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
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
• • 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 sealant, a liquid crystal display panel, and a method for producing a liquid crystal display panel.
• a liquid crystal display panel includes two transparent substrates having electrodes provided on the surface, a frame-shaped sealing member sandwiched between them, and a liquid crystal material sealed in a region surrounded by the sealing member And have.
• the liquid crystal display panel can be manufactured by a liquid crystal dropping method, for example.
• Production of a liquid crystal display panel by a liquid crystal dropping method is as follows: (1) A liquid crystal sealing agent is applied to the inner edge of a transparent substrate to form a frame for filling with liquid crystal; (2) Liquid crystal is dropped into the frame; (3) After superposing two substrates under high vacuum while the liquid crystal sealant is in an uncured state, (4) curing the liquid crystal sealant.
• liquid crystal dropping method photocuring or thermosetting is performed in a state where the uncured liquid crystal sealant and the liquid crystal material are in contact with each other. Therefore, the liquid crystal sealant is required not only to have high curability but also to reduce contamination of the liquid crystal material.
• a photocurable resin composition containing a compound having a (meth) acryloyl group in the molecule and an anthraquinone derivative as a photopolymerization initiator has been proposed (for example, Patent Document 1).
• a photocurable resin composition comprising a photopolymerizable oligomer, a compound B obtained by reacting hydroxythioxanthone as a photopolymerization initiator with a compound having two or more epoxy groups in the molecule.
• a sealing agent for liquid crystal display elements has been proposed that includes a curable resin and a compound obtained by reacting an oxime ester and a polyfunctional isocyanate as a photopolymerization initiator (for example, Patent Document 3).
• composition shown in Patent Document 3 contains a photopolymerization initiator having low light absorption in the visible light region, the curability to light in the visible light region is low. Since the compositions shown in Patent Documents 1 and 2 contain a photopolymerization initiator having an anthraquinone skeleton or a thioxanthone skeleton, the curability to light in the visible light region is good. There is a demand for further reduction of elution. Thus, it is desired to provide a photocurable resin composition that has high curability with respect to light in the visible light region and can highly suppress liquid crystal contamination.
• the present invention has been made in view of the above problems.
• the photocurability is high in visible light curing and can highly suppress liquid crystal contamination. It aims at providing a resin composition.
• a curable compound A having an ethylenically unsaturated double bond in the molecule, an anthraquinone skeleton or thioxanthone skeleton in the molecule, and an NHCO group, and an NHCO group equivalent represented by the formula (I) is The photocurable resin composition containing the compound B which is 350 g / eq or less.
• NHCO group equivalent (g / eq) molecular weight / number of NHCO groups contained in one molecule: Formula (I) [2]
• L 1 each independently represents a single bond, an alkylene group having 1 to 10 carbon atoms, an alkyleneoxy group having 1 to 10 carbon atoms, an alkylenethio group having 1 to 10 carbon atoms, Represents an arylene group having 6 to 10 carbon atoms, an aryleneoxy group having 6 to 10 carbon atoms, or an arylenethio group having 6 to 10 carbon atoms, and X is derived from a compound having at least p isocyanate groups in the molecule.
• thermosetting compound C having an epoxy group in the molecule and a thermosetting agent D, and the thermosetting compound C is different from the curable compound A, [1] to [7 ]
• the photocurable resin composition in any one of.
• the thermosetting agent D 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.
• the photocurable resin composition according to [8] which is as described above.
• a display element sealing agent comprising the photocurable resin composition according to any one of [1] to [9].
• a liquid crystal sealing agent comprising the photocurable resin composition according to any one of [1] to [9].
• the liquid crystal sealant according to [11] which is a liquid crystal sealant for a liquid crystal dropping method.
• [13] In the step of forming a seal pattern on one substrate using the liquid crystal sealant according to [11] or [12], and in the state of the seal pattern in an uncured state, or Dropping the liquid crystal on the other substrate paired with the one substrate, superimposing the one substrate and the other substrate through the seal pattern, and curing the seal pattern; A method for manufacturing a liquid crystal display panel.
• [17] including a pair of substrates, a frame-shaped sealing member disposed between the pair of substrates, and a liquid crystal layer filled in a space surrounded by the sealing member between the pair of substrates, A liquid crystal display panel, wherein the seal member is a cured product of the liquid crystal sealant according to [11] or [12].
