JP2019112356A - New compound and resin composition based on the same - Google Patents

Abstract

To provide a new curable compound and a resin composition based on the same; specifically, a resin composition excellent in adhesive strength, particularly adhesive strength to an organic film, and a new compound used for the same; where the compound realizes both flexibility and low moisture permeability.SOLUTION: The invention provides a compound represented by formula (1) in the figure. (In formula (1), R represents a hydrocarbon group with 10 or more carbon atoms, where the hydrocarbon group may include oxygen, nitrogen and sulfur; and BP represents a bisphenol skeleton.)SELECTED DRAWING: None

Description

  The present invention relates to a novel curable compound and a resin composition using the same. More specifically, the present invention relates to a resin composition which is excellent in adhesive strength, in particular, adhesive strength to an organic film, and a novel compound used therefor. In addition, the compound of the present invention realizes both the flexibility and the low moisture permeability.

The curable resin composition is widely used in adhesive applications for electronic parts such as adhesives for displays, encapsulants for solar cells, semiconductor encapsulants and the like. Adhesive strength is one of the required properties common to these, and recently, adhesive strength to organic materials may be required.
In particular, in the case of using as an adhesive for liquid crystal displays, the adhesive strength to organic films such as alignment films is often required.

In the liquid crystal display, it is necessary to align the liquid crystal molecules in a certain direction in the plane, so the alignment film is provided on the substrate surface, and by rubbing, the properties of the alignment film surface are changed to realize alignment control of the liquid crystal. doing. Most of those used in practice as this alignment film are polyimide materials.
However, the rubbing method has problems such as dust generation from cloth and alignment film, generation of static electricity, physical flaws and the like, and a noncontact non-rubbing method is desired. One of them is the photoalignment method proposed by Gibbons et al. In 1989, and has been actively studied in recent years.

  The above-mentioned alignment film for photo alignment has greatly different chemical characteristics from the alignment film for rubbing, and the surface state is also different. Therefore, it is difficult to obtain sufficient adhesive strength with conventional adhesives for liquid crystal displays.

  In the conventional liquid crystal display element, the application position of the sealing agent is mainly on an inorganic material such as glass or ITO, and the sealing agent is designed in consideration of the adhesion to these inorganic materials. However, along with the expansion of applications of liquid crystal display devices in recent years, the narrowing of the frame of the liquid crystal display unit has progressed, and substrates on which a sealing agent is applied on alignment films are rapidly spreading. There is a problem that the adhesion to the membrane is insufficient.

  Various techniques have been proposed to solve the problem of adhesion between the liquid crystal sealing agent and the alignment film. For example, Patent Document 1 proposes a sealing agent of a (meth) acrylate compound having a structure derived from a cyclic lactone. This is a method of achieving high adhesive strength by lowering the elastic modulus of the curable resin and providing flexibility, but in the case of this method, there is a problem that the moisture permeability becomes high.

In recent years, curved displays and flexible displays have been developed and commercialized. As a substrate used for such a display, a flexible one such as a plastic film is used instead of a rigid one such as conventional glass (Patent Document 2).
From such a background, the resin composition is required to have the property of following the deflection of a substrate or the like, that is, being flexible even after curing.

  In addition, the sealant having excellent flexibility is also advantageous in adhesive strength. For example, it is possible to reduce peeling and equipment destruction due to impact. From this point of view also, the demand for imparting flexibility to the sealing agent is increasing.

  On the other hand, in order to enhance the flexibility of the cured product, it is an effective means to lower the crosslink density of the cured product. However, it is normal to deteriorate the moisture permeability as the crosslink density decreases. This is considered to be due to the infiltration of water from the loose part of the network. Therefore, in order to secure low moisture permeability, it is necessary to realize contradictory characteristics of increasing flexibility without lowering the crosslinking density or lowering the crosslinking density but not deteriorating the moisture permeability.

  Heretofore, development of an adhesive for a display element having flexibility has been carried out from the viewpoint of improving adhesive strength (Patent Document 3). However, one with sufficient performance to adapt to the above flexible substrate has not been realized yet.

