TW202313710A - Curable resin composition, sealant for display elements, sealant for organic el display elements, optical adhesive, and optical member - Google Patents

Abstract

The present invention aims to provide a curable resin composition that has excellent curing characteristics and a high refractive index for cured products. In addition, the present invention aims to provide a sealant for display elements and a sealant for organic EL display elements, that includes this curable resin composition. A further purpose of the present invention is to provide: an optical adhesive containing said curable resin composition; and an optical member including a cured product of said curable resin composition. The present invention is a curable resin composition that contains: a cationic polymerizable compound; a cationic polymerization initiator; and a fluorene compound that has a phenolic hydroxyl group in the molecules thereof.

Description

Curable resin composition, sealant for display element, sealant for organic EL display element, optical adhesive, and optical member

The present invention relates to a curable resin composition with excellent curability and high refractive index of the cured product. Moreover, this invention relates to the sealing compound for display elements containing this curable resin composition, and the sealing compound for organic electroluminescence display elements. Furthermore, the present invention also relates to an optical adhesive containing the curable resin composition and an optical member containing a cured product of the curable resin composition.

Conventionally, as a curable resin composition for optical members, a cation curable resin composition containing a cation polymerizable compound and a cationic polymerization initiator has been used. Specifically, cation-curable resin compositions and cured products thereof are used in sealants and the like for display elements such as organic electroluminescence (hereinafter also referred to as "organic EL") display elements.

The organic EL display element has a laminate structure in which an organic light-emitting material layer is sandwiched between a pair of electrodes facing each other. While electrons are injected from one electrode into the organic light-emitting material layer, holes are injected from the other electrode, thereby The electrons and holes are combined in the organic light-emitting material layer to emit light. In this way, the organic EL display element is self-illuminating, so it has the advantages of better visibility, thinner thickness, and DC low-voltage drive than liquid crystal display elements that require a backlight.

The organic luminescent material layer and electrodes constituting the organic EL display element have the problem that the characteristics are easily deteriorated due to moisture, oxygen, and the like. Therefore, in order to obtain a practical organic EL display device, it is necessary to extend the lifetime by blocking the organic light-emitting material layer and the electrodes from the atmosphere. As a method of blocking the organic light-emitting material layer and electrodes from the atmosphere, sealing an organic EL display element with a sealing agent is practiced (for example, Patent Document 1). In the case of sealing the organic EL display element with a sealant, in order to sufficiently suppress the penetration of moisture or oxygen, etc., the following method is generally used: an inorganic passivation film called a passivation film is provided on a laminated body having an organic light-emitting material layer. material film, and seal the inorganic material film with a sealant.

In recent years, top-emission organic EL display elements are attracting attention instead of bottom-emission organic EL display elements. The above-mentioned bottom-emission organic EL display elements are extracted from the organic light-emitting material layer from the side of the substrate on which the light-emitting elements are formed. For the emitted light, the above-mentioned top emission type organic EL display element extracts light from the upper surface side of the organic light emitting material layer. This method has the advantage of being conducive to long life due to its high aperture ratio and low-voltage drive. In such a top-emission organic EL display element, the upper surface of the light-emitting layer must be transparent. Therefore, a transparent moisture-proof substrate such as glass is laminated on the upper surface of the light-emitting element through a transparent sealing layer. Sealing (for example, Patent Document 1).

In addition, cation-curable resin compositions are also used in optical adhesives used for bonding optical materials such as polarizing plates, or optical members such as resin lenses (for example, Patent Documents 2 and 3). [Prior Art Literature] [Patent Document]

Patent Document 1: Japanese Patent Laid-Open No. 2007-115692 Patent Document 2: Japanese Patent Laid-Open No. 2014-152194 Patent Document 3: International Publication No. 2015/098736

[Problem to be Solved by the Invention]

