrylate; Di (meth) acrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of neopentyl glycol; Diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A Di (meth) acrylate of triol obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of trimethylolpropane; bisphenol A1 Di (meth) acrylate of a diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to the above; tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate; trimethylolprop
• the curable compound A may further have an epoxy group in the molecule.
• the number of epoxy groups per molecule is 1 or 2 or more. If the curable compound A further has not only a (meth) acryloyl group but also an epoxy group in the molecule, the photocurable resin composition containing the curable compound A can be provided with photocurability and thermosetting. Thereby, the sclerosis
• the compound having a (meth) acryloyl group and an epoxy group in the molecule can be, for example, a (meth) acrylic acid glycidyl ester obtained by reacting an epoxy compound and (meth) acrylic acid in the presence of a basic catalyst. .
• the epoxy compound to be reacted may be a polyfunctional epoxy compound having two or more epoxy groups in the molecule, and suppresses the decrease in the adhesiveness of the cured product of the photocurable resin composition due to excessive increase in the crosslinking density.
• a bifunctional epoxy compound is preferable.
• bifunctional epoxy compounds include bisphenol type epoxy compounds (bisphenol A type, bisphenol F type, 2,2′-diallyl bisphenol A type, bisphenol AD type, hydrogenated bisphenol type, etc.), biphenyl type epoxy compounds, And naphthalene type epoxy compounds. Of these, bisphenol A type and bisphenol F type bisphenol type epoxy compounds are preferred from the viewpoint of good coating properties.
• the bisphenol type epoxy compound has advantages such as excellent coating properties as compared with the biphenyl ether type epoxy compound.
• the compound having a (meth) acryloyl group and an epoxy group in the molecule may be one kind or a combination of two or more kinds.
• a compound A1 having a (meth) acryloyl group in the molecule and not having an epoxy group may be combined with a compound A2 having a (meth) acryloyl group and an epoxy group in the molecule.
• the photocurable resin composition further contains an epoxy compound as the thermosetting compound D, the epoxy compound, and the compound A1 having a (meth) acryloyl group in the molecule and not having an epoxy group, Can improve the compatibility.
• the photocurable resin composition contains the compound B having moderate hydrophilicity, even if the photocurable resin composition contains the compound A1 that is more hydrophobic than the compound A2, the display element of the photocurable resin composition, in particular, Elution to the liquid crystal can be suppressed.
• the content of the compound A2 having a (meth) acryloyl group and an epoxy group in the molecule is not particularly limited, but may be, for example, 30% by mass or more based on the total of the curable compound A.
• the weight average molecular weight of the curable compound A is preferably about 310 to 1,000.
• the weight average molecular weight of the curable compound A can be measured in terms of polystyrene by, for example, gel permeation chromatography (GPC).
• Compound B contained in the photocurable resin composition of the present invention can function as a photoinitiator and is represented by the following general formula (1).
• At least one of R 1 to R 8 in the general formula (1) is —SX.
• X is an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted alkenyl group having 1 to 8 carbon atoms, or an optionally substituted aryl group.
• the remaining R 1 to R 8 are each a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted alkenyl group having 1 to 8 carbon atoms, or a substituted group.
• At least one of X and the remaining R 1 to R 8 is a hydroxyl group, an alkyl group having 1 to 8 carbon atoms substituted with a hydroxyl group or a hydroxyl group-containing group, 1 to carbon atoms substituted with a hydroxyl group or a hydroxyl group-containing group. Or an aryl group substituted with a hydroxyl group or a hydroxyl group-containing group.
• the number of hydroxyl groups in the group containing a hydroxyl group may be one or two or more.
• Examples of the alkyl group having 1 to 8 carbon atoms represented by X and the remaining R 1 to R 8 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, etc. Is included.
• the alkyl group having 1 to 8 carbon atoms may be linear or branched.
• Examples of the alkenyl group having 1 to 8 carbon atoms represented by X and the remaining R 1 to R 8 include a propenyl group and a butenyl group.
• the alkenyl group having 1 to 8 carbon atoms may be linear or branched.
• Examples of the substituent that the alkyl group and the alkenyl group may have include a hydroxyl group, a hydroxyl group-containing group, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms (for example, a methoxy group) and the like.
• Examples of the alkyl group having 1 to 8 carbon atoms substituted with a hydroxyl group or a hydroxyl group-containing group include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, —CH 2 —O—CH 2 CH (OH) —CH 2 —O—CO—C (CH 3 ) ⁇ CH and the like are included.
• Examples of the alkenyl group having 1 to 8 carbon atoms substituted with a hydroxyl group or a hydroxyl group-containing group include a hydroxybutenyl group.
• Examples of the aryl group represented by X and the remaining R 1 to R 8 include a phenyl group and a naphthyl group.
• Examples of the substituent that the aryl group may have include a hydroxyl group, a hydroxyl group-containing group, an alkyl group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a perfluoromethyl group, etc.), An alkoxy group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms (such as a methoxy group) is included.