Patent 5508001 JP, 2012-238005, A JP, 2016-24240, A

The present invention relates to a novel curable compound and a resin composition using the same, which is excellent in adhesive strength to an organic film, particularly to an alignment film for light alignment, and thus, when used for a liquid crystal sealing agent, for example, a substrate It is intended to facilitate the manufacture of the liquid crystal display cell without causing peeling.
Further, the present invention is a resin composition which can be applied to a flexible display and a display having a curved shape, and since it is compatible with flexibility and low moisture permeability, it is useful as a sealing agent for a display.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the compound which has a specific structure was especially excellent in adhesiveness with an organic film, and low moisture permeability, as a result of earnestly examining in order to solve the said subject, and came to this invention It is.
In the present specification, "(meth) acrylic" as used herein means "acrylic" and / or "methacrylic".

That is, the present invention relates to the following [1] to [12].
[1] A compound represented by the following formula (1).

(In formula (1), R represents a hydrocarbon group having 10 or more carbon atoms, and may have oxygen, nitrogen, or sulfur in the hydrocarbon group. BP represents a bisphenol skeleton.)
[2] The compound according to item 1 above, which has one or more carbon-carbon double bonds in R in the formula (1).
[3] The compound according to the above-mentioned 1 or 2, wherein in the formula (1), BP is bisphenol A.
[4] Component (A) A resin composition containing the compound according to any one of the above items 1 to 3.
[5] The resin composition according to any one of [1] to [4], further comprising a component (B) a curable compound.
[6] The resin composition according to any one of the above items 1 to 5, wherein the component (B) is a component (B-1) (meth) acrylic compound.
[7] The resin composition according to any one of the above items 1 to 6, wherein the component (B) is a mixture of the component (B-1) (meth) acrylic compound and the component (B-2) epoxy compound.
[8] The resin composition according to any one of the above items 1 to 7, further comprising a component (C) an organic filler.
[9] The resin composition according to any one of the above items 1 to 8, further comprising a component (D) an inorganic filler.
[10] The resin composition according to any one of the above items 1 to 9, further comprising a component (E) a silane coupling agent.
[11] The resin composition according to any one of the above 1 to 10, further comprising a component (F) a thermosetting agent.
[12] The resin composition according to any one of the above items 1 to 11, further comprising component (G) a photoradical polymerization initiator.

  The curable compound of the present invention is excellent in adhesive strength with an organic film and also has low moisture permeability, and thus is very useful in adhesive applications for electronic parts, particularly in resin compositions.

[(A) Curable Compound of the Present Invention]
The curable compound of the present invention has a structure represented by the above formula (1).
In the above formula (1), R represents a hydrocarbon group having 10 or more carbon atoms, and the hydrocarbon group may have a hetero atom such as oxygen, nitrogen or sulfur. BP represents a bisphenol skeleton.
Here, the three R's and BP's present in the formula (1) may be identical or different.

In said Formula (1), R represents a C10 or more hydrocarbon group, and you may have oxygen, nitrogen, and sulfur in a hydrocarbon group. BP represents a bisphenol skeleton. The hydrocarbon group may be linear, branched or cyclic, or may be a structure having both of them. In addition, the hydrocarbon group may have a double bond or a triple bond. Those having a carbon-carbon double bond in the hydrocarbon group are preferable.
The number of carbon atoms of R is preferably 12 or more, more preferably 14 or more.

  In the above formula (1), BP represents a bisphenol skeleton. The bisphenol skeleton means a skeleton represented by the following formula (2), preferably a bisphenol A skeleton.

(In formula (1), A represents CH ₂ , CH (CH ₃ ), C (CH ₃ ) ₂ , S, O, SO ₂ ).

  As a compound represented by Formula (1), the structure represented, for example by following formula (3) can be illustrated.

The resin composition of the present invention contains the component (A).
The preferable content of the component (A) is usually 5 to 50% by mass, preferably 5 to 30% by mass, and more preferably 10 to 20% by mass, based on the total amount of the resin composition.

