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
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
• • 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
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/02—Polythioethers
  • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
  • C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
  • C08L81/02—Polythioethers; Polythioether-ethers
• • 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
• • 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
  • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
  • C09K2323/05—Bonding or intermediate layer characterised by chemical composition, e.g. sealant or spacer

Definitions

• the present invention relates to a curable resin composition used as a sealing material for film liquid crystal panels.
• the curable resin composition is stable in an uncured state, and the cured product does not cause alignment disorder of the liquid crystal even when it is in contact with the liquid crystal in a harsh wet-heat environment or under acidic conditions.
• the present invention relates to a curable resin composition that forms a sealing material for film liquid crystals that is excellent in followability to substrates regardless of changes in temperature environment.
• the present invention also relates to a film liquid crystal panel using a sealing material made of the curable resin composition.
• a liquid crystal panel is widely used for image display in various electronic devices, including mobile phones and personal computers.
• a liquid crystal panel usually includes a pair of glass substrates having electrodes on their surfaces, a frame-like sealing material sandwiched between them, and a liquid crystal layer surrounded by the sealing material.
• a photocurable acrylic resin composition has been used for the sealing material.
• conventional acrylic resin compositions in addition to curing immediately with light, are stable in an uncured state, and workability such as not progressing gelation during storage at room temperature or during work. Although it is excellent in terms of productivity, there is a problem that a large amount of outgassing is generated in the manufacturing process and the adhesiveness between the sealing material and the base material is lowered.
• the sealing material is required to protect the liquid crystal in a harsh moist and hot environment. Therefore, in a moist heat environment or under an acidic condition, there is a problem that the liquid crystal is contaminated with moisture, acid, and decomposition products of the encapsulant, and the alignment of the liquid crystal is disturbed.
• Patent Document 1 a resin composition containing a thiol monomer having a thiol group and an ene monomer having a carbon-carbon double bond can suppress the generation of outgassing and improve the adhesiveness of the sealant. It is known (Patent Document 1). In addition, in Patent Document 1, it was confirmed that by improving the moisture barrier property and durability of the sealing material, even when the sealing material and the liquid crystal are in contact with each other in a harsh moist and hot environment, the alignment disorder of the liquid crystal does not occur.
• the sealing material of Patent Document 1 has a problem that liquid crystal orientation disorder occurs under acidic conditions.
• film liquid crystal panels using flexible film materials as base materials have attracted attention and are being developed.
• the sealing material used for this film liquid crystal panel is required to be highly flexible and tough and follow the film substrate. Furthermore, in view of actual use, this followability is also required after an accelerated test simulating changes in the temperature environment to which the film liquid crystal panel may be exposed.
• the sealing material of Patent Document 1 lacks flexibility in exchange for moisture barrier properties, it does not have sufficient conformability to a flexible film substrate, and the sealing material peels off from the film. occurred.
• thiol monomers and ene monomers are generally highly reactive, the sealing material of Patent Document 1 lacks stability in an uncured state, and there is also the problem of poor workability and productivity. .
• the present invention has been accomplished in view of the above-mentioned actual situation, and the problem is that the curable resin composition is stable in an uncured state, and the cured product is a liquid crystal in a harsh moist heat environment or under acidic conditions.
• a curable resin composition used as a sealing material for film liquid crystal panels which does not cause disordered alignment of liquid crystals even in a contact state, and has excellent conformability to substrates regardless of changes in temperature environment. and to provide a film liquid crystal panel using the curable resin composition as a sealing material.
• the present inventors have made intensive studies to solve the above problems, combining a specific polyfunctional (meth) acrylic compound and a specific polyfunctional (meth) allyl compound, and further containing a polyfunctional thiol compound.
• a curable resin composition By using a curable resin composition, the curable resin composition is stable in an uncured state, and the cured product is in contact with the liquid crystal in a harsh moist and heat environment or under acidic conditions.
• the present inventors have found that a sealing material for film liquid crystal panels that does not cause disorder can be obtained. Furthermore, the present inventors have found that this sealing material has both flexibility and toughness and is excellent in followability to the base material regardless of changes in the temperature environment, leading to the completion of the present invention.
• the present invention is the following [1] to [2].
• [1] (A) a polyfunctional thiol compound having 2 to 6 thiol groups; (B) a polyfunctional (meth)acrylic compound having 3 to 6 (meth)acrylic groups and having a (meth)acrylic equivalent of 100 to 250; (C) a polyfunctional allyl compound having 2 to 4 (meth)allyl groups; (D) a photopolymerization initiator,
• the mixing mass ratio (B)/(C) of (B) and (C) is 0.1 to 1.0,
• the total ratio of the functional group concentration of the thiol group in (A) and the functional group concentration of the polymerizable unsaturated bonds in (B) and (C) (thiol group/polymerizable unsaturated bond) is 0.5 to 3.0
• [2] A film liquid crystal panel whose edges are sealed with the curable resin composition described in [1
• (meth)allyl compound means a generic term including both compounds having an allyl group and compounds having a methallyl group, and the same applies to "(meth)acryl group” and the like.
• ⁇ to XX indicating a numerical range is a concept including its lower limit (“ ⁇ ") and upper limit (“XX”) unless otherwise specified. That is, it means “more than XX and less than XX” exactly.