In top-emission organic EL display elements, even when using one with sufficiently high transparency as a transparent moisture-proof substrate or sealant, there is a difference in refractive index between the electrode or passivation film and the sealant, which causes the A case where the extraction efficiency of light emitted from the laminate becomes poor. In addition, excellent curability and a further high refractive index are also required for cation-curable resin compositions used in optical adhesives and optical members. An object of the present invention is to provide a curable resin composition which is excellent in curability and has a high refractive index of the cured product. Moreover, the object of this invention is to provide the sealing compound for display elements containing this curable resin composition, and the sealing compound for organic electroluminescence display elements. Furthermore, an object of the present invention is to provide an optical adhesive containing the curable resin composition and an optical member containing a cured product of the curable resin composition. [Technical means to solve the problem]

The present invention 1 is a curable resin composition comprising a cation polymerizable compound, a cation polymerization initiator, and a terpene compound having a phenolic hydroxyl group in the molecule. Invention 2 is the curable resin composition according to Invention 1, wherein the fennel compound having a phenolic hydroxyl group in its molecule has two or more phenolic hydroxyl groups in one molecule. The present invention 3 is the curable resin composition according to the present invention 1 or 2, wherein the fennel compound having a phenolic hydroxyl group in its molecule is a compound represented by the following formula (1). The present invention 4 is the curable resin composition according to the present invention 1, 2 or 3, wherein, in 100 parts by weight of the above curable resin composition, the content of the terpene compound having a phenolic hydroxyl group in the molecule is 3 parts by weight or more 60 parts by weight or less. Invention 5 is the curable resin composition according to Invention 1, 2, 3 or 4, wherein the cationic polymerizable compound includes: a compound having a biphenyl skeleton and an epoxy group, and a compound having a biphenyl skeleton and an oxygen heterocycle At least any one of oxetanyl compounds. Invention 6 is the curable resin composition according to Invention 1, 2, 3, 4 or 5, and the cured product has a refractive index of 1.6 or more at the sodium D line at 25°C. Invention 7 is the curable resin composition as in Invention 1, 2, 3, 4, 5 or 6, which uses an E-type viscometer and has a viscosity measured at 25°C of 0.1 Pa·s to 5000 Pa·s . The present invention 8 is a sealant for a display element containing the curable resin composition of the present invention 1, 2, 3, 4, 5, 6 or 7. The present invention 9 is a sealant for an organic EL display element, which contains the curable resin composition of the present invention 1, 2, 3, 4, 5, 6 or 7. The present invention 10 is an optical adhesive comprising the curable resin composition of the present invention 1, 2, 3, 4, 5, 6 or 7. Invention 11 is an optical member comprising a cured product of the curable resin composition in Invention 1, 2, 3, 4, 5, 6 or 7.

In formula (1), R ¹ and R ² are each a hydrogen atom, or are bonded to represent one oxygen atom, and R ³ to R ⁸ each independently represent a hydrogen atom, an alkyl group with 1 to 6 carbons, and a phenyl group , or benzyl. The present invention will be described in detail below.

The inventors of the present invention have studied the addition of a terpene compound having a phenolic hydroxyl group in the molecule to a cationically curable resin composition containing a cationically polymerizable compound and a cationic polymerization initiator. As a result, they found that a curable resin composition having excellent curability and a cured product with a high refractive index can be obtained, and completed the present invention. Since the cured resin composition of the present invention has a high refractive index, when used as a sealant used in display elements such as organic EL display elements, the obtained display element has excellent light extraction efficiency. Moreover, since the curable resin composition of the present invention is excellent in curability and has a high refractive index of the cured product, it is also suitable as an optical adhesive or an optical member.

The curable resin composition of the present invention contains a fennel compound having a phenolic hydroxyl group in its molecule (hereinafter, also referred to as "the fennel compound having a phenolic hydroxyl group"). By containing the above-mentioned phenolic hydroxyl group-containing terpene compound, the curable resin composition of the present invention is excellent in curability and has a high refractive index of the cured product. Although the mechanism is not clear, the curability is greatly improved by the presence or absence of the above-mentioned phenolic hydroxyl group. Therefore, it is considered that the phenolic hydroxyl group in the fennel compound containing the above-mentioned phenolic hydroxyl group contributes to the improvement of the curability. In addition, in this specification, the said "phenolic hydroxyl group" means the hydroxyl group which exists in an aromatic substituent.