[(B) curable compound]
The resin composition of the present invention contains, as the component (B), a curable compound other than the component (A) (hereinafter, also simply referred to as "component (B)").
The component (B) is not particularly limited as long as it is a compound which is cured by light, heat and the like, but it is not limited to (B-1) (meth) acrylic compound (hereinafter, also simply referred to as "component (B-1)"). In some cases, it is preferable.
Here, "(meth) acrylic" means "acrylic" and / or "methacrylic" (the same shall apply hereinafter). As a component (B-1), a (meth) acrylic ester compound, an epoxy (meth) acrylate compound, etc. are mentioned, for example.

[(B-1) (meth) acrylate compound]
Specific examples of (meth) acrylic ester compounds include N-acryloyloxyethyl hexahydrophthalimide, acryloyl morpholine, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexane-1,4-dimethanol Mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenylpolyethoxy (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, o-phenylphenol monoethoxy Meta) acrylate, o-phenylphenol polyethoxy (meth) acrylate, p-cumyl phenoxyethyl (meth) acrylate, isobonyl (meth) acrylate, tribromophenyl Nyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6 -Hexanediol di (meth) acrylate, 1, 9 nonane diol di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, bisphenol A polyethoxy di (meth) acrylate, bisphenol A polypropoxy di (meth) acrylate, bisphenol F polyethoxy di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (acryloxyethyl) isocyanurate, pentaerys Tall tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) Acrylate, trimethylolpropane polyethoxy tri (meth) acrylate, ditrimethylol propane tetra (meth) acrylate, ester diacrylate of neopentyl glycol and hydroxypivalic acid, and ε-caprolactone adduct of neopentyl glycol and ester of hydroxypivalic acid Monomers such as diacrylate can be mentioned. Preferably, N-acryloyloxyethyl hexahydrophthalimide, phenoxyethyl (meth) acrylate, and dicyclopentenyl oxyethyl (meth) acrylate can be mentioned.
The epoxy (meth) acrylate compound is obtained by the reaction of an epoxy compound and (meth) acrylic acid by a known method. The epoxy compound as the raw material is not particularly limited, but is preferably a difunctional or higher epoxy compound, for example, resorcinol diglycidyl ether, bisphenol A epoxy compound, bisphenol F epoxy compound, bisphenol S epoxy compound , Phenol novolac epoxy compound, cresol novolac epoxy compound, bisphenol A novolac epoxy compound, bisphenol F novolac epoxy compound, alicyclic epoxy compound, aliphatic chain epoxy compound, glycidyl ester epoxy compound, glycidyl amine epoxy Compound, hydantoin type epoxy compound, isocyanurate type epoxy compound, phenol novolac type epoxy compound having triphenolmethane skeleton, and the like Catechol, bifunctional phenols diglycidyl ethers of resorcinol and the like, bifunctional alcohols diglycidyl ethers of, and their halides, and the like hydrogenated product. Among them, bisphenol A epoxy compounds and resorcin diglycidyl ether are preferable from the viewpoint of liquid crystal contamination. Moreover, the ratio of an epoxy group and a (meth) acryloyl group is not limited, It selects suitably from a viewpoint of process compatibility. In addition, the partial epoxy (meth) acrylate which acrylic-esterifies a part of epoxy group is used suitably. The proportion of acrylation in this case is preferably about 30 to 70%.
The component (B-1) may be used alone or in combination of two or more. When the component (B-1) is used in the resin composition of the present invention, it is usually 5 to 50% by mass, preferably 5 to 30% by mass, based on the total amount of the resin composition.

[(B-2) epoxy compound]
As an aspect of the present invention, it is further preferable that the component (B) further contains (B-2) an epoxy compound (hereinafter, also simply referred to as "component (B-2)").
The epoxy compound is not particularly limited, but is preferably a difunctional or higher epoxy compound, for example, resorcinol diglycidyl ether, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy Epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type Epoxy resin, isocyanurate type epoxy resin, phenol novolac type epoxy resin having triphenolmethane skeleton, other, bifunctional functional groups such as catechol and resorcinol Diglycidyl ethers of Nord acids, difunctional alcohols diglycidyl ethers of, and their halides, and the like hydrogenated product. Among them, bisphenol A epoxy resin and resorcin diglycidyl ether are preferable from the viewpoint of liquid crystal contamination.
The component (B-2) may be used alone or in combination of two or more. When the component (B-2) is used in the resin composition of the present invention, it is usually 5 to 50% by mass, preferably 5 to 30% by mass, based on the total amount of the resin composition.
In addition, in the resin composition of this invention, the compounding quantity of a component (B) is 10-80 mass% normally in the total amount of a resin composition, Preferably it is 20-70 mass%. The blending amounts in the case of mixing and using the component (B-1) and the component (B-2) are also the same.