• the curable resin composition is stable in an uncured state, and even when the cured product is in contact with the liquid crystal in a harsh wet-heat environment or under acidic conditions, the alignment disorder of the liquid crystal does not occur.
• a curable resin composition used as a sealing material for film liquid crystal panels which exhibits excellent followability to substrates regardless of changes in temperature environment.
• a film liquid crystal panel using the curable resin composition as a sealing material it is possible to provide a film liquid crystal panel using the curable resin composition as a sealing material.
• the present invention will be described in detail below.
• the curable resin composition of the present invention is used as a sealing material for film liquid crystal panels, and contains the following (A), (B), (C) and (D) as essential components.
• Polyfunctional thiol compound (A) is a compound having 2 to 6 thiol groups.
• a polyfunctional thiol compound (A) can also be used individually by 1 type, and can also use 2 or more types together. By containing such a compound, a thiol-ene reaction proceeds with other components, and curability can be enhanced.
• the formed thioether bond can change the bond angle flexibly compared to the bond of atoms such as C, O, and N, so the cured product has high flexibility and the conformability of the sealing material to the base material can be improved.
• cured products made from thioether bonds have highly flexible bond angles and can be cured at a high density so that atoms fill the gaps between bonds. It is possible to prevent alignment disorder of liquid crystals even under test or under acidic conditions.
• Polyfunctional thiol compound (A) is preferably a compound represented by the following formula 1. (In the formula, a is an integer of 2 to 6, and R 1 is a divalent to hexavalent organic group having 10 to 60 carbon atoms.)
• a is 3 to 6 from the viewpoint that the barrier properties of the sealing material for film liquid crystal panels against moisture and acid can be improved, and liquid crystal alignment disorder can be suppressed even under severe moist heat tests and under acidic conditions. is preferred. If a in the formula is within this range, a good cured product can be obtained without large shrinkage on curing and deterioration of conformability to the substrate after curing. From the same viewpoint, R 1 is also preferably trivalent to hexavalent. The carbon number of R 1 is 10-60, preferably 10-45, more preferably 12-30. If the carbon number of R 1 is within this range, the cured product of the curable resin composition has a sufficient crosslink density, and the sealing material has excellent barrier properties against moisture and acids, and can It is possible to suppress the alignment disorder of the liquid crystal even under the conditions.
• An organic group is a group that contains C and may further contain at least one element selected from the group consisting of Si, N, P, O, and S.
• the organic group may be a polymer having repeating units.
• the structure may contain, for example, a ketone group, an ester group, an ether group, a hydroxyl group, an amide group, a thioether group, an isocyanurate group, a glycoluril group, or the like.
• polyfunctional thiol compound (A) examples include dipentaerythritol hexakis (3-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate ), trimethylol ethane tris (2-mercaptoacetate), trimethylol ethane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 1, 2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7 -dimercaptomethyl-1,11-dimercapto-3,6,9-tri
• polyfunctional thiols having a pentaerythritol skeleton polyfunctional thiols having a dipentaerythritol skeleton, and polyfunctional thiols having an isocyanurate skeleton are preferred.
• 3-Mercaptopropionyloxy)-ethyl]-isocyanurate is preferred.
• a commercially available product or a synthesized product may be used as the polyfunctional thiol compound (A).
• a synthesis method for example, it can be obtained by subjecting a polyhydric alcohol such as pentaerythritol and a mercapto group-containing carboxylic acid such as 3-mercaptopropionic acid to an esterification reaction by a known method.
• the polyfunctional (meth)acrylic compound (B) is a compound having 3-6 (meth)acrylic groups and a (meth)acrylic equivalent of 100-250.
• the (meth)acrylic equivalent is the number obtained by dividing the number of (meth)acrylic groups contained from the molecular weight.
• the polyfunctional (meth)acrylic compound (B) can be used alone or in combination of two or more.
• the polyfunctional thiol compound (A) and the polyfunctional (meth)allyl compound (C) have high reactivity, and the uncured product of the curable resin composition containing them is unstable and difficult to use. Although it is a problem, since the reactivity can be suppressed by coexisting the polyfunctional (meth)acrylic compound (B), the stability of the uncured product of the curable resin composition is increased, and the usability is improved. can be done.
• the (meth)acrylic equivalent of the polyfunctional (meth)acrylic compound (B) maintains the flexibility of the cured product of the curable resin composition and barrier properties from moisture and acids, and seals regardless of changes in the temperature environment. It is preferably 120 to 200 from the viewpoint that the followability of the stopper material to the base material can be enhanced.
• the polyfunctional (meth)acrylic compound (B) is preferably a compound represented by Formula 2 below.
• b is an integer of 3 to 6.
• R 2 is a hydrogen atom or a methyl group.
• R 3 is a trivalent to hexavalent organic group having 5 to 70 carbon atoms.
• R 2 in the formula is a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of increasing the flexibility of the cured product of the curable resin composition and enhancing the conformability of the encapsulant to the base material.
• b is an integer of 3 to 6, and within this range, the cured product of the curable resin composition can be sealed regardless of changes in temperature environment while maintaining the flexibility and barrier properties against moisture and acids.
• R 3 is also trivalent to hexavalent.