From the viewpoint of improving physical properties after hardening, the above-mentioned phenolic hydroxyl group-containing fennel compound preferably has two or more phenolic hydroxyl groups in one molecule. Also, from the viewpoint of increasing the refractive index of the cured product of the curable resin composition obtained, the above-mentioned fennel compound containing a phenolic hydroxyl group preferably has an aromatic ring other than those contained in the fennel skeleton. . From the viewpoint of curability, it is preferable that the aromatic rings other than those contained in the fennel skeleton have a phenolic hydroxyl group.

As the above-mentioned fennel compound containing a phenolic hydroxyl group, a compound represented by the above-mentioned formula (1) is preferable.

]-3',6'-二醇（下述式（2-3）所表示之化合物）、下述式（2-4）所表示之化合物等。Examples of the compound represented by the above formula (1) include: 9,9-bis(4-hydroxyphenyl) stilbene (a compound represented by the following formula (2-1)), 9,9-bis(4- -Hydroxy-3-methylphenyl) fluorine (the compound represented by the following formula (2-2)), spiro[

]-3',6'-diol (a compound represented by the following formula (2-3)), a compound represented by the following formula (2-4), etc.

In 100 parts by weight of the curable resin composition of the present invention, the preferred lower limit of the content of the above-mentioned fennel compound containing phenolic hydroxyl group is 3 parts by weight, and the preferred upper limit is 60 parts by weight. The refractive index of the cured product of the obtained curable resin composition becomes higher by making content of the said phenolic hydroxyl group containing terpene compound 3 weight part or more. By making the content of the above-mentioned phenolic hydroxyl group-containing terpene compound 60 parts by weight or less, the obtained curable resin composition has better coatability. The more preferable lower limit of the content of the above-mentioned fennel compound containing phenolic hydroxyl group is 5 parts by weight, and the more preferable upper limit is 50 parts by weight.

The curable resin composition of the present invention contains a cationic polymerizable compound. It is preferable that the said cationically polymerizable compound contains at least any one of the compound which has a biphenyl skeleton and an epoxy group, and the compound which has a biphenyl skeleton and an oxetanyl group. By containing at least any one of the above-mentioned compounds having a biphenyl skeleton and an epoxy group, and the above-mentioned compounds having a biphenyl skeleton and an oxetanyl group, the cured product of the curable resin composition of the present invention can be made The refractive index becomes higher.

As the above-mentioned compound having a biphenyl skeleton and an epoxy group, and the above-mentioned compound having a biphenyl skeleton and an oxetanyl group, from the viewpoints of viscosity, refractive index, curability, etc., various types of the above-mentioned biphenyl skeleton can be appropriately selected. A compound having a skeleton and an epoxy group, and the above-mentioned compound having a biphenyl skeleton and an oxetanyl group.

Specific examples of the compound having a biphenyl skeleton and an epoxy group include o-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, 4,4-biphenyldiylbis (glycidyl ether), 4,4'-bis(glycidoxy)-1,1'-biphenyl, 3,3',5,5'-tetramethyl-4,4'-bis (Glycidoxy)-1,1'-biphenyl, etc. Among them, o-phenylphenol glycidyl ether is suitable. As a compound which has the said biphenyl skeleton and an oxetanyl group, the compound etc. which are represented specifically, for example by following formula (3) are mentioned. The compound which has the said biphenyl skeleton and an epoxy group, and the compound which has the said biphenyl skeleton and an oxetanyl group may be used individually or in combination of 2 or more types.

In formula (3), n is the number of repetitions. This n is preferably a value that satisfies the range of the following oxetanyl equivalent in the compound represented by formula (3).