[(C) organic filler]
The resin composition of the present invention may contain an organic filler (hereinafter, also simply referred to as “component (C)”) as the component (C). Examples of the organic filler include urethane particles, acryl particles, styrene particles, styrene olefin particles, and silicone particles. In addition, as silicone microparticles, KMP-594, KMP-597, KMP-598 (made by Shin-Etsu Chemical Co., Ltd.), Trefil ^RTM E-5500, 9701, EP-2001 (made by Toray Dow Corning) are preferable, and as urethane microparticles, JB- 800T, HB-800BK (Kegami Kogyo Co., Ltd.), preferred as styrene fine particles are Lavalon ^RTM T320C, T331C, SJ4400, SJ5400, SJ6400, SJ4300C, SJ5300C, SJ6300C (Mitsubishi Chemical), and as styrene olefin fine particles is Septon ^RTM SEPS 2004, SEPS 2063 is preferred.
These organic fillers may be used alone or in combination of two or more. Moreover, it is good also as core-shell structure using 2 or more types. Among these, acrylic fine particles and silicone fine particles are preferable.
When using the said acryl fine particle, the case where it is an acryl rubber of the core-shell structure which consists of 2 types of acryl rubber is preferable, Especially preferably, a thing whose core layer is n-butyl acrylate and whose shell layer is methyl methacrylate is preferable. This is marketed by Aika Industry Co., Ltd. as Zefiac ^RTM F-351.
Further, as the above-mentioned silicone fine particles, there can be mentioned organopolysiloxane crosslinked powder, linear dimethylpolysiloxane crosslinked powder and the like. Moreover, as composite silicone rubber, what coated silicone resin (for example, polyorgano silsesquioxane resin) on the surface of the said silicone rubber is mention | raise | lifted. Among these fine particles, particularly preferred are silicone rubber of linear dimethylpolysiloxane crosslinked powder or complex silicone rubber microparticles of silicone resin-coated linear dimethylpolysiloxane crosslinked powder. These may be used alone or in combination of two or more. Also, preferably, the shape of the rubber powder is spherical with less thickening of viscosity after addition. When the component (C) is used in the resin composition of the present invention, it is usually 5 to 50% by mass, preferably 5 to 40% by mass, based on the total amount of the resin composition.

[(D) inorganic filler]
The resin composition of the present invention may contain an inorganic filler (hereinafter, also simply referred to as a component (D)) as the component (D). As the inorganic filler contained in the present invention, silica, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide, aluminum hydroxide Magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc., preferably fused silica, crystalline silica, silicon nitride, nitrided Boron, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate and aluminum silicate can be mentioned, with preference given to silica, alumina and talc. These inorganic fillers may be used as a mixture of two or more.
If the average particle diameter of the inorganic filler is too large, it may be a defect factor such that the gap formation during bonding of the upper and lower glass substrates can not be well at the time of manufacturing a narrow gap liquid crystal display cell. More preferably, it is 300 nm or less. The lower limit is preferably about 10 nm, and more preferably about 100 nm. The particle diameter can be measured by a laser diffraction / scattering type particle size distribution measuring device (dry type) (manufactured by Seishin Enterprise Co., Ltd .; LMS-30).
When an inorganic filler is used in the resin composition of the present invention, it is usually 5 to 50% by mass, preferably 5 to 40% by mass, based on the total amount of the resin composition. When the content of the inorganic filler is less than 5% by mass, the adhesion strength to the glass substrate is lowered, and the reliability against moisture resistance is also poor. In addition, when the content of the inorganic filler is more than 50% by mass, the content of the filler is too large, so that it may be difficult to be crushed and the gap of the liquid crystal cell may not be formed.