• the number of substituents is not particularly limited and is preferably 1 to 3.
• the hydroxyl group-containing group is preferably a group obtained by ring-opening addition of an alkylene oxide which may be substituted with a hydroxyl group.
• a polymerizable functional group is contained in the example of the substituent in the alkylene oxide which may be substituted.
• the polymerizable functional group is a photopolymerizable functional group (for example, (meth) acryloyl group) or a thermally polymerizable functional group (for example, oxiranyl group). Since the compound B having a polymerizable functional group can undergo a polymerization reaction with the curable compound A, it is considered that elution from the cured product is easily suppressed.
• Examples of the hydroxyl group-containing group having a polymerizable functional group include a group represented by the following formula (A).
• Y alkylene group or phenylene group
• Z alkylene group
• Rb alkyl group
• Compound B has a hydroxyl group in the molecule and can satisfactorily suppress liquid crystal contamination, so it does not need to further have another hydrophilic group (for example, NHCO group).
• another hydrophilic group for example, NHCO group
• Compound B is preferably represented by the following general formula (2) and more preferably represented by the following general formula (2 ′) because of its high light absorption in the visible light region.
• X in the general formulas (2) and (2 ′) is an alkyl group having 1 to 8 carbon atoms substituted with the above-mentioned hydroxyl group or hydroxyl group-containing group, or an alkenyl having 1 to 8 carbon atoms substituted with a hydroxyl group or a hydroxyl group-containing group. Or an aryl group substituted with a hydroxyl group or a hydroxyl group-containing group.
• Specific examples of the compound represented by the general formula (1) include 2- (2-hydroxyethylthio) thioxanthone, 2- (2-hydroxypropylthio) thioxanthone, 2- (4-hydroxyphenylthio) thioxanthone and the like. included.
• the compound represented by the general formula (1) can be produced by any method.
• a halogenated thioxanthone may be reacted with a compound having a thiol group and a hydroxyl group; the compound obtained by the reaction may be further subjected to a ring-opening addition reaction with an optionally substituted alkyl oxide.
• a halogenated hydroxythioxanthone may be reacted with a compound having a thiol group.
• the compounds represented by the general formulas (2) and (2 ′) may be obtained by reacting a halogenated thioxanthone with a compound having a thiol group and a hydroxyl group (see the following reaction formula 1);
• the compound obtained in (1) may be further subjected to a ring-opening addition reaction with an optionally substituted alkylene oxide (see the following reaction formula 2).
• Y is an arylene group, an alkylene group having 1 to 8 carbon atoms, or an alkenylene group having 1 to 8 carbon atoms.
• Halo is a halogen atom such as a chlorine atom.
• Y is an arylene group, an alkylene group or an alkenylene group.
• Ra is a hydrogen atom, an alkyl group, or a group represented by the following formula (B).
• Z and Rb in the following formula (B) are the same as Z and Rb in the above formula (A), respectively.
• the thioxanthone skeleton itself has low sensitivity to visible light.
• compound B has a structure in which a thioether group is bonded to a thioxanthone skeleton, sensitivity to visible light is moderately enhanced.
• Compound B further has a hydroxyl group that is a hydrophilic group in the molecule. Therefore, not only can the elution into the liquid crystal exhibiting hydrophobicity be reduced, but also when the photocurable resin composition is cured, the compound B and other components (for example, monomer components) may have hydrogen bonds or additional bonds. A chemical bond can be made. Therefore, the elution of the compound B or its decomposition product from the obtained cured product can be reduced.
• the number of hydroxyl groups in one molecule of compound B is preferably 1 to 5, and more preferably 1 to 3.
• the hydrophilicity of Compound B is moderately enhanced, and when the photocurable resin composition is used as a liquid crystal display element sealant, the dissolution of Compound B into the liquid crystal Can be preferably suppressed.
• the number of hydroxyl groups in one molecule is 5 or less, the moisture resistance of the cured product is hardly impaired.
• the molecular weight of Compound B is preferably 274 to 500, for example. If the molecular weight of Compound B is 274 or more, elution into the liquid crystal may be difficult to occur. When the molecular weight of Compound B is 500 or less, compatibility with the curable compound A can be improved, so that sufficient curability is easily obtained.
• the molecular weight of Compound B is more preferably 280 to 350.
• the molecular weight of Compound B can be determined as the “relative molecular mass” of the molecular structure of the main peak detected when high performance liquid chromatography (HPLC: High Performance Liquid Chromatography) is performed under the following conditions.
• Compound B is dissolved in THF (tetrahydrofuran) to prepare a sample solution, and high performance liquid chromatography (HPLC) measurement is performed under the following measurement conditions. Then, the area percentage of the detected peak (ratio of the area of each peak to the sum of the areas of all peaks) is obtained, and the presence or absence of the main peak (main detection peak) is confirmed.
