JP7359064B2 - A curable resin composition used as a sealing material for a film liquid crystal panel, and a film liquid crystal panel whose edges are sealed with the curable resin composition. - Google Patents

Description

The present invention relates to a curable resin composition used as a sealant for film liquid crystal panels. Specifically, in addition to not contaminating the liquid crystal even if it comes into contact with the liquid crystal in an uncured state, and also not causing disorder in the alignment of the liquid crystal even when the cured product comes into contact with the liquid crystal in a harsh humid heat environment, The present invention relates to a curable resin composition that forms a sealing material for film liquid crystal that has excellent followability to a substrate regardless of changes in temperature environment. The present invention also relates to a film liquid crystal panel using a sealant made of the curable resin composition.

Liquid crystal panels are widely used to display images in various electronic devices such as mobile phones and personal computers. A liquid crystal panel usually includes a pair of glass substrates having electrodes on their surfaces, a frame-shaped sealant sandwiched between them, and a liquid crystal layer surrounded by the sealant.

Conventionally, a photocurable acrylic resin composition has been used as the sealing material. However, although conventional acrylic resin compositions have excellent workability and productivity, they have the problem of generating a large amount of outgas during the manufacturing process and reducing the adhesion between the sealing material and the base material. was there. In addition, encapsulants are required to protect liquid crystals in harsh humid and heat environments, but encapsulants made of conventional acrylic resin compositions have low moisture barrier properties and Because it is easily decomposed, it causes contamination of the liquid crystal by moisture and decomposed products of the sealant in a humid heat environment, resulting in a problem in that the alignment of the liquid crystal becomes disordered.

To solve these problems, by using a resin composition containing a thiol monomer having a thiol group and an ene monomer having a carbon-carbon double bond, it is possible to suppress the generation of outgas and improve the adhesiveness of the sealing material. known (Patent Document 1). Furthermore, in Patent Document 1, it has been confirmed that due to the improved moisture barrier properties and durability of the encapsulant, the alignment of the liquid crystal does not occur even when the encapsulant and the liquid crystal are in contact with each other in a harsh humid and heat environment. There is.

However, in manufacturing liquid crystal panels, there is a method in which the resin composition used for the encapsulant comes into contact with the liquid crystal in an uncured state, but in such a method, the encapsulant of Patent Document 1 There has been a problem in that the resin component is eluted into the liquid crystal, resulting in liquid crystal contamination and display defects.
Furthermore, in recent years, film liquid crystal panels based on flexible film materials have attracted attention, and development is progressing. The sealing material used for this film liquid crystal panel is different from the sealing material used for rigid glass substrates, and is required to be rich in flexibility and toughness and to follow the film base material. Furthermore, in view of actual use, this followability is required even after an accelerated test that simulates changes in the temperature environment to which a film liquid crystal panel may be exposed.
However, the encapsulant of Patent Document 1 lacks flexibility and toughness, has insufficient followability to a flexible film base material, and has problems such as the encapsulant peeling off from the film during accelerated testing. There was a problem that occurred.

Japanese Patent Application Publication No. 2016-169298

The present invention has been achieved in view of the above-mentioned circumstances, and its objective is to prevent liquid crystals from being contaminated even when they come into contact with liquid crystals in an uncured state, and to maintain liquid crystals even when they come into contact with liquid crystals in harsh humid and heat environments. To provide a curable resin composition for use in a sealing material for a film liquid crystal panel, which does not cause disordered orientation and has excellent conformability to a substrate regardless of changes in temperature environment, and the curable resin composition described above. An object of the present invention is to provide a film liquid crystal panel using a resin composition as a sealing material.

While conducting extensive research to solve the above problems, the present inventors focused on the fact that polyfunctional urethane (meth)acrylate compounds have high lyophobicity with liquid crystals. By combining a specific polyfunctional (meth)allyl compound and using a curable resin composition that further contains a polyfunctional thiol compound, the cured product does not contaminate the liquid crystal even if it comes into contact with the liquid crystal in an uncured state. It has been found that a sealing material for a film liquid crystal panel that does not cause alignment disturbance of liquid crystal even when in contact with liquid crystal under a harsh humid heat environment can be obtained. Furthermore, it was discovered that this sealing material has both flexibility and toughness, and has excellent followability to the base material regardless of changes in temperature environment, leading to the completion of the present invention.

That is, the present invention is [1] to [2] below.
[1] The following (A) to (D) components (A) a polyfunctional thiol compound having 2 to 6 thiol groups;
(B) a polyfunctional urethane (meth)acrylate compound having 2 to 3 (meth)acrylic groups;
(C) a polyfunctional allyl compound having 2 to 4 (meth)allyl groups;
(D) containing a photopolymerization initiator;
The blending weight ratio (B)/(C) of (B) and (C) is 0.1 to 1.0,
The ratio of the total number of functional groups in the thiol group in (A) and the number of functional groups in the polymerizable unsaturated bonds in (B) and (C) (thiol group/polymerizable unsaturated bond) is 0.5 to 3.0. ,
A curable resin composition used in a sealing material for film liquid crystal panels, in which (D) is 0.01 to 10.0 parts by mass based on a total of 100 parts by mass of (A), (B), and (C). thing.
[2] A film liquid crystal panel whose edges are sealed with the curable resin composition described in [1] above.

In the present invention, the term "(meth)allyl compound" refers to a general term that includes both compounds having an allyl group and compounds having a methallyl group, and the same applies to "(meth)acrylic group" and the like. In the present invention, the numerical range "○○~XX" is a concept that includes the lower limit value ("○○") and upper limit value ("XX") unless otherwise specified. That is, to be more precise, it means "more than or equal to ○○ and less than or equal to XX".