• the carbon number of R 3 is 5-70, preferably 5-60, more preferably 5-50. If the carbon number of R 3 is within this range, the flexibility of the cured product of the curable resin composition and the barrier properties from moisture and acids are maintained, and the base material of the sealing material is maintained regardless of changes in the temperature environment. followability to can be improved.
• An organic group is a group that contains C and may further contain at least one element selected from the group consisting of Si, N, P, O, and S.
• the organic group may be a polymer having repeating units.
• groups such as a ketone group, an ester group, an ether group, a hydroxyl group, an amide group, a thioether group, and an isocyanurate group may be included in the structure.
• polyfunctional (meth)acrylic compounds in which b is 3 include trimethylolpropane trimethacrylate, ethylene oxide-modified trimethylolpropane tri(meth)methacrylate, propylene oxide-modified trimethylolpropane tri(meth)methacrylate, and caprolactone.
• polyfunctional (meth)acrylic compounds in which b is 4 include ditrimethylolpropane tetra(meth)acrylate, ethylene oxide-modified ditrimethylolpropane tetra(meth)acrylate, propylene oxide-modified ditrimethylolpropane tetra(meth) Acrylate, caprolactone-modified ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetramethacrylate, ethylene oxide-modified pentaerythritol tetra(meth)acrylate, propylene oxide-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, etc.
• polyfunctional (meth)acrylic compounds in which b is 5 to 6 include dipentaerythritol hydroxypenta(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, propylene oxide-modified dipentaerythritol hexa (Meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, alkyl-modified dipentaerythritol hexa(meth)acrylate, and the like.
• the encapsulating material can be applied to the base material regardless of changes in the temperature environment.
• a (meth)acrylic compound having an isocyanurate skeleton, a (meth)acrylic compound having a dipentaerythritol skeleton, a (meth)acrylic compound having a pentaerythritol skeleton, and the like are preferable from the viewpoint of enhancing followability.
• ethoxylated isocyanuric acid tri(meth)acrylate ethylene oxide-modified isocyanuric acid tri(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, propylene oxide-modified dipentaerythritol hexa(meth)acrylate, Caprolactone-modified dipentaerythritol hexa(meth)acrylate is preferred.
• Polyfunctional allyl compound (C) is a compound having 2 to 4 (meth)allyl groups.
• the polyfunctional allyl compound (C) can be used alone or in combination of two or more.
• (C) is difficult to polymerize alone, so it is excellent in forming a crosslinked network with other components, increases the toughness of the cured product of the curable resin composition, and enhances the followability of the sealing material to the base material. I can.
• barrier properties against moisture and acid can be improved, and liquid crystal alignment disorder can be prevented even under severe wet heat tests and under acidic conditions.
• the polyfunctional allyl compound (C) is preferably a compound represented by Formula 3 below.
• R 4 in the formula is a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of increasing the flexibility of the cured product of the curable resin composition and enhancing the conformability of the encapsulant to the base material.
• c is an integer of 2 to 4, and within this range, it is possible to improve the barrier properties of the sealing material against moisture and acid, and to prevent liquid crystal alignment disorder even under severe wet heat tests and under acidic conditions. .
• R 5 is also divalent to tetravalent.
• the carbon number of R 5 is 2-40, preferably 2-30, more preferably 2-25. If the carbon number of R5 is within this range, the crosslink density of the cured product of the curable resin composition is sufficient, and the encapsulant has high barrier properties against moisture and acid. Orientation disorder can be suppressed even under acidic conditions.
• An organic group is a group that contains C and may further contain at least one element selected from the group consisting of Si, N, P, O, and S.
• the organic group may be a polymer having repeating units.
• groups such as a ketone group, an ester group, an ether group, a hydroxyl group, an amide group, a thioether group, and an isocyanurate group may be included in the structure.
• the compound in which c is 2 specifically includes 1,4-cyclohexanedicarboxylic acid di(meth)allyl ester, isophthalic acid di(meth)allyl ester, and phthalic acid di(meth)allyl ester.
• hexahydrophthalic acid di(meth)allyl ester di(meth)allylmethylglycidyl isocyanurate, magnolol, di(meth)allyldiphenylsilane, trimethylolpropane di(meth)allyl ether, 2,2′-bis( 3-(meth)allyl-4-hydroxyphenyl)propane, 2,2-bis(3-(meth)allyl-4-allyloxyphenyl)propane, 2,2-bis(3-(meth)allyl-4- glycidyloxyphenyl)propane, 1,3-di(meth)allyl-5-glycidyl isocyanurate, 1,3-di(meth)allyl cyanurate and the like.
• Specific examples of compounds in which c is 3 include triallyl isocyanurate, pentaerythritol tri(meth)allyl ether, glycerin tri(meth)allyl ether, trimethylolpropane triallyl ether, and the like.
• Specific examples of compounds in which c is 4 include 1,3,4,6 tetra(meth)allylglycoluril, 1,3,4,6tetra(meth)allyl-3a-methylglycoluril, and pentaerythritol. Tetra(meth)allyl ether, tetra(meth)allyloxyethane and the like can be mentioned.