• the present invention when used as a display element sealant, particularly a liquid crystal sealant, it is an object to provide a photocurable resin composition that has high curability to visible light and can highly suppress liquid crystal contamination.
• photocurable resin composition contains the curable compound A and the compound B, and may further contain the thermosetting compound C and the thermosetting agent D as needed.
• 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.
• the curable compound A does not have an anthraquinone skeleton or a thioxanthone skeleton.
• 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 it can be imparted with photocurability and thermosetting properties. 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 C, the epoxy compound, and a 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 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).
• the content of the curable compound A is preferably 40 to 80% by mass, and more preferably 50 to 75% by mass with respect to the photocurable resin composition.
• Compound B contained in the photocurable resin composition of the present invention has an anthraquinone skeleton or thioxanthone skeleton and an NHCO group in the molecule.
• the anthraquinone skeleton or thioxanthone skeleton contained in the compound B can excite by absorbing light in the visible light region well, and can cause a hydrogen abstraction reaction from the curable compound A. Since the NHCO group contained in Compound B exhibits moderate hydrophilicity, the elution of Compound B into the liquid crystal material can be preferably suppressed. Therefore, the compound B can preferably function as a photopolymerization initiator for a photocurable resin composition used as a display element sealant, particularly a liquid crystal sealant.
• the number of anthraquinone skeleton or thioxanthone skeleton per molecule is 1 or 2 or more. Even if the content of Compound B is small, the number of anthraquinone skeletons or thioxanthone skeletons per molecule is preferably 2 or more from the viewpoint of obtaining sufficient curability for light in the visible light region.
• the number of NHCO groups per molecule is 1 or 2 or more. From the viewpoint of highly suppressing the elution of Compound B into the liquid crystal material, the number of NHCO groups per molecule is preferably 2 or more, and more preferably 3 or more.
• Compound B preferably has a burette skeleton (—NHCO (N—) CONH—) or an allophanate skeleton (—NHCO (N—) COO—) from the viewpoint of easily increasing the number of NHCO groups per molecule. .
• Compound B may further have an ethylenically unsaturated double bond in the molecule.
• compound B and curable compound A undergo a polymerization reaction during curing, and elution of compound B into the liquid crystal material is further suppressed.
• Compound B is obtained by reacting “anthraquinone compound b1 having a hydroxy group in the molecule or thioxanthone compound b2 having a hydroxy group in the molecule” with “compound b3 having an isocyanate group in the molecule”.
• Anthraquinone compound b1 having a hydroxy group in the molecule is represented by the following formula (1).
• the “thioxanthone compound b2 having a hydroxy group in the molecule” is represented by the following formula (2).
• L 1 in the formulas (1) and (2) each independently represents a single bond or a divalent organic group.
• the divalent organic group includes an alkylene group having 1 to 10 carbon atoms (for example, a methylene group and an ethylene group), an alkyleneoxy group having 1 to 10 carbon atoms (for example, a methyleneoxy group and an ethyleneoxy group), 10 alkylenethio groups (for example, methylenethio group (—S—CH 2 —), ethylenethio group (—S—CH 2 CH 2 —), etc.), arylene groups having 6 to 10 carbon atoms (for example, phenylene groups), 6 carbon atoms Or an arylenethio group having 6 to 10 carbon atoms (for example, a phenylenethio group).
• a thioether group (—S—) is bonded to an anthraquinone skeleton or a thioxanthone skeleton, it is easy to absorb light on the long wavelength side. Therefore, an alkylenethio group having 1 to 10 carbon atoms or 6 to 10 carbon atoms is preferred. An arylenethio group is preferred.
• M in the formulas (1) and (2) is an integer of 1 or more, preferably 1.
• — (L 1 —OH) may be bonded to any one of the 1st to 8th carbon atoms of the anthraquinone skeleton or thioxanthone skeleton, but is preferably bonded to the 2nd or 7th carbon atom. .
• the compound represented by the formula (1) is preferably represented by the following formula (1 ′); the compound represented by the formula (2) is preferably represented by the following formula (2 ′).
• —L 1 —OH in the formulas (1 ′) and (2 ′) may be bonded to any one of the 1st to 8th carbon atoms of the anthraquinone skeleton or thioxanthone skeleton, but the 2nd or 7th carbon It is preferably bonded to an atom.
• the compound b3 having an isocyanate group in the molecule is a compound having one or more isocyanate groups in the molecule.
• a compound having two or more isocyanate groups in the molecule is preferable in that the NHCO group equivalent of the obtained compound B can be easily adjusted to a certain value or less.