According to the present invention, in addition to not contaminating the liquid crystal even if it comes into contact with the liquid crystal in an uncured state and causing no disturbance in the alignment of the liquid crystal even if it comes into contact with the liquid crystal in a harsh humid and heat environment, It is possible to provide a curable resin composition for use in a sealing material for a film liquid crystal panel that has excellent conformability to a substrate regardless of changes. Another object of the present invention is to provide a film liquid crystal panel using the above curable resin composition as a sealing material.

The present invention will be explained 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)>
The polyfunctional thiol compound (A) is a compound having 2 to 6 thiol groups. The polyfunctional thiol compound (A) can be used alone or in combination of two or more. By containing such a compound, a thiol-ene reaction can proceed with other components, thereby increasing curability. The formed thioether bond can change the bond angle more flexibly than the bonds of atoms such as C, O, and N, so the cured product is highly flexible and can improve the conformability of the sealant to the base material. . In addition, cured products consisting of thioether bonds have high flexibility in bond angles and can be cured at high density so that atoms fill the gaps between bonds, so they have high moisture barrier properties and retain moisture even after a moist heat test. It is possible to prevent alignment disorder of liquid crystal without being affected.

The 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.)

In the formula, a is preferably an integer of 3 to 6 from the viewpoint of improving the moisture barrier properties of the sealing material for film liquid crystal panels and suppressing alignment disorder even when exposed to severe heat and humidity tests. If a in the formula is within this range, a good cured product can be obtained without causing large curing shrinkage and decreasing conformability to the substrate after curing. Further, from the same viewpoint, R ¹ is also preferably trivalent to hexavalent. The number of carbon atoms in R ¹ is 10 to 60, preferably 10 to 45, and more preferably 12 to 30. If the number of carbon atoms in ^R1 is within this range, the crosslinking density of the cured product of the curable resin composition will be sufficient, the sealing material will have excellent moisture barrier properties, and the liquid crystal will remain stable even when exposed to severe heat and humidity tests. Orientation disorder can be suppressed.

The 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. Further, the structure thereof may contain a group such as a ketone group, an ester group, an ether group, a hydroxyl group, an amide group, a thioether group, an isocyanurate group, or a glycoluril group.

Specific examples of the polyfunctional thiol compound (A) include dipentaerythritol hexakis (3-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate), and trimethylolpropane tris (3-mercaptopropionate). ), trimethylolethane tris (2-mercaptoacetate), trimethylolethane 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-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl Mercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, 1,3,5-tris(mercapto Examples include ethyleneoxy)benzene, tris-[(3-mercaptopropiomoloxy)-ethyl]-isocyanurate, and the like.
Among the compounds represented by the above formula 1, polyfunctional thiols having a pentaerythritol skeleton, polyfunctional thiols having a dipentaerythritol skeleton, and polyfunctional thiols having an isocyanurate skeleton are preferred.
Among these, it is possible to improve the moisture barrier properties of the encapsulant, suppress alignment disorder of liquid crystal even when exposed to severe heat and humidity tests, and increase the flexibility of the cured product of the curable resin composition. Dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)- Ethyl]-isocyanurate is preferred.

As the polyfunctional thiol compound (A), a commercially available product may be used, or a synthesized product may be used. As a method of synthesis, for example, it can be obtained by carrying out an esterification reaction using a polyhydric alcohol such as pentaerythritol and a mercapto group-containing carboxylic acid such as 3-mercaptopropionic acid by a known method.

<Polyfunctional urethane (meth)acrylate compound (B)>
The polyfunctional urethane (meth)acrylate compound (B) is obtained by reacting a diisocyanate compound, a polyol compound, and a (meth)acrylate compound having a hydroxyl group by a known method. The polyfunctional urethane (meth)acrylate compound (B) can be used alone or in combination of two or more. Since such compounds have high lyophobicity with liquid crystals, the inclusion of such compounds reduces the solubility of uncured curable resin compositions in liquid crystals, and reduces the solubility of uncured curable resin compositions in case of prolonged contact with liquid crystals. However, it can prevent contamination of the liquid crystal. Further, the cured product of the curable resin composition can be made tougher, and the conformability of the sealing material to the base material can be improved. In addition, the urethane groups contained can exhibit strong interactions such as hydrogen bonds with each other and with other polar groups in the low temperature range of -30°C or lower to the high temperature range of about 100°C. First, the cured product of the curable resin composition is made tougher, and the conformability of the sealing material to the base material can be improved. The polyfunctional urethane (meth)acrylate compound (B) 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 The cured product does not become rigid and the conformability of the sealing material to the base material can be improved, and the polarity does not become too high and compatibility with other components can be maintained.

As the diisocyanate compound, known compounds can be used. 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 preferred from the viewpoint of preventing the resulting sealant from discoloring over time.

As the polyol compound, known compounds can be used. Examples include polyester polyols, polyether polyols, polycarbonate polyols, and polyols made of hydrocarbons. The polyol compound is a divalent diol compound, a trivalent diol compound, etc. from the viewpoint of not making the polarity of the polyfunctional urethane acrylate compound obtained after the reaction too high and improving the conformability of the sealing material to the base material. Preferred are triol compounds.

As the polyester polyol, a compound obtained by subjecting a dicarboxylic acid compound and a polyol compound to a condensation reaction can be used. Specific examples of dicarboxylic acid compounds include succinic acid, adipic acid, pimelic acid, and sebacic acid. Among these, adipic acid and pimelic acid are preferred. Further, examples of the polyol compound include a diol compound and a triol compound. Specifically, diol compounds include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5- Examples include pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, diethylene glycol, dipropylene glycol and the like. Specific examples of the triol compound include glycerin, 1,2,4-butanetriol, trimethylolpropane, and the like. Among them, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, diethylene glycol, and glycerin are preferred.

As the polyether polyol, known compounds can be used. 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 these, polyethylene glycol, polypropylene glycol, and polyoxypropylene triol are preferred.