• a (meth)allyl compound having an isocyanurate skeleton, a (meth)allyl compound having a pentaerythritol skeleton, and the like are preferable from the viewpoint that the toughness of the product can be improved and the conformability of the encapsulant to the base material can be improved.
• 1,3-diallyl-5-glycidyl isocyanurate, triallyl isocyanurate, pentaerythritol triallyl ether, and pentaerythritol tetraallyl ether are preferred.
• the photopolymerization initiator (D) is the above (A), the above (B), the above (C), and in the case where a polymerizable compound is added, in order to promote the curing reaction of the polymerizable compound by light. It is added to reduce the light irradiation required for curing the curable resin composition.
• a photoinitiator (D) can also be used individually by 1 type, and can also use 2 or more types together.
• Examples of photopolymerization initiators include radical photopolymerization initiators, cationic photopolymerization initiators, and anionic photopolymerization initiators. Among these, photoradical polymerization initiators are preferred from the viewpoint of shortening reaction time and improving usability.
• photoradical polymerization initiators include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-propane-1- one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- ⁇ 4-[4-(2-hydroxy- 2-methyl-propionyl)-benzyl]-phenyl ⁇ -2-methyl-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, bis( 2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 1,2-octanedione-1-[4-(phenylthio)phenyl]-2- (O-benzoyloxime), 1-[9-ethyl-6-(2-methyl)
• photocationic polymerization initiators include bis(4-tert-butylphenyl)iodonium hexafluorophosphate, bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, cyclopropyldiphenylsulfonium tetrafluoroborate, diphenyl iodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, 2-(3,4-dimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, triphenylsulfonium tetrafluoroborate, triphenylsulfonium bromide, tri-p-tolylsulfonium hexafluorophosphate, tri-p-tolylsulfonium trifluoromethanesulfonate and the like.
• photoanionic polymerization initiators include acetophenone o-benzoyloxime, nifedipine, 2-(9-oxoxanthen-2-yl)propionic acid 1,5,7-triazabicyclo[4,4,0]deca- 5-ene, 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate, 1,2-diisopropyl-3-[bis(dimethylamino)methylene]guanidinium 2-(3-benzoylphenyl)propionate, 1,2 -dicyclohexyl-4,4,5,5,-tetramethylbiguanidinium n-butyltriphenylborate and the like.
• the curable resin composition of the present invention may contain a polyfunctional urethane (meth)acrylate (E) as long as the object of the present invention is not impaired.
• Polyfunctional urethane (meth)acrylate (E) is obtained by reacting a diisocyanate compound, a polyol compound, and a (meth)acrylate compound having a hydroxyl group by a known method.
• Polyfunctional urethane (meth)acrylate (E) can be used alone or in combination of two or more. By containing such a compound, the cured product of the curable resin composition can be toughened, and the conformability of the encapsulant to the base material can be further enhanced.
• the contained urethane groups can express strong interactions such as hydrogen bonding between urethane groups and other polar groups in a low temperature range to a high temperature range
• the cured product of the curable resin composition can be obtained regardless of the temperature environment. is toughened, and the conformability of the encapsulant to the base material can be further enhanced.
• Polyfunctional urethane (meth)acrylate (E) is a compound having 2 to 3 (meth)acrylic groups, and when the number of (meth)acrylic groups is within this range, the curable resin composition can be cured.
• the object does not become rigid, and the conformability of the encapsulant to the base material can be improved, and the polarity is not excessively increased, so compatibility with other components can be maintained.
• a known compound can be used as the diisocyanate compound.
• Examples include aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates. Specifically, aliphatic diisocyanates such as pentamethylene diisocyanate, hexamethylene diisocyanate and trimethylhexamethylene diisocyanate, alicyclic diisocyanates such as isophorone diisocyanate, hydrogenated diphenyl diisocyanate and norbornene diisocyanate, xylylene diisocyanate, tolylene diisocyanate and diphenylmethane diisocyanate. aromatic diisocyanates such as Among these, aliphatic and alicyclic diisocyanates are preferable from the viewpoint of preventing the obtained encapsulant from being colored over time.
• a known compound can be used as the polyol compound.
• examples thereof include polyester polyols, polyether polyols, polycarbonate polyols, and hydrocarbon polyols.
• the polyol compound is a divalent diol compound, a trivalent is preferred.
• polyester polyol a compound obtained by condensation reaction of a dicarboxylic acid compound and a polyol compound can be used.
• dicarboxylic acid compounds include succinic acid, adipic acid, pimelic acid, and sebacic acid. Among them, adipic acid and pimelic acid are preferred.
• polyol compounds include diol compounds and triol compounds.
• Diol compounds are specifically ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5- pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, diethylene glycol, dipropylene glycol and the like.
• triol compounds include glycerin, 1,2,4-butanetriol, and trimethylolpropane. Among them, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, diethylene glycol and glycerin are preferred.
• a known compound can be used as the polyether polyol.
• Specific examples include diol compounds such as polyethylene glycol, polypropylene glycol, polybutylene glycol and polytetramethylene glycol, and triol compounds such as polyoxypropylene triol and polyoxyethylene polyoxypropylene triol. Among them, polyethylene glycol, polypropylene glycol and polyoxypropylene triol are preferable.
• polycarbonate polyol a compound obtained by transesterification of a diester carbonate and a polyol compound can be used.