• Main peak (main detection peak) refers to a peak having the highest intensity (peak having the highest peak height) among all peaks detected at a detection wavelength of 400 nm.
• the relative molecular mass corresponding to the peak apex of the detected main peak can be measured by liquid chromatography mass spectrometry (LC / MS).
• Equipment Acquity TM H-Class system / SQ Detector made by waters
• Column Acquity UPLC BEH C18, 2.1mmID ⁇ 100mm Particle size: 1.7 ⁇ m
• Mobile phase A: Acetonitrile B: 5 mM ammonium acetate aqueous solution
• a / B 60/40 (0-4 minutes) 95/5 (4-9 minutes) 95/5 (9-10 minutes)
• Ionization ESI (electrospray ionization), positive / negative ion measurement
• PDA detector Measurement wavelength: 190-500 nm, Extraction wavelength: 400 nm
• Compound B may be one type or a combination of two or more types.
• the content of compound B is preferably 0.01 to 10% by mass with respect to curable compound A. If the content of Compound B is 0.01% by mass or more, sufficient photocurability is easily obtained. When the content of Compound B is 10% by mass or less, since the elution into the liquid crystal is small, the contamination of the liquid crystal can be further reduced.
• the content of the compound B is more preferably 0.1 to 5% by mass, further preferably 0.1 to 3% by mass, and more preferably 0.1 to 2.5% by mass with respect to the curable compound A. % Is particularly preferred.
• the structure of Compound B contained in the photocurable resin composition can be specified by combining high performance liquid chromatography (HPLC) and liquid chromatography mass spectrometry (LC / MS) with NMR measurement or IR measurement. .
• HPLC high performance liquid chromatography
• LC / MS liquid chromatography mass spectrometry
• NMR measurement or IR measurement IR measurement
• the following procedure can be used. 1) A solution in which a photocurable resin composition is dissolved in tetrahydrofuran (THF) is centrifuged by a centrifugal separator to precipitate particle components such as silica particles and thermoplastic resin particles. The obtained solution is filtered through a filter to remove the particle component, thereby obtaining a sample solution. 2) The sample solution obtained in 1) is subjected to high performance liquid chromatography (HPLC) measurement.
• HPLC high performance liquid chromatography
• the HPLC measurement methods and conditions are the same as the HPLC measurement methods and conditions in the measurement of the molecular weight of Compound B.
• HPLC measurement the relative molecular mass and composition formula of the main peak detected by a detector with a wavelength of 400 nm characteristic of the thioxanthone skeleton are measured by liquid chromatography mass spectrometry (LC / MS).
• LC / MS measurement method and conditions are the same as the LC / MS measurement method and conditions in the measurement of the molecular weight of Compound B.
• the NMR measurement or IR measurement is performed on the sample solution obtained in 1) above. Thereby, the presence or absence of a spectrum characteristic of the thioxanthone skeleton, thioether group, or hydroxyl group is confirmed, and the chemical structure is specified.
• the photoinitiator has higher sensitivity to visible light.
• the photoinitiator is too sensitive to visible light, the eluted photoinitiator may cause an unnecessary reaction with the liquid crystal.
• Compound B that can function as a photoinitiator has a structure in which a thioether group is bonded to a thioxanthone skeleton, and therefore has an appropriate sensitivity to visible light (sensitivity is not too high). Therefore, it is possible to suppress unnecessary reaction with the liquid crystal when eluted into the liquid crystal while having good curability in the visible light region. Furthermore, since the compound B has a hydroxyl group that is hydrophilic, elution into the liquid crystal that is hydrophobic can also be reduced. By these, the contamination of the liquid crystal resulting from the elution of the compound B into the liquid crystal and the unnecessary reaction with the liquid crystal can be highly suppressed without impairing the curability in the visible light region.
• Amine sensitizer C is an alkylamine compound, an amine-modified (meth) acrylate compound, an aminobenzoyl structure (—R 1 R 2 N—C 6 H 4 —CO—, R 1 and R 2 : hydrogen atom or alkyl group ) And the like.
• alkylamine compound examples include n-butylamine, di-n-butylamine, tri-n-butylphosphine, allylthiouric acid, triethylamine, diethylaminoethyl methacrylate, diethanolamine and the like.
• amine-modified (meth) acrylate compounds include amine-modified polyester (meth) acrylate oligomers, amine-modified epoxy (meth) acrylate oligomers, amine-modified (meth) acrylate monomers, and the like.
• Examples of compounds having an aminobenzoyl structure include benzophenone compounds having an amino group such as 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone; 4-dimethylaminobenzoic acid, Methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, butoxyethyl 4-dimethylaminobenzoate, 2- (dimethylaminobenzoic acid) )
• a benzoic acid having an amino group such as ethyl or an ester thereof; and a compound represented by the following general formula (3).
• P in the general formula (3) is a group derived from a polyhydric alcohol compound.