As the polycarbonate polyol, a compound obtained by transesterification of a carbonic acid diester and a polyol compound can be used. Specific examples of the carbonic diester include diphenyl carbonate, dimethyl carbonate, diethylene carbonate, and the like. Among them, diphenyl carbonate is preferred. Examples of the polyol compound include diol compounds and triol compounds. Specifically, diol compounds include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5- Examples include pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, diethylene glycol, dipropylene glycol and the like. Specific examples of the triol compound include glycerin, 1,2,4-butanetriol, trimethylolpropane, and the like. Among them, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, diethylene glycol, and glycerin are preferred.

As the polyol made of hydrocarbon, known compounds can be used. 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.

As the (meth)acrylate compound having a hydroxyl group, a known compound can be used. 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, etc. can be used. Among these, it is possible to prevent the encapsulant from discoloring over time, increase the flexibility of the cured product of the curable resin composition, and improve the conformability of the encapsulant to the base material. 2-hydroxyethyl acrylate and propylene glycol monoacrylate are preferred.

The weight average molecular weight of the polyfunctional urethane (meth)acrylate compound (B) is such that the curable resin composition does not contaminate the liquid crystal even if it comes into contact with the liquid crystal in an uncured state, and that the sealing material is not exposed to a severe moist heat test. 1,000~ It is preferably 15,000, more preferably 3,000 to 10,000. The weight average molecular weight of urethane (meth)acrylate is determined by gel permeation chromatography (GPC) using a standard polystyrene calibration curve.

<Polyfunctional (meth)allyl compound (C)>
The 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. By containing (C), the toughness of the cured product of the curable resin composition increases, and the conformability of the sealing material to the base material can be improved. In addition, because it is excellent in forming a crosslinked network with other components, the sealing material has excellent moisture barrier properties.Furthermore, it is less likely to be hydrolyzed during a humidity test compared to (meth)acrylic compounds, so it can be used for sealing during a humidity test. It is possible to maintain high moisture barrier properties of the stopper material, and it is possible to suppress alignment disorder of liquid crystals even when exposed to severe heat and humidity tests.
The polyfunctional allyl compound (C) is preferably a compound represented by the following formula 2.
(b in the formula is an integer of 2 to 4. R ² is a hydrogen atom or a methyl group. R ³ is a divalent to tetravalent organic group having 2 to 40 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 improving the conformability of the sealing material to the base material. b is an integer from 2 to 4, and by being within this range, the moisture barrier properties of the sealing material can be improved, orientation disorder can be suppressed even when exposed to severe moist heat tests, and the curable resin composition The flexibility of the cured product increases, and the conformability of the encapsulant to the base material can be improved. Further, from the same viewpoint, R ³ is also divalent to tetravalent. The number of carbon atoms in R ³ is 2 to 40, preferably 2 to 30, and more preferably 2 to 25. If the number of carbon atoms in ^R23 is within this range, the crosslinking density of the cured product of the curable resin composition is sufficient, and the sealing material has good moisture barrier properties, so it cannot be exposed to severe heat and humidity tests. Orientation disorder can be suppressed.

The 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. Further, the structure thereof may contain 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.

For example, as a compound in which b is 2, specifically, 1,4-cyclohexanedicarboxylic acid di(meth)allyl ester, isophthalic acid di(meth)allyl ester, 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- Examples include glycidyloxyphenyl)propane, 1,3-di(meth)allyl-5-glycidyl isocyanurate, and 1,3-di(meth)allyl cyanurate.
Specific examples of the compound where b is 3 include triallylisocyanurate, pentaerythritol tri(meth)allyl ether, glycerin tri(meth)allyl ether, trimethylolpropane triallyl ether, and the like.
Examples of the compound where b is 4 include 1,3,4,6 tetra(meth)allyl glycoluril, 1,3,4,6 tetra(meth)allyl-3a-methylglycoluril, and pentaerythritol. Examples include tetra(meth)allyl ether and tetra(meth)allyloxyethane.
Among the above (meth)allyl compounds, it is possible to prevent discoloration of the encapsulant over time, improve the moisture barrier properties of the encapsulant, and suppress orientation disorder even when exposed to severe heat and humidity tests. Furthermore, pentaerythritol, a (meth)allyl compound having an isocyanurate skeleton, can be used from the viewpoint of increasing the toughness of the cured product of the curable resin composition and improving the conformability of the sealing material to the base material. Preferred are (meth)allyl compounds having a skeleton. Among these, specifically preferred are 1,3-diallyl-5-glycidyl isocyanurate, triallyl isocyanurate, pentaerythritol triallyl ether, and pentaerythritol tetraallyl ether.

<Photopolymerization initiator (D)>
The photopolymerization initiator (D) is used to promote the curing reaction of the polymerizable compound by light when a polymerizable compound is added to the above (A), the above (B), the above (C), and other polymerizable compounds. It is possible to reduce the amount of light irradiation necessary for curing the curable resin composition. The photopolymerization initiator (D) can be used alone or in combination of two or more. Examples of the photopolymerization initiator include radical photopolymerization initiators, cationic photopolymerization initiators, and anionic photopolymerization initiators. A photoradical polymerization initiator is preferably used to shorten reaction time, a cationic photopolymerization initiator is preferably used to improve flexibility, and an anionic photopolymerization initiator is used to impart adhesiveness. It is preferable to use it on occasion.

Examples of the photoradical polymerization initiator include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1- 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-methylbenzoyl)-9H-carbazol-3yl]ethanone-1-(O-acetyloxime), and the like.

Examples of 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, Examples include triphenylsulfonium bromide, tri-p-tolylsulfonium hexafluorophosphate, tri-p-tolylsulfonium trifluoromethanesulfonate.