• the carbonic acid diester include diphenyl carbonate, dimethyl carbonate, diethylene carbonate, and the like. Among them, diphenyl carbonate is preferred.
• polyol compounds include diol compounds and triol compounds.
• Diol compounds are specifically ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5- pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, diethylene glycol, dipropylene glycol and the like.
• triol compounds include glycerin, 1,2,4-butanetriol, and trimethylolpropane. Among them, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, diethylene glycol and glycerin are preferred.
• a known compound can be used as the polyol composed of the hydrocarbon. Specifically, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1 ,6-hexanediol, 1,7-heptanediol and 1,8-octanediol, and triol compounds such as glycerin, 1,2,4-butanetriol and trimethylolpropane. Among them, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol and glycerin are preferred.
• a known compound can be used as the (meth)acrylate compound having the hydroxyl group. Specifically, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate, 5-hydroxycyclooctyl (meth)acrylate , 2-hydroxy-3-phenyloxypropyl (meth)acrylate, propylene glycol monoacrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate and the like can be used.
• the weight-average molecular weight of the polyfunctional urethane (meth)acrylate (E) is such that the sealant maintains its barrier properties against moisture and acids, and has high conformability to the base material regardless of the temperature environment. From the viewpoint of ease of handling, it is preferably 1,000 to 15,000.
• the weight average molecular weight of the urethane (meth)acrylate is determined by gel permeation chromatography (GPC) using a standard polystyrene calibration curve.
• the content of the polyfunctional urethane (meth)acrylate (E) in the curable resin composition of the present invention is 0 to 20 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C). Yes, preferably 1 to 15 parts by mass.
• the curable resin composition of the present invention may contain a surfactant (F) as long as the object of the present invention is not impaired.
• Surfactant (F) is highly lyophobic, so when it is contained in the curable resin composition, the moisture barrier property of the encapsulating material is improved, and even when exposed to severe wet heat tests and acidic conditions, Disturbance of liquid crystal alignment can be further suppressed.
• the surfactant (F) known silicon-based surfactants, fluorine-based surfactants, acrylic surfactants, and the like can be used without particular limitation. Activators are preferred.
• fluorosurfactants include "Megafac F-410", “F-430", “F-444”, and “F-472SF” manufactured by DIC Corporation. , F-477, F-552, F-553, F-554, F-555, F-556, F-558, The same "F-559”, the same "F-561”, the same “R-94", the same "RS-72-K”, the same "RS-75” and the like. These surfactants may be used alone or in combination of two or more.
• the content of the surfactant (F) in the curable resin composition of the present invention is 0 to 3 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), preferably , 0.01 to 1 part by mass.
• the curable resin composition of the present invention may contain a silane coupling agent (G) as long as the object of the present invention is not impaired.
• the silane coupling agent (G) improves the interaction with other components and the substrate, and is contained in the curable resin composition to improve the toughness of the cured product of the curable resin composition and the resistance to the substrate. Adhesiveness is improved, and conformability to the base material can be further enhanced regardless of changes in the temperature environment.
• a known silane coupling agent can be used without any particular limitation. Those having reactive functional groups such as acryl groups, vinyl groups, thiol groups, epoxy groups and isocyanate groups are preferred.
• silane coupling agents may be used alone or in combination of two or more.
• the content of the silane coupling agent (G) in the curable resin composition of the present invention is preferably 0 to 15 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C). is 1 to 10 parts by mass.
• the curable resin composition of the present invention in addition to the polyfunctional urethane (meth)acrylate (E), the surfactant (F), and the silane coupling agent (G), as long as the object of the present invention is not hindered.
• Epoxy compounds, curing accelerators, UV absorbers, light stabilizers, antioxidants, polymerization inhibitors, leveling agents, adhesion promoters, plasticizers, antifoaming agents, fillers, light shielding materials, conductive materials, spacers, etc. may contain additives.
• the curable resin composition of the present invention comprises a thiol group of the polyfunctional thiol compound (A), and a polymerizable unsaturated bond of the polyfunctional (meth)acrylic compound (B) and the polyfunctional (meth)allyl compound (C).
• a thiol-ene reaction proceeds during this time to obtain a cured product. Since the formed thioether bond can flexibly change the bond angle, the flexibility of the cured product of the curable resin composition is increased, and the atoms can be cured at a high density so that the gaps between the bonds are filled.
• the polyfunctional (meth)allyl compound (C) does not polymerize by itself, the inclusion of the polyfunctional (meth)allyl compound (C) enables efficient formation of thioether bonds, resulting in a flexible and tough cured product. Become.
• the cross-linking density is improved, the barrier property is further improved, and the sealing material has excellent conformability to the base material, and the liquid crystal can be maintained even when it is in contact with the liquid crystal in a harsh moist and hot environment or under acidic conditions. Orientation disorder can be prevented.
• the polyfunctional (meth)acrylic compound (B) suppresses the reactivity between the polyfunctional thiol compound (A) and the polyfunctional (meth)allyl compound (C), and stabilizes the uncured product of the curable resin composition. It is possible to increase the flexibility and improve the usability. Furthermore, the polyfunctional (meth)acrylic compound (B) imparts appropriate flexibility and polarity to the cured product of the curable resin composition, and enhances the followability of the sealing material to the base material regardless of temperature changes. be able to. From this, the curable resin composition of the present invention is stable in an uncured state, and the sealing material made of the cured product is in contact with the liquid crystal under a severe moist and heat environment or under acidic conditions.