• polyhydric alcohol compounds include (poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, and caprolactone polyol.
• the molecular weight of the group represented by P is preferably 100 to 2000. When the molecular weight of the group represented by P is 100 or more, elution into the liquid crystal is difficult to occur, and when it is 2000 or less, an excessive increase in the viscosity of the photocurable resin composition can be suppressed.
• N in the general formula (3) represents an integer of 1 or more, preferably an integer of 2 to 6.
• n 2 or more
• the molecular weight can be set to a certain value or more, so that elution into the liquid crystal can be easily suppressed. It is easy to suppress the excessive increase in the viscosity of a photocurable resin composition as n is 6 or less.
• n is preferably 2 and P is preferably a group derived from polyethylene glycol.
• a compound having an aminobenzoyl structure is preferable because the reaction activity of Compound B can be preferably increased.
• the compound having an aminobenzoyl structure may not further have an NHCO group.
• the molecular weight of the sensitizer C is preferably 200 or more and 3000 or less, for example.
• the molecular weight of the sensitizer C is 200 or more, it is difficult to elute into the liquid crystal, and thus liquid crystal contamination is easily reduced.
• the molecular weight of the sensitizer C is 3000 or less, the compatibility with the curable compound A is hardly impaired.
• the molecular weight of sensitizer C is more preferably 250 or more and 1000 or less.
• the content of sensitizer C is preferably 0.01 to 10% by mass with respect to curable compound A.
• the content of the sensitizer C is 0.01% by mass or more, the compound B can be sufficiently activated, so that sufficient curability is easily obtained.
• the content of the sensitizer C is 10% by mass or less, elution into the liquid crystal hardly occurs without impairing curability.
• the content of the sensitizer C is more preferably 0.1 to 5% by mass with respect to the curable compound A, further preferably 0.1 to 3% by mass, and 0.1% by mass or more. It is particularly preferred that it is less than 2% by weight.
• thermosetting compound D is preferably an epoxy compound having an epoxy group in the molecule. However, the thermosetting compound D is different from the curable compound A.
• the thermosetting compound D is more preferably an epoxy compound having no (meth) acryloyl group in the molecule.
• the epoxy compound may be any of a monomer, an oligomer or a polymer. Epoxy compounds, for example, when using a photocurable resin composition as a liquid crystal display element sealing agent, have low solubility and diffusibility in liquid crystals, and not only improve the display characteristics of the resulting liquid crystal panel, but also cured products. Can improve the moisture resistance.
• the epoxy compound may be an aromatic epoxy compound having a weight average molecular weight of 500 to 10,000, preferably 1,000 to 5,000.
• the weight average molecular weight of the epoxy compound can be measured in terms of polystyrene by gel permeation chromatography (GPC).
• aromatic epoxy compounds include the reaction of aromatic diols typified by bisphenol A, bisphenol S, bisphenol F, bisphenol AD, etc., and diols modified with ethylene glycol, propylene glycol, alkylene glycol, and epichlorohydrin.
• Polyvalent glycidyl ether compounds; xylylene phenol resin glycidyl ether compounds and the like are included.
• cresol novolac type epoxy compound cresol novolac type epoxy compound, phenol novolac type epoxy compound, bisphenol A type epoxy compound, bisphenol F type epoxy compound, triphenolmethane type epoxy compound, triphenolethane type epoxy compound, trisphenol type epoxy compound, dicyclopentadiene type Epoxy compounds, diphenyl ether type epoxy compounds and biphenyl type epoxy compounds are preferred.
• the epoxy compound may be one type or a combination of two or more types.
• the epoxy compound may be liquid or solid.
• a solid epoxy compound is preferable from the viewpoint of easily improving the moisture resistance of the cured product.
• the softening point of the solid epoxy compound is preferably 40 ° C. or higher and 150 ° C. or lower.
• the content of the thermosetting compound D is preferably 3 to 20% by mass with respect to the photocurable resin composition.
• the content of the thermosetting compound D is preferably 3 to 20% by mass with respect to the photocurable resin composition.
• the content of the thermosetting compound D is more preferably 3 to 15% by mass, and further preferably 5 to 15% by mass with respect to the photocurable resin composition.
• thermosetting agent E is a compound that does not cure the thermosetting compound D under normal storage conditions (room temperature, under visible light, etc.), but cures the compound when given heat.
• the photocurable resin composition containing the thermosetting agent E is excellent in storage stability and thermosetting.
• the thermosetting agent E is preferably an epoxy curing agent.
• the melting point of the epoxy curing agent is 50 ° C. or more and 250 ° C. or less, although it depends on the thermosetting temperature from the viewpoint of enhancing the viscosity stability of the photocurable resin composition and not impairing the moisture resistance of the cured product.
• the temperature is preferably 100 ° C. or higher and 200 ° C. or lower, and more preferably 150 ° C. or higher and 200 ° C. or lower.