Examples of the photoanionic polymerization initiator include acetophenone o-benzoyloxime, nifedipine, 1,5,7-triazabicyclo[4,4,0]dec-2-(9-oxoxanthen-2-yl)propionic acid, and 5-ene, 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate, 1,2-diisopropyl-3-[bis(dimethylamino)methylene]guanidium 2-(3-benzoylphenyl)propionate, 1,2 -dicyclohexyl-4,4,5,5,-tetramethylbiguanidium n-butyltriphenylborate and the like.

<Polyfunctional (meth)acrylic compound (E)>
The curable resin composition of the present invention may contain a polyfunctional (meth)acrylic compound (E) within a range that does not impede the object of the present invention. The polyfunctional (meth)acrylic compound (E) acts as a compatibilizer between the polyfunctional urethane (meth)acrylate compound (B) and other components, and when the uncured product of the curable resin composition comes into contact with the liquid crystal for a long time, However, it can improve the ability to prevent liquid crystal contamination. The polyfunctional (meth)acrylic compound preferably has two or more (meth)acrylic groups from the viewpoint of not inhibiting the curability of the curable resin composition. Further, from the viewpoint of not reducing the flexibility of the cured product of the curable resin composition and preventing the followability to the substrate from being inhibited, it is preferable to use one having 6 or less (meth)acrylic groups. Known compounds can be used as such polyfunctional (meth)acrylic compounds. Among these, the compound represented by the following formula 3 is preferred from the viewpoint of working better as a compatibilizer, not reducing the flexibility of the cured product of the curable resin composition, and not inhibiting the conformability to the substrate.
(c in the formula is an integer of 2 to 4. R ⁴ is a hydrogen atom or a methyl group. R ⁵ is a group consisting of a hydrocarbon group having 2 to 14 carbon atoms, an ether oxygen having 2 to 14 carbon atoms, A group consisting of (-O-) and a hydrocarbon group, a group consisting of a hydroxyl group having 2 to 14 carbon atoms and a hydrocarbon group, an isocyanurate skeleton, and at least one group selected from ether oxygen, a hydroxyl group, and a hydrocarbon group. or a group consisting of a bisphenol skeleton and at least one group selected from ether oxygen, hydroxyl group, and hydrocarbon).

Specifically, the polyfunctional (meth)acrylic compound in which c is 2 includes 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, and 1,6-hexanediol. Di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, Dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ethylene oxide added bisphenol A di(meth)acrylate, propylene oxide added bisphenol A di(meth)acrylate, ethylene oxide added bisphenol F di(meth)acrylate, dimethylol dicyclopentadiene di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide modified isocyanuric acid di(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl Examples include (meth)acrylate, polyether diol di(meth)acrylate, and the like.

Examples of polyfunctional (meth)acrylic compounds in which c is 3 or 4 include trimethylolpropane tri(meth)acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, and ethylene oxide-added trimethylolpropane tri(meth)acrylate. ) acrylate, propylene oxide added trimethylolpropane tri(meth)acrylate, ethylene oxide added isocyanuric acid tri(meth)acrylate, ethoxylated isocyanuric acid triacrylate, pentaerythritol tri(meth)acrylate, glycerin tri(meth)acrylate, propylene oxide added Examples include glycerin tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and pentaerythritol tetra(meth)acrylate.

The content of the polyfunctional (meth)acrylic compound (E) in the curable resin composition of the present invention is 0 to 25 parts by mass based on the total of 100 parts by mass of (A), (B), and (C). The amount is preferably 1 to 15 parts by mass.

<Surfactant (F)>
The curable resin composition of the present invention may contain a surfactant (F) to the extent that the object of the present invention is not impaired. Since the surfactant (F) is highly hydrophobic, its inclusion in the curable resin composition improves the moisture barrier properties of the encapsulant and prevents the alignment of liquid crystals from being disturbed even when exposed to severe heat and humidity tests. This can be further suppressed. As the surfactant (F), known silicone surfactants, fluorine surfactants, acrylic surfactants, etc. can be used without any particular restrictions, but from the viewpoint of improving moisture barrier properties, fluorine surfactants may be used. Activators are preferred. Commercially available 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", Examples include the same "F-559", the same "F-561", the same "R-94", the same "RS-72-K", and the same "RS-75". 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 1 part by mass, preferably 0 to 1 part by mass, based on 100 parts by mass in total of (A), (B), and (C). , 0.01 to 0.2 parts by mass.

<Silane coupling agent (G)>
The curable resin composition of the present invention may contain a silane coupling agent (G) to the extent that the object of the present invention is not impaired. The silane coupling agent (G) improves the interaction with other components and the base material, and by containing it in the curable resin composition, it improves the toughness of the cured product of the curable resin composition and the base material. Adhesion is improved, and the ability to follow the base material can be further enhanced regardless of changes in temperature environment. Known silane coupling agents can be used without particular restrictions, but (meth)acrylic groups or Those having reactive functional groups such as vinyl groups, thiol groups, epoxy groups, and isocyanate groups are preferred. Specifically, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyltrimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 3-(meth)acryloxy Propylmethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltri Examples include methoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-isocyanatepropyltriethoxysilane. These 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 10 parts by mass, based on a total of 100 parts by mass of (A), (B), and (C). is 1 to 5 parts by mass.

<Other ingredients>
The curable resin composition of the present invention may contain, in addition to the polyfunctional (meth)acrylic compound (E), surfactant (F), and silane coupling agent (G), as long as the object of the present invention is not impaired. Epoxy compounds, curing accelerators, ultraviolet absorbers, light stabilizers, antioxidants, polymerization inhibitors, leveling agents, adhesion agents, plasticizers, antifoaming agents, fillers, light shielding materials, conductive materials, spacers, etc. may contain additives.