• All of (A), (B), and (C) are indispensable in order to prevent the alignment disorder of the liquid crystal from occurring and to exhibit excellent conformability to the substrate regardless of changes in the temperature environment. Further, by using (D) in addition to the curable resin composition containing (A), (B), and (C), it is possible to achieve the above effect by curing only by light irradiation.
• the blending mass ratio (B)/(C) of (B) and (C) is 0.1 to 1.0, and the functional group concentration of the thiol group of (A) and the concentration of (B) and (C)
• the curable resin composition is not It is stable in the cured state, and the sealing material obtained by curing does not cause alignment disorder of the liquid crystal even when it is in contact with the liquid crystal in a harsh moist heat environment or under acidic conditions.
• the followability to the base material is excellent regardless of the change in the thickness.
• the functional group concentration of the thiol group is the number of parts by mass of (A) in a total of 100 parts by mass of (A), (B) and (C) ⁇ the number of functional groups of the thiol group of (A) / the molecular weight of (A). It is the number represented, and the sum of the functional group concentrations of the polymerizable unsaturated bonds of (B) and (C) is [(B) Number of parts by mass of (B) (meth)acrylic groups / molecular weight of (B)] + [(A) and (B) and (C) total 100 parts by weight of (C) in the number of parts by weight of (C) number of allyl groups/molecular weight of (C)].
• the curable resin composition of the present invention has excellent stability in an uncured state, and in order to further improve usability, the blending mass ratio of (B) and (C) (B ) / (C) is 0.2 to 1.0, the toughness of the cured product of the curable resin composition is improved, and the followability of the sealing material to the base material is further improved.
• the blending mass ratio (B) of (B) and (C) / (C) is 0.2 to 0.9, the barrier property from moisture and acid of the cured product of the curable resin composition is improved, and the alignment disorder of the liquid crystal is increased even under severe wet heat tests and under acidic conditions.
• the blending mass ratio (B)/(C) of (B) and (C) is preferably 0.2 to 0.8.
• the thiol group of (A) The total ratio of the functional group concentration to the functional group concentrations of the polymerizable unsaturated bonds of (B) and (C) (thiol group/polymerizable unsaturated bond) is preferably 0.7 to 3.0, and the low temperature
• (A) The total ratio of the functional group concentration of the thiol group and the functional group concentration of the polymerizable unsaturated bonds of (B) and (C) (thiol group / polymerizable unsaturated bond) is 0.7 to 2.8 is preferable, and in order to improve the barrier properties of the cured product of the curable resin
• the total ratio of the functional group concentration of the thiol group in (A) and the functional group concentration of the polymerizable unsaturated bonds in (B) and (C) (thiol group/polymerizable unsaturated bond) is It is preferably between 0.7 and 2.6.
• the ratio of (D) to a total of 100 parts by mass of (A), (B) and (C) is preferably 0.01 to 10.0 parts by mass, More preferably, it is 0.1 to 10.0 parts by mass.
• the film liquid crystal panel of the present invention includes, for example, a light control member that only controls transparency or opacity by the orientation of liquid crystals, and a member that displays an image like a display.
• a pair of substrates are arranged to face each other, the periphery of which is sealed with the sealing material for the film liquid crystal panel, and a liquid crystal material exists between them.
• the substrate is a plastic transparent film base material such as polyethylene terephthalate, polycarbonate, cycloolefin (co)polymer, PMMA, polyimide, etc. on which a silver or copper electrode or a transparent electrode such as ITO or PEDOT is applied. .
• the film liquid crystal panel of the present invention is a liquid crystal panel formed of a substrate using the above plastic transparent film substrate, and the sealing material for the film liquid crystal panel is the sealing material used for the above film liquid crystal panel. be.
• the film liquid crystal panel of the present invention After applying the curable resin composition of the present invention to one of the pair of substrates, the other substrate is superimposed while interposing the liquid crystal on the inside thereof, and light is irradiated to cure the above. It is formed by curing a flexible resin composition.
• a polymer-dispersed liquid crystal containing a liquid crystal and a curable resin composition is applied to one of the pair of substrates, the other substrate is superimposed, and light is irradiated to cure the polymer-dispersed liquid crystal.
• the curable resin composition of the present invention is applied to the periphery, and light is irradiated to cure the curable resin composition.
• the method of applying the curable resin composition is not particularly limited, and for example, a method using coating equipment such as dispenser coating, an inkjet method, or a screen printing method, a method of hand-coating with a syringe or a brush, etc. are applied. be.
• the light source for irradiating the curable resin composition with light is not particularly limited. , LED fluorescent lamps, sunlight, electron beam irradiation equipment, and the like are applied.
• the curable resin compositions produced in Examples and Comparative Examples were coated on a polyethylene terephthalate (PET) film having a thickness of 100 ⁇ m with an applicator so that the film thickness was 100 ⁇ m, and irradiated with ultraviolet rays ( 1000 mJ/cm 2 ) to cure the curable resin composition.