• epoxy curing agent examples include organic acid dihydrazide thermal latent curing agent, imidazole thermal latent curing agent, amine adduct thermal latent curing agent, and polyamine thermal latent curing agent.
• organic acid dihydrazide thermal latent curing agents include adipic acid dihydrazide (melting point 181 ° C.), 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin (melting point 120 ° C.), 7,11-octa Decadiene-1,18-dicarbohydrazide (melting point 160 ° C.), dodecanedioic acid dihydrazide (melting point 190 ° C.), sebacic acid dihydrazide (melting point 189 ° C.) and the like.
• imidazole-based thermal latent curing agents examples include 2,4-diamino-6- [2′-ethylimidazolyl- (1 ′)]-ethyltriazine (melting point 215 to 225 ° C.) and 2-phenylimidazole (melting point) 137-147 ° C.) and the like.
• the amine adduct thermal latent curing agent is a thermal latent curing agent comprising an addition compound obtained by reacting an amine compound having catalytic activity with an arbitrary compound, and examples thereof include Ajinomoto Fine Techno Co., Ltd. ) Amicure PN-40 (melting point 110 ° C.), Ajinomoto Fine Techno Co., Ltd.
• the polyamine thermal latent curing agent is a thermal latent curing agent having a polymer structure obtained by reacting an amine and an epoxy.
• the epoxy curing agent may be only one kind or a combination of two or more kinds.
• the content of the thermosetting agent E is preferably 3 to 30% by mass, more preferably 3 to 20% by mass, and more preferably 5 to 20% by mass with respect to the photocurable resin composition. Further preferred.
• the photocurable resin composition containing the thermosetting agent E can be a one-component curable resin composition.
• the one-component curable resin composition is excellent in workability because it is not necessary to mix the main agent and the curing agent in use.
• the total content of the thermosetting compound D and the thermosetting agent E is preferably 6 to 50% by mass, more preferably 6 to 35% by mass, with respect to the photocurable resin composition. More preferably, it is 30 mass%.
• the photocurable resin composition of the present invention may further contain thermoplastic resin particles as necessary.
• the thermoplastic resin particles include a thermoplastic resin having a softening point temperature measured by the ring and ball method of 50 to 120 ° C., preferably 70 to 100 ° C., and a number average particle diameter of 0.05 to 5 ⁇ m, preferably 0.8. It can be 1 to 3 ⁇ m.
• the photocurable resin composition containing such thermoplastic resin particles can relieve the shrinkage stress generated in the cured product.
• the number average particle diameter is set to the upper limit value or less, it is possible to prevent the coating stability from being lowered by the thermoplastic resin particles when forming a seal member having a thin line width.
• the number average particle size can be measured with a dry particle size distribution meter.
• thermoplastic resin particles include fine particles obtained by suspension polymerization of a resin containing an epoxy group and a double bond group with a monomer capable of radical polymerization.
• the resin containing an epoxy group and a double bond group include a resin obtained by reacting a bisphenol F type epoxy resin and methacrylic acid in the presence of a tertiary amine.
• radically polymerizable monomers include butyl acrylate, glycidyl methacrylate, and divinylbenzene.
• the content of the thermoplastic resin particles is preferably 5 to 40% by mass, more preferably 7 to 30% by mass with respect to the photocurable resin composition.
• the thermoplastic resin particles can preferably relieve the shrinkage stress during the heat curing of the photocurable resin composition, and it is easy to form a seal member with a target line width. .
• the photocurable resin composition of the present invention may further contain a filler as necessary.
• a photocurable resin composition containing a filler may have good viscosity, strength of a cured product, linear expansion, and the like.
• the filler can be an inorganic filler or an organic filler.
• inorganic fillers include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium oxide, titanium nitride, aluminum oxide (alumina), zinc oxide, silicon dioxide, potassium titanate , Kaolin, talc, glass beads, sericite, activated clay, bentonite, aluminum nitride, silicon nitride and the like. Of these, silicon dioxide and talc are preferable.
• the shape of the filler may be a regular shape such as a spherical shape, a plate shape, or a needle shape, or may be an irregular shape.
• the average primary particle diameter of the filler is preferably 1.5 ⁇ m or less, and the specific surface area is preferably 0.5 to 20 m 2 / g.
• the average primary particle diameter of the filler can be measured by a laser diffraction method described in JIS Z8825-1.
• the specific surface area of the filler can be measured by the BET method described in JIS Z8830.
• the content of the filler is preferably 1 to 50% by mass with respect to the photocurable resin composition.
• the coating stability of a photocurable resin composition is hard to be impaired as content of a filler is 50 mass% or less.
• the content of the filler is more preferably 10 to 30% by mass with respect to the photocurable resin composition.
• the photo-curable resin composition of the present invention is optionally combined with a thermal radical polymerization initiator, a coupling agent such as a silane coupling agent, an ion trapping agent, an ion exchange agent, a leveling agent, a pigment, a dye, a plasticizer, and a quenching agent.