[(E) Silane coupling agent]
The resin composition of the present invention can improve adhesion strength and moisture resistance by adding a silane coupling agent (hereinafter, also simply referred to as "component (E)") as the component (E).
As the component (E), 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl tritrile Methoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3- Aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropyl Chill dimethoxysilane, 3-chloropropyl trimethoxy silane, and the like. Since these silane coupling agents are sold by Shin-Etsu Chemical Co., Ltd. as KBM series, KBE series etc., they are easily available from the market. When the component (E) is used in the resin composition of the present invention, 0.05 to 3% by mass is preferable in the total amount of the resin composition.

[(F) curing catalyst]
In the resin composition of the present invention, the reactivity can be improved by adding a curing catalyst (hereinafter, also simply referred to as "component (F)") as the component (F).
As a curing catalyst, although amines and imidazoles can be mentioned, imidazoles are especially suitable. As imidazoles, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2 -Methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2'-methylimidazole (1 ')) Ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-ethyl-4-methylimidazole (1 ')) Ethyl-s-triazine, 2,4-diamino-6 (2'-methyl imida Zole (1 ')) Ethyl-s-triazine isocyanuric acid adduct, 2: 3 adduct of 2-methylimidazole isocyanuric acid, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole And 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole and the like.

[(G) photoradical polymerization initiator]
The resin composition of the present invention may contain a radical photopolymerization initiator (hereinafter, also simply referred to as “component (G)”) as component (G). The photo radical polymerization initiator is not particularly limited as long as it is a compound which generates a radical or an acid upon irradiation with ultraviolet light or visible light to initiate a chain polymerization reaction. For example, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone Diethylthioxanthone, benzophenone, 2-ethylanthraquinone, 2-hydroxy-2-methylpropiophenone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propane, 2,4,6- Trimethyl benzoyl diphenyl phosphine oxide, camphor quinone, 9-fluorenone, diphenyl dishydride etc. can be mentioned. Specifically, IRGACURE ^RTM 651, 184, 2959, 127, 907, 369, 379 EG, 819, 784, 754, 500, OXE01, OXE02, OXE03, OXE04, DAROCURE ^RTM 1173, LUCIRIN ^RTM TPO (all manufactured by BASF Corporation) , Seikol ^RTM Z, BZ, BEE, BIP, BBI (all manufactured by Seiko Instruments Inc.) and the like. Among these, preferred are oxime ester initiators OXE01, OXE02, OXE03 and OXE04.
Further, from the viewpoint of liquid crystal staining, it is preferable to use one having a (meth) acryl group in the molecule, for example, 2-methacryloyloxyethyl isocyanate and 1- [4- (2-hydroxyethoxy) -phenyl]- The reaction product with 2-hydroxy-2 methyl-1-propan-1-one is preferably used. This compound can be obtained by preparation according to the method described in WO 2006/027982.
When the component (G) is used in the resin composition of the present invention, it is usually 0.001 to 3% by mass, preferably 0.002 to 2% by mass, based on the total amount of the resin composition.

[(H) thermal radical polymerization initiator]
The resin composition of the present invention can contain (H) thermal radical polymerization initiator (hereinafter, also simply referred to as “component (H)”) to improve the curing speed and the curability.
The thermal radical polymerization initiator is not particularly limited as long as it generates a radical by heating to initiate chain polymerization reaction, but organic peroxides, azo compounds, benzoin compounds, benzoin ether compounds, acetophenone compounds, benzopinacol, etc. Preferably, benzopinacol is used. For example, as organic peroxides, Kayamec ^RTM A, M, R, L, LH, SP-30C, Percadox CH-50L, BC-FF, Cadox B-40 ES, Percadox 14, Trigonox ^RTM 22-70E, 23-C70, 121, 121-50E, 121-LS50E, 21-LS50E, 42, 42LS, Kayaester ^RTM P-70, TMPO-70, CND-C70, OO-50 E, AN, Kayabutyl ^RTM B, Perka Dox 16 Kayacaron ^RTM BIC-75, AIC-75 (manufactured by Kayaku Akzo Co., Ltd.), Permec ^RTM N, H, S, F, D, G, Perhexa ^RTM H, HC, TMH, C, V, 22, MC, Percure ^RTM AH, AL, HB, Perbutyl ^{RTM H, C, ND, L} , Percumyl ^RT H, D, PEROYL ^RTM IB, IPP, Perocta ^RTM ND (manufactured by NOF Corporation) and the like are commercially available.