<Composition ratio (mixing ratio)>
The curable resin composition of the present invention can reduce liquid crystal contamination in an uncured state by containing the above-mentioned (B), which has a property of being difficult to mix with liquid crystal. The curable resin composition of the present invention also includes a thiol group of the polyfunctional thiol compound (A) and a polymerizable inorganic compound of the polyfunctional urethane (meth)acrylate compound (B) and the polyfunctional (meth)allyl compound (C). A thiol-ene reaction proceeds between the saturated bonds and a cured product is obtained. The formed thioether bond can change the bond angle more flexibly than bonds due to atoms such as C, O, and N, so it increases the flexibility of the cured product of the curable resin composition and improves the conformability of the encapsulant to the base material. can be increased. In addition, the urethane groups contained in the polyfunctional urethane (meth)acrylate compound (B) can exhibit strong interactions such as hydrogen bonds with each other and with other polar groups even at low to high temperatures. The cured product is made tougher regardless of the environment, and the conformability of the sealing material to the base material can be improved. In addition, cured products made of thioether bonds have high flexibility in bond angles and can be cured to a high density so that atoms fill the gaps between bonds, so they have high moisture barrier properties and can withstand harsh heat and humidity tests. It is possible to suppress the alignment disorder of liquid crystal without being affected by moisture. This shows that even if the curable resin composition of the present invention comes into contact with the liquid crystal in an uncured state, the liquid crystal non-staining properties are reduced, and the sealing material made of the cured product of the curable resin composition is In addition to suppressing the alignment disorder of the liquid crystal even when it is in contact with the liquid crystal in a humid heat environment, in order to improve the ability to follow the substrate regardless of the temperature environment, (A), (B), and (C) are necessary. Both are indispensable. Further, by further using (D) in the curable resin composition containing (A), (B), and (C), the composition can be cured by only light irradiation and exhibit the above effects. In addition, the blending weight ratio (B)/(C) of (B) and (C) is 0.1 to 1.0, and the number of functional groups of the thiol group of (A) and the polymerization of (B) and (C). The ratio of the total number of functional groups of functional unsaturated bonds (thiol group/polymerizable unsaturated bond) is 0.5 to 3.0, and furthermore, the total number of (A), (B) and (C) is 100 parts by mass. On the other hand, by blending (D) in a proportion of 0.01 to 10.0 parts by mass, the curable resin composition does not contaminate the liquid crystal even if it comes into contact with the liquid crystal in an uncured state. The encapsulant obtained by curing the curable resin composition does not cause any disturbance in the alignment of the liquid crystal even when it comes into contact with the liquid crystal in a harsh humid heat environment, and it also maintains the stability of the base material regardless of changes in the temperature environment. It has excellent followability.

In the curable resin composition of the present invention, the liquid crystal non-staining property is improved, the liquid crystal is not contaminated even when it comes into contact with the liquid crystal in an uncured state, and the cured product of the curable resin composition is flexible and strong. In order to improve the conformability of the sealing material to the base material regardless of changes in the temperature environment, (B) out of a total of 100 parts by mass of (A), (B), and (C) should be added. It is preferable to contain 10 parts by mass or more. In addition, in order to improve the moisture barrier properties of the encapsulant and further suppress orientation disorder under severe moist heat tests, (B) out of a total of 100 parts by mass of (A), (B), and (C) must be It is preferable to contain 20 parts by mass or less. In other words, the curable resin composition does not contaminate the liquid crystal even if it comes into contact with the liquid crystal in an uncured state, the encapsulant suppresses the alignment disorder of the liquid crystal even when exposed to severe heat and humidity tests, and the encapsulant is compatible with the temperature environment. In order to achieve higher performance, such as having high conformability to the base material regardless of the shape, 10 parts by mass of (B) out of a total of 100 parts by mass of (A), (B), and (C) should be added. The content is preferably 20 parts by mass or less.
In addition, in the curable resin composition of the present invention, in order to improve the moisture barrier properties of the sealing material and further suppress orientation disorder under severe moist heat tests, the blending weight ratio of (B) and (C) is (B)/(C) is 0.1 to 0.6, which increases the flexibility and toughness of the cured product of the curable resin composition, and improves the conformability of the sealing material to the base material. In order to achieve this, the blending weight ratio (B)/(C) of (B) and (C) should be 0.2 to 1.0, and the flexibility of the cured product of the curable resin composition should be maintained at low to high temperatures. In order to increase the properties and toughness of the sealing material and to make it more conformable to the base material regardless of changes in the temperature environment, the blending weight ratio of (B) and (C) is (B)/(C). is preferably 0.3 to 1.0, that is, the sealing material suppresses alignment disorder of the liquid crystal even when exposed to severe heat and humidity tests, and the sealing material has a property that the sealing material does not adhere to the base material regardless of the temperature environment. In order to achieve high levels of performance such as high followability, it is preferable that the blending weight ratio (B)/(C) of (B) and (C) is 0.3 to 0.6.
Furthermore, in the curable resin composition of the present invention, in order to improve the moisture barrier properties of the sealing material and further suppress orientation disorder under severe moist heat tests, it is necessary to adjust the number of functional groups of the thiol group in (A). The ratio of the total number of functional groups in the polymerizable unsaturated bonds (thiol group/polymerizable unsaturated bond) in (B) and (C) is preferably 0.7 to 2.3, and the curable resin composition In order to increase the flexibility and toughness of the cured product and to make the conformability of the sealing material to the base material higher, it is necessary to It is preferable that the ratio of the total number of functional groups of saturated bonds (thiol group/polymerizable unsaturated bond) is 0.7 to 2.5, and the flexibility of the cured product of the curable resin composition is improved at low to high temperatures. In order to increase the toughness and the conformability of the sealing material to the base material regardless of changes in temperature environment, it is necessary to increase the number of functional groups of the thiol group in (A) and the polymerization of (B) and (C). It is preferable that the ratio of the total number of functional groups of functional unsaturated bonds (thiol group/polymerizable unsaturated bond) is 0.8 to 2.4, that is, even if the sealing material is exposed to a severe moist heat test In order to achieve higher performance, such as suppressing the alignment disorder of the liquid crystal and ensuring that the sealant has high conformability to the base material regardless of the temperature environment, it is necessary to increase the number of functional groups in the thiol group in (A) and ( The ratio of the total number of functional groups in the polymerizable unsaturated bonds in B) and (C) (thiol group/polymerizable unsaturated bond) is preferably 0.8 to 2.3.