The preferred lower limit of the epoxy equivalent of the above-mentioned compound having a biphenyl skeleton and an epoxy group and the oxetanyl equivalent of the above-mentioned compound having a biphenyl skeleton and an oxetanyl group is 110, and a preferable upper limit is 500. By making the epoxy equivalent of the above-mentioned compound having a biphenyl skeleton and an epoxy group and the oxetanyl equivalent of the above-mentioned compound having a biphenyl skeleton and an oxetanyl group fall within this range, the obtained hardened The permanent resin composition is more excellent in adhesiveness, low outgassing property, and coatability. Furthermore, in this specification, the epoxy equivalent of the compound having a biphenyl skeleton and an epoxy group means (molecular weight of a compound having a biphenyl skeleton and an epoxy group)/(molecular weight of a compound having a biphenyl skeleton and an epoxy group)/(molecular weight of a compound having a biphenyl skeleton and an epoxy group) The number of epoxy groups in the compound 1 molecule). Also, in this specification, the oxetanyl equivalent of the above-mentioned compound having a biphenyl skeleton and an oxetanyl group means (molecular weight of a compound having a biphenyl skeleton and an oxetanyl group)/( The number of oxetanyl groups in the compound 1 molecule of the skeleton and oxetanyl groups).

A preferable lower limit of the molecular weight of the compound having a biphenyl skeleton and an epoxy group, and a molecular weight of the compound having a biphenyl skeleton and an oxetanyl group is 200, and a preferable upper limit is 1,000. By setting the molecular weight of the compound having a biphenyl skeleton and an epoxy group and the molecular weight of the compound having a biphenyl skeleton and an oxetanyl group within this range, the obtained curable resin composition becomes adhesive. , low outgassing properties, and better coatability. Furthermore, in this specification, for a compound whose molecular structure is specified, the above-mentioned "molecular weight" refers to the molecular weight obtained from the structural formula, and for a compound with a wide distribution of polymerization degrees and a compound with an unspecified modification site. In other words, the above-mentioned "molecular weight" may be represented by a weight average molecular weight. In addition, the said "weight average molecular weight" is the value calculated|required by the polystyrene conversion measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. As a column used when measuring the weight average molecular weight by polystyrene conversion by GPC, Shodex LF-804 (made by Showa Denko Co., Ltd.) etc. are mentioned, for example.

It is preferable that the compound which has the said biphenyl skeleton and an epoxy group, and the compound which has the said biphenyl skeleton and an oxetanyl group are liquid at 25 degreeC. The curable resin composition obtained is made coatable by making the above-mentioned compound having a biphenyl skeleton and an epoxy group, and the above-mentioned compound having a biphenyl skeleton and an oxetanyl group into a liquid state at 25°C. more excellent.

As what is marketed among the compounds which have the said biphenyl skeleton and an epoxy group, OPP-EP (made by Yokkaichi Gosei Co., Ltd.) etc. are mentioned, for example. As what is marketed among the compounds which have the said biphenyl skeleton and an oxetanyl group, ETERNACOLL OXBP (made by Ube Industries, Ltd.) etc. are mentioned, for example.

The cationically polymerizable compound may contain other cationically polymerizable compounds in addition to at least any one of the above-mentioned compound having a biphenyl skeleton and an epoxy group, and the above-mentioned compound having a biphenyl skeleton and an oxetanyl group. . Examples of the above-mentioned other cationically polymerizable compounds include: epoxy compounds other than the above-mentioned compounds having a biphenyl skeleton and an epoxy group, other oxa compounds other than the above-mentioned compounds having a biphenyl skeleton and an oxetanyl group, etc. Cyclobutane compounds, vinyl ether compounds, etc.

When the above-mentioned other cationically polymerizable compound is contained, the above-mentioned compound having a biphenyl skeleton and an epoxy group, and the above-mentioned compound having a biphenyl skeleton and an oxetanyl group in 100 parts by weight of the above-mentioned cationically polymerizable compound The preferred lower limit of the content is 30 parts by weight, and the preferred upper limit is 97 parts by weight. The cured product of the curable resin composition obtained by making the content of the above-mentioned compound having a biphenyl skeleton and an epoxy group, and the above-mentioned compound having a biphenyl skeleton and an oxetanyl group to be 30 parts by weight or more The refractive index becomes higher. The curable resin composition obtained is curable by making the content of the compound having a biphenyl skeleton and an epoxy group and the compound having a biphenyl skeleton and an oxetanyl group 97 parts by weight or less. , low outgassing properties, and better coatability. The above-mentioned compound with biphenyl skeleton and epoxy group, and the content of the compound with above-mentioned biphenyl skeleton and oxetanyl group have a better lower limit of 50 parts by weight, a better upper limit of 90 parts by weight, and a better upper limit of 80 parts by weight.