  Moreover, as an azo compound, VA-044, 086, V-070, VPE-0201, VSP-1001 (made by Wako Pure Chemical Industries Ltd.) etc. are available as a commercial item.

  The content of the component (H) is preferably 0.0001 to 10% by mass, more preferably 0.0005 to 5% by mass in the total amount of the resin composition of the present invention, and 0.001 to 1% by mass. 3% by weight is particularly preferred.

  In the resin composition of the present invention, additives such as a radical polymerization inhibitor, a pigment, a leveling agent, an antifoaming agent, and a solvent can be further blended, as necessary.

[Radical polymerization inhibitor]
The radical polymerization inhibitor is not particularly limited as long as it is a compound which reacts with radicals generated from photo radical polymerization initiators, thermal radical polymerization initiators, etc. to prevent polymerization, and quinones, piperidines, Hindered phenol type, nitroso type etc. can be used. Specifically, naphthoquinone, 2-hydroxynaphthoquinone, 2-methylnaphthoquinone, 2-methoxynaphthoquinone, 2,2,6,6-tetramethylpiperidine-1-oxyl, 2,2,6,6-tetramethyl-4 -Hydroxypiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-methoxypiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-phenoxypiperidine-1-oxyl, hydroquinone 2-Methylhydroquinone, 2-methoxyhydroquinone, parabenzoquinone, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butylcresol, stearyl β- (3 5-Di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis 4-ethyl-6-t-butylphenol), 4,4'-thiobis-3-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 3,9 -Bis [1,1-dimethyl-2- [β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl], 2,4,8,10-tetraoxaspiro [5,5 5] Undecane, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl propionate) methane, 1,3,5-tris (3 ′, 5′-di- t-Butyl-4'-hydroxybenzyl) -sec-triazine-2,4,6- (1H, 3H, 5H) trione, paramethoxyphenol, 4-methoxy-1-naphthol, thiodiphenylamine, N-dimethane Nitroso aluminum salts of phenyl hydroxy amine, trade name ADK STAB LA-81, but such trade name ADK STAB LA-82 (manufactured by KK ADEKA) and the like, but is not limited thereto. Among them, naphthoquinone type, hydroquinone type and nitroso type piperazine type radical polymerization inhibitors are preferable, and naphthoquinone, 2-hydroxynaphthoquinone, hydroquinone, 2,6-di-tert-butyl-P-cresol, polystop 7300P More preferably manufactured by company, and most preferably Polystop 7300P (manufactured by Shoto Co., Ltd.).
The content of the radical polymerization inhibitor is preferably 0.0001 to 1% by mass, more preferably 0.001 to 0.5% by mass, and still more preferably 0.01 to 0%, based on the total amount of the photocurable resin composition of the present invention. 2% by weight is particularly preferred.

  As an example of the method for obtaining the photocurable resin composition of the present invention, the following methods are available. First, the component (G) is heated and dissolved in the components (A) and (B) as required. Then, after cooling to room temperature, components (C), (D), (E), (F), (H), an antifoaming agent, a leveling agent, a solvent, etc. are added as necessary, and known mixing devices, For example, the resin composition of the present invention can be produced by uniformly mixing with a three-roll, sand mill, ball mill or the like and filtering through a metal mesh.

  Further, the resin composition of the present invention is very useful as an adhesive for liquid crystal display cells, particularly as a liquid crystal sealing agent. An example is shown below about a liquid crystal display cell at the time of using the resin composition of this invention as a liquid-crystal sealing compound.