• the number of isocyanate groups per molecule is not particularly limited, but is preferably 2 to 4 and more preferably 2 to 3 from the viewpoint that the NHCO group equivalent of Compound B can be easily kept below a certain level.
• the compound having two or more isocyanate groups in the molecule preferably has an NHCO group in the molecule, and a burette skeleton (—NHCO (N—) CONH—), an allophanate skeleton (—NHCO (N—) COO—) Alternatively, it preferably has a urethane skeleton, and more preferably has a burette skeleton or an allophanate skeleton. That is, a compound having two or more isocyanate groups in the molecule can be represented by, for example, the following formula (3a) or (3b).
• R 1 in formula (3a) and R 2 in formula (3b) are each a linear, branched or cyclic saturated aliphatic hydrocarbon group or aromatic hydrocarbon group which may have an NHCO group. .
• the number of NHCO groups contained in R 1 and R 2 is 0 or 1 or more, and preferably 2 or more.
• R 1 and R 2 preferably include a structure represented by the following formula ( ⁇ ), ( ⁇ ) or ( ⁇ ); and may have a structure represented by the following formula ( ⁇ ) or formula ( ⁇ ). More preferred.
• (R 3 in the formula ( ⁇ ) represents a saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group derived from a polyol described later, and n is an integer of 1 or more)
• the compound having two or more isocyanate groups in the molecule is, for example, a burette body or allophanate body obtained from diisocyanate, or a urethane prepolymer obtained by reacting polyisocyanate and polyol, and having an isocyanate group at the molecular end. It is possible.
• diisocyanates used as raw materials for burettes or allophanates include aliphatic diisocyanates having 1 to 10 carbon atoms such as tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate; cyclohexylene diisocyanate, hydrogenated C6-C15 alicyclic diisocyanates such as xylylene diisocyanate and isophorone diisocyanate; and C6-C15 such as tolylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate Aromatic diisocyanates are included.
• the polyisocyanate used as a raw material for the urethane prepolymer is a polyfunctional aliphatic, alicyclic or aromatic isocyanate, and examples thereof include the aforementioned diisocyanate.
• the polyol used as a raw material for the urethane prepolymer include aliphatic polyols such as ethylene glycol, 1,3-propanediol, polyethylene glycol, dipropylene glycol, and pentaerythritol; 1,4-cyclohexanedimethanol, 1,4- Examples include alicyclic polyols such as cyclohexanediol, hydrogenated bisphenol A, and hydrogenated bisphenol F; aromatic polyols such as phenol A and bisphenol F, and the like.
• Compound B is preferably obtained by reacting “compound represented by formula (1 ′) or formula (2 ′)” with “compound having two or more isocyanate groups in the molecule”; 1 ′) or a compound represented by formula (2 ′) ”and“ a compound represented by formula (3a) or (3b) (preferably R 1 or R 2 has an NHCO group) ” It is more preferable to be obtained.
• reaction scheme shows an example in which compound B is obtained by reacting a compound represented by formula (1 ′) with a compound represented by formula (3b).
• “Hydroxy group-containing compound b4” is a compound having a hydroxy group in the molecule.
• the hydroxy group of the compound having a hydroxy group in the molecule can react with the isocyanate group of the “compound having two or more isocyanate groups in the molecule” to further form —O—CONH—.
• Examples of the compound having a hydroxy group in the molecule include monoalcohols having 1 to 20 carbon atoms such as methanol, ethanol, propanol, butanol, pentanol, hexanol, 1-octadecanol and the like.
• the compound having a hydroxy group in the molecule may further have an ethylenically unsaturated double bond. Thereby, an ethylenically unsaturated double bond can be introduced into the compound B.
• the hydroxy group-containing compound having an ethylenically unsaturated double bond in the molecule include (meth) acrylate substituted with a hydroxy group such as 4-hydroxybutyl acrylate.
• the compound B is represented by following formula (4) or (5).
• L 1 of formula (4) and (5) are the same meaning as L 1 in formula (1) and (2).
• X in the formulas (4) and (5) represents an organic group derived from a compound having at least p isocyanate groups in the molecule.
• the group derived from a compound having at least p isocyanate groups in the molecule is preferably a group derived from a compound having two or more isocyanate groups in the molecule, and is represented by the formula (3a). More preferably, it is a divalent group derived from the compound represented by formula (3b) or a trivalent group derived from the compound represented by formula (3b).