• PET polyethylene terephthalate
• the obtained PET film with a cured film was cut into a rectangular shape having a length of 100 mm and a width of 10 mm to obtain a sample.
• the resulting sample was subjected to a bending test using an MIT testing machine (BE-202 manufactured by Tester Sangyo Co., Ltd.) (conditions: load 1 N, bending speed 175 cpm, bending radius 2.5 mm, bending speed 135°).
• the test sample was visually observed every time it was bent 5000 times to confirm the presence or absence of cracks and peeling. It should be noted that the greater the number of times of bending until cracks or peeling occurred, the better the substrate followability was, and the number of times of bending at which cracks or peeling occurred was described in each table.
• A No cracks or peeling even after bending 20000 times (5000 times x 4).
• ⁇ Cracks or peeling occurred after 20000 times (5000 times ⁇ 4) or after 15000 times (5000 times ⁇ 3).
• x Cracks and peeling occur within 10000 times (5000 times x 2).
• the curable resin compositions produced in Examples and Comparative Examples were coated on a polyethylene terephthalate (PET) film having a thickness of 100 ⁇ m with an applicator so that the film thickness was 100 ⁇ m, and irradiated with ultraviolet rays ( 1000 mJ/cm 2 ) to cure the curable resin composition.
• PET polyethylene terephthalate
• the obtained PET film with a cured film was cut into a rectangular shape having a length of 100 mm and a width of 10 mm to obtain a sample.
• the obtained sample was exposed to (-30 ° C., 30 minutes ⁇ 80 ° C., 30 minutes) ⁇ 200 heating and cooling shocks, and then subjected to MIT tester (BE manufactured by Tester Sangyo Co., Ltd. -202) was used to perform a bending test (conditions: load 1 N, bending speed 175 cpm, bending radius 2.0 mm, bending speed 135°).
• the test sample was visually observed every time it was bent 5000 times to confirm the presence or absence of cracks and peeling. It should be noted that the greater the number of times of bending until cracks or peeling occurred, the better the substrate followability was, and the number of times of bending at which cracks or peeling occurred was described in each table.
• A No cracks or peeling even after bending 20000 times (5000 times x 4).
• ⁇ Cracks or peeling occurred after 20000 times (5000 times ⁇ 4) or after 15000 times (5000 times ⁇ 3).
• x Cracks and peeling occur within 10000 times (5000 times x 2).
• a 40 mm ⁇ 45 mm glass substrate (RT-DM88-PIN manufactured by EHC Co., Ltd.) on which a transparent electrode and an alignment film are applied in this order on the glass, using a dispenser (Shot Master manufactured by Musashi Engineering Co., Ltd.) Then, the curable resin compositions produced in Examples and Comparative Examples were applied to a square frame of 35 mm ⁇ 40 mm (line width: 1 mm), and a liquid crystal (Merck Company MLC-11900-000) was added dropwise. Next, the glass substrate and the opposing glass substrate were bonded together under reduced pressure.
• Ultraviolet irradiation 1000 mJ/cm 2
• a high-pressure mercury lamp 100 mJ/cm 2
• exposing the prepared liquid crystal panel under conditions of 60° C. and 95% RH for 1000 hours it is driven in a halftone display state at a voltage of AC 5 V, and the vicinity of the sealing material made of the cured product of the curable resin composition.
• Orientation disorder of the liquid crystal was observed with a polarizing microscope. It should be noted that the shorter the distance over which the disordered orientation spreads from the end of the encapsulant, the less likely the disordered orientation is, and the distance over which the disordered orientation spreads is shown in each table.
• ⁇ Orientation disorder does not extend beyond 0.4 mm from the edge of the sealing material.
• ⁇ Disturbed orientation spread beyond 0.4 mm from the edge of the sealing material, but did not spread beyond 0.8 mm.
• x Orientation disorder spread beyond 0.8 mm from the end of the sealing material.
• Ultraviolet irradiation 1000 mJ/cm 2
• a high-pressure mercury lamp to obtain a liquid crystal panel.
• the prepared liquid crystal panel was attached to a combined cycle tester CYP-90A manufactured by Suga Test Instruments Co., Ltd., and nitric acid, sulfuric acid, and a 10% sodium hydroxide aqueous solution were added to a 5% sodium chloride aqueous solution to adjust the pH to 3.5.
• ⁇ Orientation disorder does not extend beyond 0.4 mm from the edge of the sealing material.
• ⁇ Disturbed orientation spread beyond 0.4 mm from the edge of the sealing material, but did not spread beyond 0.8 mm.
• x Orientation disorder spread beyond 0.8 mm from the end of the sealing material.