In a liquid crystal display cell manufactured using the adhesive for liquid crystal display cell of the present invention, a pair of substrates having a predetermined electrode formed on the substrate is disposed opposite to each other at a predetermined distance, and the periphery is sealed with the liquid crystal sealant of the present invention The liquid crystal is sealed in the gap. The type of liquid crystal to be enclosed is not particularly limited. Here, the substrate is composed of a combination of light transmitting property to at least one of glass, quartz, plastic, silicon and the like. As the manufacturing method, after adding a spacer (space control material) such as glass fiber to the liquid crystal sealing agent of the present invention, the liquid crystal sealing agent is applied to one of the pair of substrates using a dispenser or a screen printing apparatus. After curing, temporary curing is performed at 80 to 120 ° C., if necessary. Thereafter, liquid crystal is dropped on the inner side of the ridge of the liquid crystal sealing agent, the other glass substrate is superposed in vacuum, and the gap is taken out. After forming the gap, the liquid crystal display cell of the present invention can be obtained by curing at 90 to 130 ° C. for 30 minutes to 2 hours. In the case of using as a light and heat combination type, the liquid crystal sealing agent portion is irradiated with ultraviolet light by an ultraviolet light irradiator and light curing is performed. UV irradiation dose is preferably 500~6000mJ / cm ^2, more preferably the dose of 1000~4000mJ / cm ² is preferred. Thereafter, the liquid crystal display cell of the present invention can be obtained by curing at 90 to 130 ° C. for 30 minutes to 2 hours as required. The liquid crystal display cell of the present invention thus obtained is free from display defects due to liquid crystal contamination, and is excellent in adhesion and moisture resistance. As a spacer, glass fiber, a silica bead, a polymer bead etc. are mention | raise | lifted, for example. The diameter varies depending on the purpose, but is usually 2 to 8 μm, preferably 4 to 7 μm. The amount thereof used is usually about 0.1 to 4 parts by mass, preferably 0.5 to 2 parts by mass, and more preferably about 0.9 to 1.5 parts by mass with respect to 100 parts by mass of the liquid crystal sealing agent of the present invention is there.

  The resin composition of the present invention is very suitable for use in adhesive applications where curing, adhesion to different adherends, wet heat reliability are required. For example, a liquid crystal sealing agent, a sealant for an organic EL, and an adhesive for a touch panel.

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the examples. In the following description, "part" and "%" are based on mass unless otherwise specified.

Example 1
[Acrylateation of castor oil modified epoxy resin]
In a flask equipped with a stirrer, a reflux condenser and a thermometer, 104 g of castor oil-modified epoxy resin (product name: EPOX-MKR151, manufactured by Printech Co., Ltd.) is dissolved in 120 g of toluene, 0.4 g of toluene was added, and the temperature was raised to 60.degree. Thereafter, 18.9 g of 100% equivalent acrylic acid of epoxy group is added and the temperature is further raised to 80 ° C. 0.6 g of trimethyl ammonium hydroxide as a reaction catalyst is added to this and stirred at 98 ° C. for about 40 hours The reaction solution was obtained. The reaction solution was washed with water and toluene was distilled off to obtain 110 g of the target compound.

[Examples 1-2, Comparative Examples 1-5]
The components (A) and (B) are mixed in the proportions shown in Table 1 below, the component (G) is dissolved by heating at 90 ° C., and then cooled to room temperature, and the components (C), (D) and (E) , (F), (H) and (O) are added and stirred, then dispersed by a three-roll mill, filtered through a metal mesh (635 mesh), and Examples 1 and 2 of a photocurable resin composition Was prepared. Moreover, it changed to the component (A), and prepared the comparative examples 1-5 using component (O-3)-(O-6).