• a coupling agent such as a silane coupling agent, an ion trapping agent, an ion exchange agent, a leveling agent, a pigment, a dye, a plasticizer, and a quenching agent.
• An additive such as a foaming agent may be further included.
• silane coupling agent examples include vinyltrimethoxysilane, ⁇ - (meth) acryloxypropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, and the like.
• the content of the silane coupling agent may be 0.01 to 5% by mass with respect to the photocurable resin composition. When the content of the silane coupling agent is 0.01% by mass or more, the cured product of the photocurable resin composition tends to have sufficient adhesiveness.
• the photocurable resin composition of the present invention may further contain a spacer for adjusting the gap of the liquid crystal display panel.
• the viscosity of the photocurable resin composition of the present invention at 25 ° C. and 2.5 rpm of the E-type viscometer is preferably 200 to 450 Pa ⁇ s, and preferably 300 to 400 Pa ⁇ s. It is more preferable that When the viscosity is in the above range, the applicability of the photocurable resin composition by the dispenser is good.
• the photocurable resin composition of the present invention can be used as, for example, a sealing agent.
• the sealing agent is preferably a display element sealing agent used for sealing display elements such as liquid crystal display elements, organic EL elements, and LED elements.
• the display element sealant is particularly preferably a liquid crystal display element sealant, and more preferably a liquid crystal display element sealant for a liquid crystal dropping method.
• the display element panel of the present invention includes a pair of substrates, a display element disposed between the pair of substrates, and a seal member for sealing the display element.
• the seal member can be a cured product of the display element sealant of the present invention.
• the display element sealing agent of the present invention is composed of the photocurable resin composition of the present invention.
• Examples of display elements include liquid crystal display elements, organic EL elements, LED elements, and the like.
• a liquid crystal display element is preferable because the photocurable resin composition of the present invention can satisfactorily suppress liquid crystal contamination.
• the liquid crystal display panel of the present invention includes a space surrounded by a pair of substrates, a frame-shaped seal member disposed between the pair of substrates, and a frame-shaped seal member between the pair of substrates.
• a sealing member can be made into the hardened
• the liquid crystal display element sealing agent of the present invention comprises the photocurable resin composition of the present invention.
• the pair of substrates are both transparent substrates.
• the material of the transparent substrate can be glass or plastic such as polycarbonate, polyethylene terephthalate, polyethersulfone and PMMA.
• a matrix-like TFT, a color filter, a black matrix, or the like can be disposed on the surface of one of the pair of substrates.
• An alignment film may be further disposed on the surface of the one substrate.
• the alignment film contains a known organic alignment agent or inorganic alignment agent.
• the liquid crystal display panel is manufactured using the liquid crystal display element sealant of the present invention.
• a liquid crystal dropping method and a liquid crystal injecting method as a method for manufacturing a liquid crystal display panel, but the liquid crystal display panel of the present invention is preferably manufactured by a liquid crystal dropping method.
• the manufacturing method of the liquid crystal display panel by the liquid crystal dropping method is 1) forming a seal pattern of the liquid crystal display element sealant of the present invention on one substrate; 2) dropping the liquid crystal in a region surrounded by the seal pattern of the substrate or a region of the other substrate facing the region surrounded by the seal pattern in a state where the seal pattern is uncured; 3) a step of superimposing one substrate and the other substrate through a seal pattern; 4) curing the seal pattern.
• the state where the seal pattern is uncured means a state where the curing reaction of the liquid crystal display element sealant has not progressed to the gel point. For this reason, in the process of 2), in order to suppress dissolution of the liquid crystal display element sealant into the liquid crystal, the seal pattern may be semi-cured by light irradiation or heating.
• the step 4 only curing by light irradiation may be performed, but curing by light irradiation may be performed and then curing by heating may be performed. That is, the step 4) includes a step of irradiating the seal pattern with light to cure the seal pattern; when the liquid crystal display element sealant further includes the above-described thermosetting agent E, the seal pattern irradiated with light A step of heating and curing may be further included. Since the liquid crystal display element sealing agent can be cured in a short time by curing by light irradiation, dissolution in the liquid crystal can be suppressed. By combining curing by light irradiation and curing by heating, damage to the liquid crystal layer due to light can be reduced compared to the case of only curing by light irradiation.
• the light to be irradiated is preferably light having a wavelength of 370 to 450 nm. This is because the light having the above wavelength causes relatively little damage to the liquid crystal and the drive electrode.
• a known light source that emits ultraviolet light or visible light can be used.
• a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a xenon lamp, a fluorescent lamp, or the like can be used.
• the light irradiation energy may be energy that can cure the curable compound A.
• the photocuring time is, for example, about 10 minutes although it depends on the composition of the liquid crystal display element sealant.
• thermosetting temperature depends on the composition of the liquid crystal display element sealant, it is 120 ° C., for example, and the thermosetting time is about 2 hours.