Examples of other epoxy compounds include: 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate, 4,4'-bis(1,2-epoxy Cyclohexane), bis(3,4-epoxycyclohexylmethyl)ether, bis(3,4-epoxycyclohexane-1-ylmethyl)adipate, 2,2- 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of bis(hydroxymethyl)-1-butanol, methacrylic acid [(3,4-epoxy Cyclohexane)-1-yl]methyl ester, fennel-type epoxy compound, 1,7-octadiene diepoxide, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether , Diethylene Glycol Diglycidyl Ether, Polyethylene Glycol Diglycidyl Ether, Propylene Glycol Diglycidyl Ether, Dipropylene Glycol Diglycidyl Ether, Tripropylene Glycol Diglycidyl Ether, Polyethylene Glycol Diglycidyl Ether, Polyethylene Glycol Diglycidyl Ether Propylene Glycol Diglycidyl Ether, 1,6-Hexanediol Diglycidyl Ether, Glycerin Diglycidyl Ether, Trimethylolpropane Triglycidyl Ether, Phenyl Glycidyl Ether, phenylene diglycidyl ether, etc.

Examples of the above-mentioned other oxetane compounds include 3-ethyl-3-(((3-ethyloxetan-3-yl)methoxy)methyl)oxetane , 3-ethyl-3-((2-ethylhexyloxy)methyl)oxetane, 3-ethyl-3-((3-(triethoxysilyl)propoxy) Methyl)oxetane, phenol novolac oxetane, 1,4-bis((3-ethyl-3-oxetanyl)methoxy)methyl)benzene and the like.

Examples of the vinyl ether compound include benzyl vinyl ether, cyclohexanedimethanol monovinyl ether, dicyclopentadiene vinyl ether, 1,4-butanediol divinyl ether, cyclohexane Dimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, and the like.

The curable resin composition of the present invention contains a cationic polymerization initiator. In the case of using an anionic polymerization catalyst, the curable resin composition obtained may be poor in storage stability, curability or discoloration resistance, but the curable resin composition of the present invention is improved by using the above-mentioned cationic polymerization. Initiator, and become those who are also excellent in these characteristics. As said cationic polymerization initiator, a cationic thermal polymerization initiator or a cationic photopolymerization initiator is mentioned.

As the above-mentioned cationic thermal polymerization initiator, it can be mentioned that the anion part is substituted by BF ₄ ^- , PF ₆ ^- , SbF ₆ ^- , or (BX ₄ ) ^- (wherein, X represents that substituted by at least 2 or more fluorine or trifluoromethyl groups) Phenyl) salts, phosphonium salts, ammonium salts, diazonium salts, iodonium salts, etc. Among them, cobalt salt is preferred.

Examples of the above-mentioned cobalt salts include triphenyl percolium tetrafluoroborate, triphenyl percalcium hexafluoroantimonate, and the like.

As said phosphonium salt, ethyltriphenylphosphonium hexafluoroantimonate, tetrabutylphosphonium hexafluoroantimonate, etc. are mentioned.

As said ammonium salt, for example, dimethylphenyl (4-methoxybenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methoxybenzyl) ammonium hexafluoroantimonate, Dimethylphenyl(4-methoxybenzyl)ammonium tetrakis(pentafluorophenyl)borate, dimethylphenyl(4-methylbenzyl)ammonium hexafluorophosphate, dimethylphenyl( 4-methylbenzyl)ammonium hexafluoroantimonate, dimethylphenyl(4-methylbenzyl)ammonium hexafluorotetrakis(pentafluorophenyl)borate, methylphenyldibenzylammonium hexafluoro Phosphate, Methylphenyldibenzylammonium Hexafluoroantimonate, Methylphenyldibenzylammonium Tetrakis(pentafluorophenyl)borate, Phenyltribenzylammonium Tetrakis(pentafluorophenyl)borate , Dimethylphenyl(3,4-dimethylbenzyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethyl-N-benzylanilinium hexafluoroantimonate, N, N-diethyl-N-benzylanilinium tetrafluoroborate, N,N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N,N-diethyl-N-benzylpyridine Onium triflate, etc.