• A-1 Dipentaerythritol hexakis (3-mercaptopropionate) [number of thiol groups: 6, molecular weight: 783.0]
• A-2 Pentaerythritol tetrakis (3-mercaptopropionate) [number of thiol groups: 4, molecular weight: 488.6]
• A-3 Tris-[(3-mercaptopropiomoloxy)-ethyl]-isocyanurate [number of thiol groups: 3, molecular weight: 525.6]
• B-1 Ethoxylated isocyanuric acid triacrylate [number of acrylic groups: 3, acrylic equivalent: 141, molecular weight: 423.0]
• B-2 trimethylolpropane trimethacrylate [number of methacrylic groups: 3, methacrylic equivalent: 113, molecular weight: 338.0]
• B-3 Caprolactone-modified dipentaerythritol hexaacrylate [number of acrylic groups: 6, acrylic equivalent: 131, molecular weight: 783.0]
• B-4 Caprolactone-modified ditrimethylolpropane tetraacrylate [number of acrylic groups: 4, acrylic equivalent: 231, molecular weight: 922.5]
• B-5 Dipropylene glycol diacrylate [number of acrylic groups: 2, acrylic equivalent: 121, molecular weight: 242.0]
• B-6 Pentaerythritol tetraacrylate [number of acrylic groups: 4,
• D-1 bis (2,4,6-trimethylbenzoyl)-phenylphosphine oxide
• D-2 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3yl]ethanone-1 -(O-acetyloxime)
• D-3 1-hydroxycyclohexyl phenyl ketone
• F-1 Megafac F-554 manufactured by DIC Corporation
• F-2 Megafac F-477 manufactured by DIC Corporation
• Examples 1 to 20, Comparative Examples 1 to 15 The above components were added to a stirring pot in the proportions shown in Tables 1-1, 1-2, 2-1 and 2-2 below, and mixed and stirred for 2 hours to obtain 1 kg of a curable resin composition. Each evaluation was performed using the curable resin composition. The results are shown in each table.
• the curable resin composition of each example contained components (A) to (D) in an appropriate amount specified in the present invention, so that the uncured product was highly stable and cured.
• the material had high conformability to the substrate regardless of the temperature environment, and furthermore, it had the property of not causing disorder of liquid crystal alignment after the wet heat test and the acid condition test.
• Comparative Example 1 since the polyfunctional thiol compound (A) is not contained, the sealing material for film liquid crystal panels obtained by curing the curable resin composition has low followability to the substrate, and However, the orientation of the liquid crystal was disturbed in severe wet heat tests and acid condition tests.
• Comparative Example 2 since the polyfunctional (meth)acrylic compound (B) is not contained, the curable resin composition has low stability, and the sealing film for the liquid crystal panel obtained by curing the curable resin composition The stopper material had low followability to the base material.
• Comparative Example 3 since the polyfunctional allyl compound (C) was not contained, the sealing material for a film liquid crystal panel obtained by curing the curable resin composition had low conformability to the substrate and was used under harsh conditions.
• Comparative Example 5 since the number of functional groups of the polyfunctional (meth)acrylic compound (B) is small, the sealing material for a film liquid crystal panel obtained by curing the curable resin composition is obtained after the temperature environment change accelerated test. Underability to the base material was low.
• Comparative Example 6 since the (meth)acrylic equivalent of the polyfunctional (meth)acrylic compound (B) is small, the sealing material for the film liquid crystal panel obtained by curing the curable resin composition accelerates changes in the temperature environment.
• the base material after the test was low.
• Comparative Example 7 since the (meth)acrylic equivalent of the polyfunctional (meth)acrylic compound (B) is large, the sealing material for the film liquid crystal panel obtained by curing the curable resin composition was tested under acidic conditions. However, the alignment disorder of the liquid crystal is caused.
• Comparative Example 8 since the blending mass ratio (B)/(C) is larger than the specified range, the followability to the substrate is low, and the alignment disorder of the liquid crystal is caused in severe wet heat tests and acid condition tests. It was something that could happen.
• Comparative Example 9 since the blending mass ratio (B)/(C) is smaller than the specified range, the curable resin composition has low stability, and the film liquid crystal obtained by curing the curable resin composition The sealing material for panels has low followability to the base material.
• Comparative Example 12 since the number of functional groups of the polyfunctional allyl compound (C) is small, the sealing material for film liquid crystal panels obtained by curing the curable resin composition has low conformability to the substrate, and However, the orientation of the liquid crystal was disturbed in severe wet heat tests and acid condition tests. In Comparative Example 13, since the amount of the photopolymerization initiator (D) is large, the sealing material for a film liquid crystal panel obtained by curing the curable resin composition was subjected to a severe wet heat test and an acidic condition test. This causes alignment disorder of the liquid crystal.
• the polyfunctional urethane (meth)acrylate of component (E) is contained as an additional component, but since the blending mass ratio (B)/(C) is smaller than the specified range, the curable resin composition The product has low stability, and the sealing material for film liquid crystal panels obtained by curing the curable resin composition has low conformability to the base material.
• the surfactant of component (F) is contained as other components, but the functional group concentration of the thiol group of (A) and the functional group of the polymerizable unsaturated bond of (B) and (C) Since the total concentration ratio is larger than the specified range, the sealing material for film liquid crystal panels obtained by curing the curable resin composition has low followability to the substrate after the accelerated temperature environment change test.
• the alignment disorder of the liquid crystal occurs in a severe wet heat test and acid condition test.
• the silane coupling agent of component (G) is contained as another component, but the functional group concentration of the thiol group of (A) and the functionality of the polymerizable unsaturated bonds of (B) and (C) Since the ratio of the total group concentration is smaller than the specified range, the sealing material for film liquid crystal panels obtained by curing the curable resin composition has low conformability to the base material.

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