<Film LCD panel>
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 crystal, a display element that displays an image like a display, and the like. The film liquid crystal panel of the present invention has, for example, a pair of substrates placed opposite each other, the periphery of which is sealed with the sealing material for film liquid crystal panels, and a liquid crystal material is present between them. Here, 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, PEDOT, etc. is applied. . It also includes those in which an alignment film or the like is further formed on the transparent electrode.
The film liquid crystal panel of the present invention is a liquid crystal panel formed from a substrate using the above-mentioned plastic transparent film base material, and the sealing material for the film liquid crystal panel is the sealing material used for the above-mentioned film liquid crystal panel. be.

<Formation of film liquid crystal panel>
The film liquid crystal panel of the present invention is produced by applying the curable resin composition of the present invention to one of the above-mentioned pair of substrates, dropping the liquid crystal on the inside thereof, overlapping the other substrate, and irradiating the above-mentioned curable resin composition with light. It is formed by curing a resin composition. Further, after applying a polymer dispersed liquid crystal containing a liquid crystal and a curable resin composition to one of the pair of substrates, stacking the other substrate and irradiating the substrate with light to cure the polymer dispersed liquid crystal, Some are formed by applying the curable resin composition of the present invention to the outer periphery and irradiating the curable resin composition with light to cure the curable resin composition.
The method of applying the above-mentioned curable resin composition is not particularly limited, and for example, methods using coating equipment such as dispenser coating, inkjet method, and screen printing method, and methods of applying by hand with a syringe or brush are applicable. Ru.
The light source for irradiating the curable resin composition with light is not particularly limited, and includes, for example, mercury lamps such as high-pressure mercury lamps and ultra-high-pressure mercury lamps, black light lamps, LED lamps, halogen lamps, electrodeless lamps, xenon lamps, and mercury fluorescent lamps. , LED fluorescent lamps, sunlight, electron beam irradiation equipment, etc. are applied.
In addition to the method of forming a film liquid crystal panel as described above and actually applying a voltage to check the degree of alignment, the contamination property of a film liquid crystal panel can also be evaluated by measuring the voltage holding rate. Voltage retention rate is an evaluation method that applies voltage to a liquid crystal cell and checks how much charge is retained after a certain period of time.If the liquid crystal is contaminated, the charge is not retained and the voltage retention rate decreases. decreases. A good voltage holding rate without contamination is preferably 90% or more, more preferably 95% or more.

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
<Evaluation method>
The performance of the curable resin compositions in each Example and Comparative Example was evaluated by the method described below.

<Liquid crystal non-staining property>
0.025 g of the curable resin composition was added to a sample bottle, and 1 g of liquid crystal (MLC-7021-000 manufactured by Merck & Co., Ltd.) was added, and the mixture was allowed to stand at 25° C. for 1 hour. Thereafter, ultraviolet irradiation (1000 mJ/cm ² ) was performed using a high-pressure mercury lamp to cure the curable resin composition, and the composition was heated at 100° C. for 2 hours. After 2 hours, the cured product and liquid crystal were separated using a centrifuge, and the liquid crystal was injected into a glass substrate liquid crystal cell with ITO (KSSZ-05/B107MINX05 manufactured by EHC Co., Ltd.). Using a liquid crystal physical property evaluation system (6245 manufactured by Toyo Technica Co., Ltd.), an initial voltage of AC 5 V was applied to the liquid crystal cell at 25°C for 64 μs, and the value obtained by multiplying the voltage ratio before and after a frame time of 16.7 ms by 100 (voltage retention rate) was calculated. Note that the higher the voltage holding rate, the more difficult it is to contaminate the liquid crystal, and in Tables 2 and 3, the voltage holding rate is described as liquid crystal non-contamination.

<Orientation disturbance under harsh humid heat environment>
Using a dispenser (Shot Master manufactured by Musashi Engineering Co., Ltd.) on a 40 mm x 45 mm glass substrate (RT-DM88-PIN manufactured by EHC Co., Ltd.) on which a transparent electrode and an alignment film were applied in this order on glass, The curable resin compositions produced in Examples and Comparative Examples were applied to a rectangular frame of 35 mm x 40 mm (line width: 1 mm), and liquid crystal (Merck) was applied inside the curable resin composition drawn on the frame. MLC-11900-000) manufactured by Co., Ltd.) was added dropwise. Next, the above glass substrate and the opposing glass substrate were bonded together under reduced pressure, and left at 25° C. for 1 hour. Ultraviolet irradiation (1000 mJ/cm ² ) was performed using a high-pressure mercury lamp to obtain a liquid crystal panel. After exposing the liquid crystal panel prepared in the same manner as above for 1000 hours under the conditions of 60°C and 90% RH, it was driven with a voltage of AC5V in a half-tone display state, and sealed with a cured product of the curable resin composition. Disturbances in the alignment of liquid crystals near the material were observed using a polarizing microscope. Note that the shorter the distance over which the alignment disorder spreads from the end of the sealing material, the less likely the alignment is to be disordered, and in Tables 2 and 3, the distance over which the alignment disorder spreads is listed.
◎: Orientation disorder does not spread beyond 0.3 mm from the end of the sealing material. ○: Orientation disorder spreads beyond 0.3 mm from the end of the sealant, but it does not extend beyond 0.6 mm. Orientation disorder has not spread ×: Orientation disorder has spread beyond 0.6 mm from the end of the sealing material