As what is marketed among the said cationic thermal-polymerization initiators, the cationic thermal-polymerization initiator by Sanshin Chemical Industry Co., Ltd., the cationic thermal-polymerization initiator by King Industries, etc. are mentioned, for example. Examples of the above-mentioned cationic thermal polymerization initiator manufactured by Sanshin Chemical Industry Co., Ltd. include: San-Aid SI-60, San-Aid SI-80, San-Aid SI-B3, San-Aid SI-B3A, San-Aid Aid SI-B4, etc. As a thermal cationic polymerization initiator manufactured by the said King Industries company, CXC-1612, CXC-1821 etc. are mentioned, for example.

The photocationic photopolymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid by light irradiation, and may be an ionic photoacid generating type or a nonionic photoacid generating type.

Examples of the anionic moiety of the above-mentioned ionic photoacid-generating cationic photopolymerization initiator include: BF ₄ ^- , PF ₆ ^- , SbF ₆ ^- , (BX ₄ ) ^- (wherein, X represents at least 2 or more Fluorine or trifluoromethyl substituted phenyl), etc. Also, examples of the above-mentioned anion moiety include PF _m (C _n F _2n+1 ) _6-m ^- (wherein, in the formula, m is an integer of 0 to 5 and n is an integer of 1 to 6) and the like. As the cationic photopolymerization initiator of the above-mentioned ionic photoacid generation type, for example, aromatic percite salts, aromatic indium salts, aromatic diazonium salts, aromatic ammonium salts, (2,4 -cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe salt, etc.

Examples of the above-mentioned aromatic cobaltium salts include: bis(4-(diphenylpermeyl)phenyl)sulfide bishexafluorophosphate, bis(4-(diphenylpermeyl)phenyl)sulfide bis Hexafluoroantimonate, bis(4-(diphenylpersidyl)phenyl)sulfide bistetrafluoroborate, bis(4-(diphenylpersidyl)phenyl)sulfide tetrakis(pentafluorophenyl) ) borate, diphenyl-4-(phenylsulfanyl)phenylpercited hexafluorophosphate, diphenyl-4-(phenylthio)phenylcuredium hexafluoroantimonate, diphenyl-4-( Phenylthio)phenylpercitetetrafluoroborate, diphenyl-4-(phenylthio)phenylpercitetetrakis(pentafluorophenyl)borate, triphenylpercite hexafluorophosphate, triphenylpercite hexafluoroborate Fluoroantimonate, triphenylpermetrafluoroborate, triphenylpermetrakis(pentafluorophenyl)borate, bis(4-(bis(4-(2-hydroxyethoxy))phenylpermedium ) phenyl) sulfide bishexafluorophosphate, bis(4-(bis(4-(2-hydroxyethoxy))phenylpermeyl)phenyl)sulfide bishexafluoroantimonate, bis(4 -(bis(4-(2-hydroxyethoxy))phenylperidyl)phenyl)sulfide bistetrafluoroborate, bis(4-(bis(4-(2-hydroxyethoxy))benzene Perulidyl)phenyl)sulfide tetrakis(pentafluorophenyl)borate, tris(4-(4-acetylphenyl)phenylsulfanyl)percolium tetrakis(pentafluorophenyl)borate, etc. Among them, triaryl permetrakis (pentafluorophenyl) borate such as triphenyl permetrakis tetrakis (pentafluorophenyl) borate is preferable.