• P in the formulas (4) and (5) represents an integer of 1 to 5, preferably 2 or 3.
• the group represented by —L 1 —OX may be bonded to any one of the 1st to 8th carbon atoms of the anthraquinone skeleton or thioxanthone skeleton, but may be bonded to the 2nd or 7th carbon atom. It is preferable.
• compound B examples include a compound obtained by reacting 2- (2-hydroxyethylthio) -9,10-anthraquinone with a modified product of hexamethylene diisocyanate biuret, 2-hydroxymethylanthraquinone and modified with hexamethylene diisocyanate biuret.
• a compound obtained by reacting with a compound, a compound obtained by reacting 2- (2-hydroxyethylthio) -9,10-anthraquinone with a modified product of hexamethylene diisocyanate allophanate, 2-hydroxythioxanthone and hexamethylene diisocyanate biuret A compound obtained by reacting with a modified product, a compound obtained by reacting 2-hydroxythioxanthone with a modified product of hexamethylene diisocyanate allophanate, 2- (2-hydroxyethylthio) -thioxanthen-9-one;
• Compounds obtained by reacting with a hexamethylene diisocyanate biuret-modified product, compounds obtained by reacting 2- (2-hydroxyethylthio) -thioxanthen-9-one with a hexamethylene diisocyanate allophanate-modified product and these Examples include compounds obtained by further reacting compounds with octadecanol or 4-
• the NHCO group equivalent of Compound B is preferably 350 g / eq or less. If the NHCO group equivalent of Compound B is 350 g / eq or less, the number of NHCO groups contained in Compound B is relatively large, so that the hydrophilicity is moderately increased and the photocurable resin composition is used as a liquid crystal sealant. Elution of the compound B into the liquid crystal material can be suppressed.
• the NHCO group equivalent of Compound B is more preferably 200 to 350 g / eq, and further preferably 230 to 330 g / eq.
• NHCO group equivalent of Compound B is 200 g / eq or more, the moisture resistance of the cured product of the photocurable resin composition is hardly impaired.
• the NHCO group equivalent of compound B is defined by the following formula (I).
• NHCO group equivalent (g / eq) molecular weight / number of NHCO groups contained in one molecule: Formula (I)
• the molecular weight of Compound B is preferably 500 or more and 5000 or less, for example.
• the “molecular weight” of compound B is the “relative molecular mass” of the molecular structure of the main peak when a main peak is detected when high performance liquid chromatography (HPLC: High Performance Liquid Crystal) is performed under the following conditions. When the main peak is not detected, the weight average molecular weight is assumed.
• 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 weight average molecular weight of Compound B can be measured in terms of standard polystyrene by gel permeation chromatography (GPC).
• the molecular weight of Compound B is more preferably 500 or more and 3000 or less, and further preferably 700 or more and 1500 or less.
• the NHCO group equivalent of compound B can be confirmed by combining high performance liquid chromatography (HPLC) and liquid chromatography mass spectrometry (LC / MS) with NMR measurement or IR measurement. Specifically, 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.
• the relative molecular mass and the composition formula of the main peak detected by a detector having a wavelength of 400 nm characteristic of the anthraquinone skeleton or thioxanthone skeleton are analyzed by liquid chromatography mass spectrometry (LC / MS ) To measure.
• the 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. 3)
• NMR measurement or IR measurement is performed on the sample solution obtained in 1).
• Compound B may be one type or a combination of two or more types. For example, a compound having an anthraquinone skeleton in the molecule and a compound having a thioxanthone skeleton in the molecule may be combined.
• 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, elution into the liquid crystal material is unlikely to occur, and sufficient photocurability is easily obtained.
• the content of the compound B is more preferably 0.1 to 5% by mass with respect to the curable compound A, preferably 0.1 to It is more preferable that it is 3 mass%, and it is especially preferable that it is 0.1 to 2 mass%.
• the content of the compound B is more preferably 0.1 to 6% by mass with respect to the curable compound A, and 0.1% by mass. % Or more and less than 4% by mass.
• thermosetting compound C is preferably an epoxy compound having an epoxy group in the molecule. However, the thermosetting compound C is different from the curable compound A.
• the thermosetting compound C 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, have low solubility and diffusibility in liquid crystal when using a photocurable resin composition as a liquid crystal sealant, and not only improve the display characteristics of the resulting liquid crystal panel, but also the moisture resistance of the cured product. Can improve sex.