[Evaluation]
Adhesive strength
(Initial bond strength, photo alignment film)
An alignment film liquid (Nissan Chemical Industries, Ltd .: RN2880) was spin-coated on a glass substrate, calcined at 80 ° C. for 3 minutes on a hot plate, and baked in an oven at 230 ° C. for 30 minutes. Furthermore, the substrate with the alignment film was irradiated with ultraviolet light of 500 mJ / cm ² (measurement wavelength: 254 nm) by a UV irradiator, and was further baked in an oven at 230 ° C. for 30 minutes.
1 g of 5 μm glass fiber is added as a spacer to 100 g of the liquid crystal sealing material manufactured in Examples and Comparative Examples, and mixed and stirred. This liquid crystal sealant is applied on a glass substrate coated with an alignment film in a form that reproduces a corner of 1 cm × 1 cm, the opposite alignment film coated substrate is bonded, and UV light of 3000 mJ / cm ² is irradiated by a UV irradiator. Thereafter, it was put into an oven and thermally cured at 120 ° C. for 1 hour. The peel adhesion strength of the alignment film-coated glass substrate was measured with a bond tester (manufactured by Nishishin Shoji Co., Ltd .: SS-30 WD) by pressing the corner portion. The strengths are shown in Table 1.
(Post-PCT adhesive strength photo alignment film)
The liquid crystal sealant was applied onto the alignment film coated substrate and cured, and the test piece was subjected to PCT test (conditions: temperature 121 ° C., humidity 100%, atmospheric pressure 2 atm, test time 12 hours), and adhesive strength was similarly measured. The strengths are shown in Table 1.
[Glass transition temperature measurement]
The liquid crystal sealing agent manufactured in Examples and Comparative Examples is sandwiched between polyethylene terephthalate (PET) films and made into a thin film of 100 μm thick, irradiated with UV light of 3000 mJ / cm ^{2 by} a UV irradiator, and then put into an oven 120 It was thermally cured for 1 hour. After curing, the PET film was peeled off to obtain a cured sealant film, which was cut into strips of 50 mm × 5 mm to obtain sample pieces. This sample piece is measured at a frequency of 10 Hz and a temperature elevation temperature of 5 ° C./min in a tensile mode of a dynamic viscoelasticity measuring apparatus (DMS-6100: manufactured by SII Nano Technology Inc.), and a curve of the loss coefficient Tan δ The result is obtained as the glass transition temperature, which is the temperature at which the maximum value in. The results are shown in Table 1.
Moisture Permeability
The liquid crystal sealing agent manufactured in Examples and Comparative Examples is sandwiched between polyethylene terephthalate (PET) films and irradiated with UV light of 3000 mJ / cm ² by a UV irradiator to a thin film of 100 μm thick and then charged in an oven at 120 ° C. After heat curing for 40 minutes and curing, the PET film was peeled off to prepare a sample. The moisture permeability at 60 ° C. and 90% of the sample was measured with a moisture permeability measuring device (Lessy: L80-5000). The results are shown in Table 1.

  From the results of Table 1, the resin composition using the compound of the present invention achieves high adhesion strength and achieves both of the characteristics of low moisture permeability. In particular, in Example 1, the glass transition temperature is high, and it is considered to be advantageous also in long-term high reliability.

  The resin composition of the present invention is excellent in adhesive strength with the adherend and has both of low moisture permeability, and in particular, displays, flexible displays, and resin compositions having a curved shape that are required to have adhesiveness with organic films. It is useful as a thing.

Claims (12)

The compound represented by following formula (1).

(In formula (1), R represents a hydrocarbon group having 10 or more carbon atoms, and may have oxygen, nitrogen, or sulfur in the hydrocarbon group. BP represents a bisphenol skeleton.)   The compound according to claim 1, wherein in the formula (1), R has one or more carbon-carbon double bonds.   The compound according to claim 1 or 2, wherein in the formula (1), BP is bisphenol A.   The resin composition containing the compound as described in any one of components (A) 1 thru | or 3.   Furthermore, the resin composition as described in any one of the Claims 1 thru | or 4 containing a component (B) curable compound.   The resin composition according to any one of claims 1 to 5, wherein the component (B) is a component (B-1) (meth) acrylic compound.   The resin composition according to any one of claims 1 to 6, wherein the component (B) is a mixture of the component (B-1) (meth) acrylic compound and the component (B-2) epoxy compound.   The resin composition according to any one of claims 1 to 7, further comprising component (C) an organic filler.   The resin composition according to any one of claims 1 to 8, further comprising component (D) an inorganic filler.   The resin composition according to any one of claims 1 to 9, further comprising component (E) a silane coupling agent.   Furthermore, the resin composition as described in any one of the Claims 1 thru | or 10 containing a component (F) thermosetting agent.   The resin composition according to any one of claims 1 to 11, further comprising component (G) a photoradical polymerization initiator.