Examples of the above-mentioned aromatic iodonium salts include: diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis(pentafluorophenyl) Borate, bis(dodecylphenyl)iodonium hexafluorophosphate, bis(dodecylphenyl)iodonium hexafluoroantimonate, bis(dodecylphenyl)iodonium tetrafluoroborate, bis(dodecylphenyl)iodonium tetrafluoroborate, (Dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluorophosphate, 4-methylphenyl -4-(1-methylethyl)phenyliodonium hexafluoroantimonate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrafluoroborate, 4-methylbenzene Base-4-(1-methylethyl)phenyliodonium tetrakis(pentafluorophenyl)borate, etc.

Examples of the aromatic diazonium salts include: phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, phenyldiazonium tetrafluoroborate, phenyldiazonium tetrafluoroborate, (Pentafluorophenyl) borate, etc.

Examples of the aromatic ammonium salts include: 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2 -cyanopyridinium tetrafluoroborate, 1-benzyl-2-cyanopyridinium tetrakis(pentafluorophenyl)borate, 1-(naphthylmethyl)-2-cyanopyridinium hexafluorophosphate , 1-(naphthylmethyl)-2-cyanopyridinium hexafluoroantimonate, 1-(naphthylmethyl)-2-cyanopyridinium tetrafluoroborate, 1-(naphthylmethyl) -2-cyanopyridinium tetrakis(pentafluorophenyl) borate and the like.

Examples of the (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe salt include: (2,4-cyclopentadien-1-yl)( (1-methylethyl)benzene)-Fe(II) hexafluorophosphate, (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe(II) Hexafluoroantimonate, (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe(II) tetrafluoroborate, (2,4-cyclopentadiene -1-yl)((1-methylethyl)benzene)-Fe(II)tetrakis(pentafluorophenyl)borate and the like.

Examples of the above-mentioned nonionic photoacid-generating cationic photopolymerization initiator include nitrobenzyl esters, sulfonic acid derivatives, phosphoric acid esters, phenolsulfonic acid esters, diazonaphthoquinones, and N-hydroxyacylamides. sulfamate, etc.

As what is marketed among the said cationic photopolymerization initiators, the cationic photopolymerization initiator by the Nippon Green Chemical Co., Ltd., the cationic photopolymerization initiator by the Union Carbide company, the cationic photopolymerization by ADEKA company are mentioned, for example Initiator, cationic photopolymerization initiator made by 3M company, cationic photopolymerization initiator made by BASF company, cationic photopolymerization initiator made by Solvay company, cationic photopolymerization initiator made by San-Apro company, etc. . DTS-200 etc. are mentioned as a cationic photoinitiator by the said Nippon Midori Chemical Co., Ltd., for example. As a cationic photoinitiator manufactured by the said Union Carbide company, UVI6990, UVI6974 etc. are mentioned, for example. As a cationic photoinitiator by the said ADEKA company, SP-150, SP-170 etc. are mentioned, for example. As a cationic photopolymerization initiator manufactured by the said 3M company, FC-508, FC-512 etc. are mentioned, for example. As a cationic photoinitiator manufactured by the said BASF company, IRGACURE261, IRGACURE290 etc. are mentioned, for example. As a cationic photoinitiator manufactured by the said Solvay company, PI2074 etc. are mentioned, for example. As a cationic photoinitiator by the said San-Apro company, CPI-100P, CPI-200K, CPI-210S etc. are mentioned, for example.

Among the above cationic polymerization initiators, a borate-based quaternary ammonium salt (hereinafter also referred to as "borate-based quaternary ammonium salt") as a counter anion is preferably used. The counter anion of the borate quaternary ammonium salt is preferably BF ₄ ^- or (BX ₄ ) ^- (where X represents a phenyl group substituted by at least two fluorine or trifluoromethyl groups).

With respect to 100 parts by weight of the above-mentioned cationically polymerizable compound, the preferable lower limit of the content of the above-mentioned cationic polymerization initiator is 0.05 parts by weight, and the preferable upper limit is 10 parts by weight. By setting the content of the above-mentioned cationic polymerization initiator within this range, the obtained curable resin composition becomes more excellent in curability, storage stability, and moisture resistance of the cured product. The more preferable lower limit of the content of the above-mentioned cationic polymerization initiator is 0.1 parts by weight, and the more preferable upper limit is 5 parts by weight.