• the liquid crystal display element sealant of the present invention has reduced elution into the liquid crystal. Therefore, the liquid crystal display panel having a cured product of the liquid crystal display element sealant of the present invention has little liquid crystal contamination and can have high quality display performance.
• the photocurable resin composition of this invention contains the compound B which shows sufficient light absorptivity also to long wavelength light, it may have favorable sclerosis
• good curability is obtained, not only the dissolution of compound B from the cured product can be reduced, but also compound B exhibits moderate hydrophilicity, so that it is difficult to elute into a liquid crystal exhibiting hydrophobicity. Even if a small amount of compound B is eluted into the liquid crystal, the sensitivity to visible light is not too high, so that an unnecessary reaction with the liquid crystal hardly occurs. Accordingly, good curability in the visible light region can be obtained, and contamination of the liquid crystal can be highly suppressed.
• the peak with the highest intensity (peak with the highest peak height) among all peaks relative to the total area of all detected peaks was defined as the “main peak”.
• Voltage holding ratio of liquid crystal 0.1 g of compound B and 1 g of liquid crystal (MLC-7021-000, manufactured by Merck & Co., Inc.) were put into a vial and heated at 120 ° C. for 1 hour to obtain a liquid crystal mixture. Next, this liquid crystal mixture is taken out and injected into a glass cell (KSSZ-10 / B111M1NSS05, manufactured by EHC) in which a transparent electrode is formed in advance, a voltage of 1 V is applied, and a voltage holding ratio at 60 Hz is measured by a 6254 type measuring device. It was measured by (Toyo Technica). The case where the voltage holding ratio was 95% or more was marked with ⁇ , the case where it was 90% or more and less than 95%, and the case where it was less than 90%. A higher voltage holding ratio means that contamination of the liquid crystal is suppressed.
• NI point drop of liquid crystal 0.1 g of compound B and 1 g of liquid crystal (MLC-7021-000, manufactured by Merck & Co., Inc.) were put into a vial and heated at 120 ° C. for 1 hour to obtain a liquid crystal mixture.
• 10 mg of this liquid crystal mixture was placed in an aluminum open pan (Epolide Service), and the NI point (Nematic-Isotropic transition temperature) was measured with a DTA-TG apparatus (Seiko Instruments). The measurement was performed by heating the liquid crystal mixture from 55 ° C. to 150 ° C. at a temperature rising rate of 2 ° C./min.
• the case where the amount of change with respect to the NI point of the liquid crystal was less than 2 ° C. was evaluated as ⁇ : the case where it was 2 ° C. or higher and lower than 5 ° C.
• the compounds B-1 and B-2 of Experimental Examples 1 and 2 have a higher liquid crystal voltage holding ratio and N than the comparative compounds R-1 to R-3 of Comparative Experimental Examples 1 to 3. -The point I descent result was good. This is probably because the compounds B-1 and B-2 have a hydroxyl group in the molecule and show moderate hydrophilicity, so that elution into the liquid crystal showing hydrophobicity was reduced.
• Curing compound A-1 A methacrylic acid-modified bisphenol F type epoxy resin (95% partially methacrylic product) was synthesized by the following method. 160 g of liquid bisphenol F type epoxy resin (YDF-8170C, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 160 g / eq), 0.1 g of p-methoxyphenol as a polymerization inhibitor, 0.2 g of triethanolamine as a catalyst, and 81.7 g of methacrylic acid was charged into the flask, dried air was fed into the flask, and the mixture was reacted at 90 ° C. with stirring under reflux for 5 hours.
• liquid bisphenol F type epoxy resin YDF-8170C, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 160 g / eq
• 0.1 g of p-methoxyphenol as a polymerization inhibitor 0.1 g of p-methoxyphenol as a polymerization inhibitor
• the obtained reaction product was washed 20 times with ultrapure water to obtain a methacrylic acid-modified bisphenol F type epoxy resin (curable compound A-1).
• a methacrylic acid-modified bisphenol F type epoxy resin curable compound A-1
• 95% of the epoxy groups were methacrylic acid-modified bisphenol F type epoxy resin modified with methacrylic acid.
• the weight average molecular weight was 792.
• Curing compound A-2 An acrylic acid-modified bisphenol F-type epoxy resin (50% partially acrylated product) was synthesized by the following method. First, 175 g of bisphenol F type epoxy resin (YDF-8170C, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 160 g / eq) in a 500 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube, acrylic acid : 37 g, triethanolamine: 0.2 g as a catalyst, and hydroquinone monomethyl ether: 0.2 g as a polymerization inhibitor were mixed and heated and stirred at 110 ° C. for 12 hours while blowing dry air.
• bisphenol F type epoxy resin YDF-8170C, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 160 g / eq
• acrylic acid 37 g
• triethanolamine 0.2 g as a catalyst
• the obtained reaction product was repeatedly washed with ultrapure water 12 times to obtain an acrylic acid-modified bisphenol F type epoxy resin (curable compound A-2).