• 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 softening point can be measured by the ring and ball method defined in JIS K7234.
• the content of the thermosetting compound C is preferably 3 to 20% by mass with respect to the photocurable resin composition.
• the content of the thermosetting compound C with respect to the photocurable resin composition is 3% by mass or more, the moisture resistance of the cured product of the photocurable resin composition can be easily improved.
• the content of the thermosetting compound C with respect to the photocurable resin composition is 20% by mass or less, an excessive increase in the viscosity of the photocurable resin composition can be suppressed.
• the content of the thermosetting compound C is more preferably 3 to 15% by mass, and further preferably 4 to 15% by mass with respect to the photocurable resin composition.
• the content of the thermosetting compound C is preferably 3.8 to 50% by mass, more preferably 5 to 30% by mass with respect to the curable compound A.
• the content of the thermosetting compound C with respect to the curable compound A is 5% by mass or more, the moisture resistance of the cured product and the adhesive strength to the glass substrate can be further enhanced.
• the compatibility with the conductive compound A tends to be further improved.
• thermosetting agent D is a compound that does not cure the thermosetting compound C 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 D is excellent in storage stability and excellent in thermosetting.
• the thermosetting agent D is preferably an epoxy curing agent.
• Epoxy curing agent is an epoxy curing agent having a melting point of 50 ° C. or more and 250 ° C. or less, although it depends on the heat curing temperature from the viewpoint of enhancing the viscosity stability of the photo-curable resin composition and not impairing the moisture resistance of the cured product
• An epoxy curing agent having a melting point of 100 ° C. or higher and 200 ° C. or lower is more preferable, and an epoxy curing agent having a melting point of 150 ° C. or higher and 200 ° C. or lower is further preferable.
• epoxy curing agents include organic acid dihydrazide thermal latent curing agents, imidazole thermal latent curing agents, dicyandiamide thermal latent curing agents, amine adduct thermal latent curing agents, and polyamine thermal latent curing. Agent is included.
• 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.
• Examples of the dicyandiamide-based heat latent curing agent include dicyandiamide (melting point: 209 ° C.).
• 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. Amicure PN-23 (melting point 100 ° C.), Ajinomoto Fine Techno Co., Ltd. Amicure PN-31 (melting point 115 ° C.), Ajinomoto Fine Techno ( Amicure PN-H (melting point 115 ° C.) manufactured by Ajinomoto Fine Techno Co., Ltd. Amycure MY-24 (melting point 120 ° C.), Amicure MY-H (melting point 131 ° C.) manufactured by Ajinomoto Fine Techno Co., etc. It is.
• the polyamine thermal latent curing agent is a thermal latent curing agent having a polymer structure obtained by reacting an amine and an epoxy.
• examples thereof include ADEKA HARDNER EH4339S (softening point 120 to 130, manufactured by ADEKA Corporation).
• Adeka Hardener EH4357S softening point 73 to 83 ° C. manufactured by ADEKA Corporation.
• dihydrazide thermal latent curing agents, imidazole thermal latent curing agents, amine adduct thermal latent curing agents, and polyamine thermal latent curing agents are preferred.
• the epoxy curing agent may be only one type or a combination of two or more types.
• the content of the thermosetting agent D 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 D 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 content of the thermosetting agent D is preferably 3.8 to 75% by mass, more preferably 3.8 to 50% by mass with respect to the curable compound A, and 10 to 40% by mass. More preferably.
• the content of the thermosetting agent D with respect to the curable compound A is 10% by mass or more, the curability of the curable compound A at the time of heating is further enhanced, and when it is 40% by mass or less, liquid crystal contamination is further suppressed. It's easy to do.
• the total content of the thermosetting compound C and the thermosetting agent D is preferably 6 to 50% by mass, more preferably 6 to 35% by mass, and 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 polymer fine particles as necessary.
• the thermoplastic polymer fine particles contain a thermoplastic polymer 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 size of 0.05 to 5 ⁇ m, preferably 0.8. It can be 1 to 3 ⁇ m.
• the photocurable resin composition containing such thermoplastic polymer fine 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 polymer fine particles when forming a seal member having a narrow line width.
• the number average particle diameter can be measured with a dry particle size distribution meter.
• thermoplastic polymer fine 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 polymer fine particles is preferably 5 to 40% by mass, more preferably 7 to 30% by mass with respect to the photocurable resin composition.