<Substrate followability>
The curable resin compositions produced in Examples and Comparative Examples were applied onto a 100 μm thick polyethylene terephthalate (PET) film using an applicator to a film thickness of 100 μm, and irradiated with ultraviolet light ( 1000 mJ/cm ² ) to cure the curable resin composition. The obtained PET film with a cured film was cut into a rectangular shape with a length of 100 mm and a width of 10 mm to prepare a sample. The obtained sample was subjected to a bending test using an MIT testing machine (BE-202 manufactured by Tester Sangyo Co., Ltd.) (conditions: load 1N, bending speed 175 cpm, bending radius 2.5 mm, bending speed 135°). The test sample was visually observed every 5000 times to check for cracks or peeling. Note that the greater the number of bends before cracking or peeling occurs, the better the substrate followability, and in Tables 2 and 3, the number of bends at which cracks or peeling occurred are listed.
◎: No cracks or peeling even after bending 20,000 times.
○: Cracks and peeling occur after 20,000 cycles, but no cracks or peeling occur up to 15,000 cycles.
×: Cracks and peeling occur within 10,000 times.

<Substrate followability after accelerated temperature environment change test>
The curable resin compositions produced in Examples and Comparative Examples were applied onto a 100 μm thick polyethylene terephthalate (PET) film using an applicator to a film thickness of 100 μm, and irradiated with ultraviolet light ( 1000 mJ/cm ² ) to cure the curable resin composition. The obtained PET film with a cured film was cut into a rectangular shape with a length of 100 mm and a width of 10 mm to prepare a sample. The obtained sample was exposed to 200 heating and cooling shocks (-30°C, 30 minutes ⇔ 80°C, 30 minutes) as a temperature environment change acceleration test. -202) was used to conduct a bending test (conditions: load 1N, bending speed 175 cpm, bending radius 2.0 mm, bending speed 135°). The test sample was visually observed every 5000 times to check for cracks or peeling. Note that the greater the number of bends before cracking or peeling occurs, the better the substrate followability, and in Tables 2 and 3, the number of bends at which cracks or peeling occurred are listed.
◎: No cracks or peeling even after bending 20,000 times.
○: Cracks and peeling occur after 20,000 cycles, but no cracks and peeling occur after 15,000 cycles.
×: Cracks and peeling occur within 10,000 times.

<Polyfunctional thiol compound (A)>
A-1: Dipentaerythritol hexakis (3-mercaptopropionate) [Number of thiol groups: 6]
A-2: Pentaerythritol tetrakis (3-mercaptopropionate) [Number of thiol groups: 4]
A-3: Tris-[(3-mercaptopropiomoloxy)-ethyl]-isocyanurate [Number of thiol groups: 3]

<Synthesis of polyfunctional urethane (meth)acrylate (B)>
[Synthesis of polyol compound (b-1)]
151.5 parts by mass of pimelic acid and 187.3 parts by mass of diethylene glycol were charged into a reaction vessel equipped with a stirrer, a rectification column, a nitrogen introduction tube, and a thermometer, and the mixture was heated to 140° C. and stirred under a nitrogen atmosphere. To this, 0.01 part by mass of tetrabutyl titanate was added, and the temperature was raised to 220°C to perform a dehydration reaction. Thereafter, the mixture was held at 220° C. to perform a dehydration reaction. 18 hours after the start of the dehydration reaction, the contents were cooled to obtain diol compound (b-1) (weight average molecular weight: 1,000).

[Synthesis of polyol compound (b-2)]
150.2 parts by mass of adipic acid and 158.3 parts by mass of 3-methyl-1,5-pentanediol were charged into a reaction vessel equipped with a stirrer, a rectification column, a nitrogen introduction tube, and a thermometer, and the mixture was heated to 140 parts by mass under a nitrogen atmosphere. The mixture was heated to ℃ and stirred. To this, 0.01 part by mass of tetrabutyl titanate was added, and the temperature was raised to 220°C to perform a dehydration reaction. Thereafter, the mixture was held at 220° C. to perform a dehydration reaction. 18 hours after the start of the dehydration reaction, the contents were cooled to obtain diol compound (b-2) (weight average molecular weight: 1,500).

[Synthesis of polyol compound (b-3)]
In a reaction vessel equipped with a stirrer, a rectification column, an air condenser, a thermometer, a receiver, and a vacuum device, 160.3 parts by mass of diphenyl carbonate, 234.1 parts by mass of 1,6-hexanediol, and 0.1 parts by mass of tetrabutyl titanate were added. Parts by mass were charged, heated to 100° C. under reduced pressure of 10 Torr, and stirred for 5 hours. The by-produced phenol was removed by distillation, and the contents were cooled to obtain a diol compound (b-3) (weight average molecular weight: 600).

[Synthesis of urethane (meth)acrylate (B-1)]
101.1 parts by mass of polyol compound (b-1) was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, and stirring was started. Next, 0.1 parts by mass of dibutyltin laurate and 32.1 parts by mass of isophorone diisocyanate as a diisocyanate were added, the internal temperature was raised to 80°C while being careful not to generate heat, and then the temperature was maintained for 3 hours. Stirred. Furthermore, 0.1 parts by mass of methquinone as a polymerization inhibitor and 24.0 parts by mass of 2-hydroxyethyl acrylate as a (meth)acrylate having a hydroxyl group were added, and the mixture was stirred at 85°C for 2 hours. ) Acrylate (B-1) was obtained (weight average molecular weight: 3000).

[Synthesis of (B-2) to (B-5)]
Polyfunctional urethane (meth)acrylates (B-2) to (B-5) were obtained in the same manner as above except that the polyol compound, diisocyanate compound, and (meth)acrylate compound having a hydroxyl group in Table 1 were used. Ta.