• curable compound A-2 acrylic acid-modified bisphenol F type epoxy resin
• it was a bisphenol F type epoxy resin in which 50% of the epoxy groups were modified with acryloyl acid.
• the weight average molecular weight was 692.
• Polyethylene glycol diacrylate represented by the following formula: manufactured by Kyoeisha Chemical Co., Ltd., light acrylate 14EG-A, molecular weight 600
• Compound C-1 Polyethylene glycol bis (p-dimethylaminobenzoate) (IGM Resins, Omnipol ASA, see formula below)
• Compound C-2 4,4′-bis (dimethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd., see formula below)
• thermosetting compound D Epoxy resin: jER1004 manufactured by Mitsubishi Chemical Corporation, softening point 97 ° C
• thermosetting agent E Adipic acid dihydrazide: Nippon Kasei Co., Ltd., ADH, melting point 177-184 ° C
• Example 1 420 parts by mass of curable compound A-1 as curable compound A, 200 parts by mass of polyethylene glycol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light acrylate 14EG-A), and compound B obtained in Synthesis Example 1 as compound B -1 is 10 parts by mass, epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER1004) is 50 parts by mass as thermosetting compound D, and adipic acid dihydrazide (manufactured by Nippon Kasei Co., Ltd., ADH) is 90 parts by mass as thermosetting agent E And 130 parts by mass of silica particles (S-100, manufactured by Nippon Shokubai Co., Ltd.) as filler, 70 parts by mass of F351 (manufactured by Aika Kogyo Co., Ltd.) as thermoplastic resin particles, and ⁇ -glycid as a silane coupling agent 20 parts by mass of xylpropyltrimethoxysilane (Shin
• Examples 2 to 9, Comparative Examples 1 to 9 A photocurable resin composition was obtained in the same manner as in Example 1 except that the composition shown in Table 2 or 3 was changed.
• the display characteristics of the obtained photocurable resin composition were evaluated by the following methods.
• a 40 mm ⁇ 45 mm glass substrate (RT-DM88-PIN, manufactured by EHC) on which a transparent electrode and an alignment film were formed in advance using a dispenser (shot master: manufactured by Musashi Engineering)
• a 35 mm ⁇ 40 mm square seal pattern cross-sectional area 3500 ⁇ m 2 ) (main seal) and a similar seal pattern (38 mm ⁇ 43 mm square seal pattern) were formed on the outer periphery.
• liquid crystal MLC-7021-000, manufactured by Merck & Co., Inc.
• a pair of glass substrates was bonded together under reduced pressure, and then bonded to the atmosphere.
• the two glass substrates bonded together are held in a light shielding box for 3 minutes, and then light with a wavelength of 370 to 450 nm is 3000 mJ in a state where the main seal is masked with a substrate coated with a square black matrix of 36 mm ⁇ 41 mm. / Cm 2 irradiation and further heating at 120 ° C. for 1 hour.
• a polarizing film was stuck on both sides of the obtained panel to obtain a liquid crystal display panel.
• ⁇ When the liquid crystal is aligned until the main seal of the obtained liquid crystal display panel and there is no color unevenness, ⁇ , when the color unevenness has occurred over the range of less than 1 mm in the vicinity of the main seal, The case where color unevenness occurred over a range of 1 mm or more from the vicinity was evaluated as x.
• liquid crystal display panel (LCD panel display characteristics test when energized) A liquid crystal display panel was produced in the same manner as the liquid crystal display panel display characteristic test described above. When this liquid crystal display panel is driven with an applied voltage of 5 V using a DC power supply, the liquid crystal display function in the vicinity of the main seal can be exhibited. The case where it occurred was marked as ⁇ , and the case where white unevenness occurred over a range of 1 mm or more from the vicinity of the main seal and it was not driven normally was marked as x.
• the combination of Compound B and the amine sensitizer allows the display of the liquid crystal display panel when not energized. It can be seen that unevenness can be further reduced. This is presumably because the sensitivity of visible light to Compound B can be moderately increased by the amine sensitizer.
• the photocurable resin compositions of Comparative Examples 1 to 9 containing the comparative compound are all poor in display characteristics. This is because the comparative compounds R-1 to R-3 do not have a structure in which a thioether group is bonded to the thioxanthone skeleton, so that the sensitivity to visible light is low and the sealant cannot be sufficiently cured. This is probably because the elution of the sealant component into the liquid crystal could not be sufficiently suppressed. In addition, it is considered that the comparative compounds R-1 to R-3 did not have a hydrophilic hydroxyl group in the molecule, and thus their elution into the liquid crystal itself could not be sufficiently suppressed.
• the present invention is a photocurable resin composition that has sufficient curability for visible light and can highly suppress contamination of liquid crystal when used as, for example, a display element sealant, particularly a liquid crystal display element sealant. Things can be provided.

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