• the thermoplastic polymer fine particle can preferably relieve the shrinkage stress during the heat curing of the photocurable resin composition, and can easily form a seal member with a desired 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.
• 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, Inorganic fillers such as kaolin, talc, glass beads, sericite activated clay, bentonite, aluminum nitride, silicon nitride are included. 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 45% by mass with respect to the photocurable resin composition.
• the content of the filler is more preferably 10 to 30% by mass with respect to the photocurable resin composition.
• the photocurable resin composition of the present invention includes 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 sensitizer, as necessary. Additives such as plasticizers and antifoaming agents may further be 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 curable compound A.
• 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 total content of other components E is preferably 1 to 50% by mass with respect to the photocurable resin composition.
• the total content of other components E is 50% by mass or less, the viscosity of the photocurable resin composition is hardly excessively increased, and the coating stability is not easily impaired.
• 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 sealant and more preferably a liquid crystal sealant for a liquid crystal dropping method because the photocurable resin composition of the present invention can satisfactorily suppress liquid crystal contamination. preferable.
• Compound B contained in the photocurable resin composition of the present invention exhibits good light absorption even for light having a long wavelength, so that curing in a short time while reducing damage to the liquid crystal layer due to light. Is possible.
• compound B since compound B contains a relatively large number of NHCO groups per molecule, it has moderate hydrophilicity and can highly suppress elution into the liquid crystal material.
• 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 display substrate, a counter substrate that is paired with the display substrate, a frame-shaped sealing member disposed between the display substrate and the counter substrate, and a space between the display substrate and the counter substrate. And a liquid crystal layer filled in a space surrounded by the seal member.
• the seal member can be a cured product of the liquid crystal sealant of the present invention.
• the liquid crystal sealing agent of the present invention comprises the photocurable resin composition of the present invention.
• the display substrate and the counter substrate 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 the display substrate or the counter substrate.
• An alignment film may be further disposed on the surface of the display substrate or the counter 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 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 sealant of the present invention on one substrate; 2) a step of dropping 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 when the seal pattern is in an uncured state; 3) a step of superimposing one substrate and the other substrate through a seal pattern; 4) curing the seal pattern.
• the uncured state of the seal pattern means a state in which the curing reaction of the liquid crystal sealant has not progressed to the gel point. For this reason, in the step 2), in order to suppress dissolution of the liquid crystal sealant in the liquid crystal, the seal pattern may be semi-cured by light irradiation or heating.
• One substrate and the other substrate are a display substrate and a counter substrate, respectively.
• 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. Since the liquid crystal sealant 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 material 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 sealant.
• thermosetting temperature is 120 ° C., for example, although it depends on the composition of the liquid crystal sealant, and the thermosetting time is about 2 hours.
• the liquid crystal sealant of the present invention has reduced dissolution in liquid crystals. Therefore, a liquid crystal display panel having a cured product of the liquid crystal sealant of the present invention is less contaminated with liquid crystals and can have high quality display performance.
• Synthesis and Evaluation of Compound B and Comparative Compound (1) Synthesis (Synthesis Example 1) 2. Hexamethylene diisocyanate biuret modified (manufactured by Mitsui Chemicals, Takenate D-165N, isocyanate equivalent 179.5 g / eq) into a four-necked flask equipped with a stirrer, nitrogen gas inlet tube, reflux condenser, and thermometer. 16 g and 40 g of toluene were added and stirred at 80 ° C.
• the peak with the highest intensity (peak with the highest peak height) among all peaks detected at a detection wavelength of 400 nm was defined as “main peak”, and the presence or absence of the main peak was confirmed.
• compounds B-1 to B-9, compounds R-1 to R-3, R-5 to R-7, 2- (2-hydroxyethylthio) -9,10-anthraquinone, 2-hydroxymethyl- Main peaks were detected for 9,10-anthraquinone (HMAQ) and 2- (2-hydroxyethylthio) -thioxanthen-9-one.
• HMAQ 9,10-anthraquinone
• 2- (2-hydroxyethylthio) -thioxanthen-9-one On the other hand, no main peak was detected for compound R-4.
• Voltage holding ratio of liquid crystal 0.1 g of the above compound 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, poured 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 the contamination of the liquid crystal is suppressed.
• NI point drop of liquid crystal 0.1 g of the above compound 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 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.
• Table 5 shows the measurement results of Experimental Examples 1 to 9, and Table 6 shows the measurement results of Comparative Experimental Examples 1 to 10.