<Polyfunctional allyl compound (C)>
C-1: 1,3-diallyl-5-glycidyl isocyanurate [number of allyl groups: 2]
C-2: Triallyl isocyanurate [number of allyl groups: 3]
C-3: Pentaerythritol tetraallyl ether [number of allyl groups: 4]
C-4: Ethylene glycol monoallyl ael [number of allyl groups: 1]

<Photopolymerization initiator (D)>
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

<(E) component: polyfunctional (meth)acrylate>
E-1: Pentaerythritol tetraacrylate E-2: Trimethylolpropane trimethacrylate

<(F) component: surfactant>
F-1: Megafac F-477 Manufactured by DIC Corporation F-2: Megafac F-554 Manufactured by DIC Corporation

<(G) component: silane coupling agent>
G-1: 3-methacryloxypropyltrimethoxysilane G-2: 3-mercaptopropyltrimethoxysilane

[Example 1]
The above components were added to a stirring pot in the amounts shown in Tables 2 and 3 below, and mixed and stirred for 2 hours to obtain a curable resin composition. Each evaluation was performed using the curable resin composition. The results are shown in Tables 2 and 3.

As a result of the above tests, the curable resin compositions of each example showed excellent liquid crystal non-staining properties by containing the components (A) to (C) in appropriate amounts specified in the present invention, and It did not cause any disturbance in the alignment of the liquid crystal afterward, and had high followability to the substrate regardless of the temperature environment.

On the other hand, in Comparative Example 1, since it does not contain the polyfunctional thiol compound (A), the encapsulant for a film liquid crystal panel obtained by curing the curable resin composition does not have any alignment disorder in the liquid crystal when subjected to a severe heat and humidity test. This resulted in poor followability to the base material. In Comparative Examples 2 and 3, since the polyfunctional urethane (meth)acrylate compound (B) is not contained, the curable resin composition has poor liquid crystal non-staining property, and the film liquid crystal obtained by curing the curable resin composition Encapsulants for panels caused alignment disturbances in liquid crystals during severe heat-and-moisture tests, and had poor followability to the substrate. In Comparative Example 4, 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 caused alignment disorder of the liquid crystal in a severe heat and humidity test. This resulted in poor followability to the base material. Comparative Example 5 does not contain a photopolymerization initiator (D), so the encapsulant for a film liquid crystal panel obtained by curing the curable resin composition does not cause alignment disorder of liquid crystals in a severe heat and humidity test. This resulted in poor followability to the base material.

In Comparative Example 6, the blended weight ratio (B)/(C) was larger than the specified range, so the encapsulant for film liquid crystal panels obtained by curing the curable resin composition could not be subjected to the severe moist heat test. This caused alignment disorder of the liquid crystal. In Comparative Example 7, the blending weight ratio (B)/(C) was smaller than the specified range, so the curable resin composition had poor liquid crystal non-staining properties, and the film liquid crystal obtained by curing the curable resin composition Encapsulants for panels caused alignment disturbances in liquid crystals during severe heat-and-moisture tests, and had poor followability to the substrate.

In Comparative Example 8, the curable resin composition was The film liquid crystal panel encapsulant obtained by curing caused liquid crystal alignment disorder in the severe heat and humidity test, and had poor followability to the substrate after the accelerated temperature environment change test. In Comparative Example 9, the curable resin composition was The film liquid crystal panel encapsulant obtained by curing caused liquid crystal alignment disorder in severe heat and humidity tests, and had poor followability to the substrate.

In Comparative Example 10, since the number of functional groups in the polyfunctional allyl compound (C) is small, the encapsulant for a film liquid crystal panel obtained by curing the curable resin composition showed disordered alignment of liquid crystals in a severe moist heat test. This resulted in poor followability to the base material. In Comparative Example 11, since the amount of the photopolymerization initiator (D) was large, the encapsulant for a film liquid crystal panel obtained by curing the curable resin composition showed disordered alignment of the liquid crystal in a severe heat and humidity test. It was something that would cause something to happen.

Comparative Example 12 contains polyfunctional (meth)acrylate as component (E) as another component, but since the blending weight ratio (B)/(C) is smaller than the specified range, the curable resin composition The encapsulating material for film liquid crystal panels obtained by curing a curable resin composition has poor liquid crystal non-contamination properties, and the liquid crystal alignment disorder occurs in harsh heat and humidity tests, making it difficult to follow the substrate. was also low. In Comparative Example 13, the surfactant component (F) is included as another component, but the blended weight ratio (B)/(C) is larger than the specified range, so the film liquid crystal panel encapsulant is , which caused alignment disturbances in the liquid crystal during severe heat and humidity tests. Comparative Example 14 contains a silane coupling agent as component (G) as other components, but the number of functional groups in the thiol group in (A) and the number of functional groups in the polymerizable unsaturated bonds in (B) and (C) Because the total ratio of The ability to follow the substrate after the accelerated environmental change test was also low.

Claims (2)

(A) a polyfunctional thiol compound having 2 to 6 thiol groups;
(B) a polyfunctional urethane (meth)acrylate compound having 2 to 3 (meth)acrylic groups;
(C) a polyfunctional allyl compound having 2 to 4 (meth)allyl groups;
(D) a photopolymerization initiator;
The blending weight ratio (B)/(C) of (B) and (C) is 0.1 to 1.0,
The ratio of the total number of functional groups in the thiol group in (A) and the number of functional groups in the polymerizable unsaturated bonds in (B) and (C) (thiol group/polymerizable unsaturated bond) is 0.5 to 3.0. ,
A curable resin composition used in a sealing material for film liquid crystal panels, in which (D) is 0.01 to 10.0 parts by mass based on a total of 100 parts by mass of (A), (B), and (C). thing. A film liquid crystal panel whose edges are sealed with the curable resin composition according to claim 1.