• “molecular weight” in Tables 5 and 6 since the main peak was not detected by HPLC measurement in compound R-4, “weight average molecular weight” was described. Since the main peak of other compounds was detected by HPLC measurement, the “relative molecular mass” (molecular weight measured by LC / MS) corresponding to the apex of the main peak was described.
• compounds B-6 to B-9 of Experimental Examples 6 to 9 having an NHCO group equivalent of 350 g / eq or less are compounds R-5 of Comparative Experimental Examples 7 to 9 having an NHCO group equivalent of more than 350 g / eq. It can be seen that there is less NI point depression than ⁇ R-7.
• 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 (Epototo 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 were charged into the flask, dried air was fed, and the mixture was reacted at 90 ° C. with reflux stirring for 5 hours.
• liquid bisphenol F type epoxy resin Epoto 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 polymer
• thermosetting compound C JER resin 1004 manufactured by Mitsubishi Chemical Corporation (bisphenol A type epoxy resin, epoxy equivalent 875-975 g / eq, molecular weight 1650, softening point 97 ° C.)
• thermosetting agent D ADH (Nippon Kasei Co., Ltd., adipic acid dihydrazide, melting point 177-184 ° C)
• Silica particles S-100 manufactured by Nippon Shokubai Co., Ltd.
• Fine particle polymer F351 thermoplastic resin particles, manufactured by Aika Kogyo Co., Ltd., softening point 120 ° C., average particle diameter 0.3 ⁇ m
• KBM-403 ⁇ -glycidoxypropyltrimethoxysilane, silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd.
• Example 1 As the curable compound A, 430 parts by mass of the synthesized curable compound A-1 and 200 parts by mass of Kyoeisha Chemical Light Acrylate 14EG-A, and as the compound B, 10% of the compound B-1 obtained in Synthesis Example 1 were used. 50 parts by mass of jER resin 1004 manufactured by Mitsubishi Chemical Corporation as thermosetting compound C, 90 parts by mass of ADH manufactured by Nippon Kasei Co., Ltd. as thermosetting agent D, and silica produced by Nippon Shokubai Co., Ltd. as other components E 130 parts by mass of particles S-100, 70 parts by mass of fine polymer F351 manufactured by Aika and 20 parts by mass of silane coupling agent KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd. are converted into a uniform liquid using a three-roll mill. The mixture was sufficiently mixed to obtain a photocurable resin composition.
• Examples 2 to 9, Comparative Examples 1 to 10 A photocurable resin composition was obtained in the same manner as in Example 1 except that the composition shown in Table 7 or 8 was changed.
• the display characteristics of the obtained photocurable resin composition were evaluated by the following methods.
• LCD display panel display characteristics test A 40 mm ⁇ 45 mm glass substrate (RT-DM88-PIN, manufactured by EHC) in which a transparent electrode and an alignment film were formed in advance using a dispenser (manufactured by Musashi Engineering) with the obtained photocurable resin composition
• a 35 mm ⁇ 40 mm square seal pattern cross-sectional area 3500 ⁇ m 2
• a 38 mm ⁇ 43 mm square seal pattern were formed as the main seal.
• a liquid crystal material 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. Then, after holding the two bonded glass substrates in a light shielding box for 3 minutes, the main seal was masked with a substrate coated with a square black matrix of 36 mm ⁇ 41 mm, and 3000 mJ / cm 2 of visible light was emitted. The main seal was cured by irradiating the contained light (light having a wavelength of 370 to 450 nm) and further heating at 120 ° C. for 1 hour. Then, a polarizing film was affixed on both surfaces of the obtained liquid crystal cell, and the liquid crystal display panel was obtained.
• a liquid crystal display panel was produced in the same manner as the liquid crystal display panel display characteristic test, and was driven with an applied voltage of 5 V using a DC power source. At that time, when there is no white unevenness in the vicinity of the main seal and the liquid crystal display function is sufficiently exerted, ⁇ : when white unevenness occurs in the vicinity of the main seal over a range of less than 1 mm, ⁇ : 1 mm from the vicinity of the main seal A case where white unevenness occurred over the above range and the device was not driven normally was marked as x. O or more was defined as the present invention.
• the present invention can provide a photocurable resin composition that is highly curable with respect to visible light and can highly suppress liquid crystal contamination when used as, for example, a display element sealant, particularly a liquid crystal sealant.

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