The curable resin composition of the present invention preferably contains a stabilizer. By containing the above-mentioned stabilizer, the curable resin composition of the present invention becomes more excellent in storage stability.

As said stabilizer, triethanolamine, benzylamine, triglycidyl-p-aminophenol etc. are mentioned, for example. These stabilizers may be used alone or in combination of two or more.

The preferable lower limit of the content of the said stabilizer is 0.001 weight part with respect to 100 weight part of said cationically polymerizable compounds, and a preferable upper limit is 2 weight part. By making content of the said stabilizer into this range, the curable resin composition obtained becomes one more excellent in storage stability, maintaining excellent curability. The more preferable lower limit of the content of the said stabilizer is 0.005 weight part, and the more preferable upper limit is 1 weight part.

The curable resin composition of the present invention may also contain a silane coupling agent. The above-mentioned silane coupling agent has the effect of improving the adhesion between the curable resin composition of the present invention and the substrate.

Examples of the silane coupling agent include: 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanate Propyltrimethoxysilane, etc. These silane coupling agents may be used alone or in combination of two or more.

The preferable lower limit of the content of the said silane coupling agent is 0.1 weight part with respect to 100 weight part of said cationic polymerizable compounds, and a preferable upper limit is 10 weight part. By making the content of the above-mentioned silane coupling agent within this range, the bleed-out of the remaining silane coupling agent is suppressed, and the effect of improving adhesiveness is more excellent. The more preferable lower limit of the content of the above-mentioned silane coupling agent is 0.5 parts by weight, and the more preferable upper limit is 5 parts by weight. Also, from the viewpoint of low outgassing properties, a preferable upper limit of the content of the above-mentioned silane coupling agent is 0.5 parts by weight, a more preferable upper limit is 0.1 parts by weight, and a further preferable upper limit is 100 parts by weight of the above-mentioned cationic polymerizable compound. 0.01 parts by weight.

The curable resin composition of the present invention may further contain a surface modifier within a range that does not interfere with the object of the present invention. By containing the above-mentioned surface modifying agent, the flatness of the coating film of the curable resin composition of the present invention can be improved. As said surface modifier, a surfactant, a leveling agent, etc. are mentioned, for example.

Examples of the surface modifying agent include silicone-based, acrylic-based, and fluorine-based agents. As what is marketed among the said surface modifying agents, the surface modifying agent by BYK-Chemie Japan company make, the surface modifying agent by AGC Seimi Chemical company, etc. are mentioned, for example. As a surface modifying agent manufactured by said BYK-Chemie Japan company, BYK-330, BYK-340, BYK-345 etc. are mentioned, for example. As the surface modifying agent manufactured by the said AGC Seimi Chemical company, Surflon S-611 etc. are mentioned, for example.

The curable resin composition of the present invention may also contain a compound or ion exchange resin that reacts with acid generated in the curable resin composition in order to improve the durability of the device electrodes, etc. within the range that does not interfere with the object of the present invention.

Examples of the compound that reacts with the generated acid include substances that neutralize the acid, for example, carbonates or bicarbonates of alkali metals, or carbonates or bicarbonates of alkaline earth metals. Specifically, for example, calcium carbonate, calcium hydrogencarbonate, sodium carbonate, sodium hydrogencarbonate, etc. can be used.

As the above-mentioned ion exchange resin, any of cation exchange type, anion exchange type, and amphoteric ion exchange type can be used, and the cation exchange type or amphoteric ion exchange type capable of adsorbing chloride ions is particularly suitable.

The curable resin composition of the present invention can also contain a solvent for the purpose of viscosity adjustment, etc., but there is a risk of causing the following problems, such as outgassing due to the remaining solvent, or when used as a sealant for organic EL display elements Occasionally degrades the organic light-emitting material layer, so it is preferable not to contain a solvent, or the content of the solvent is 0.05% by weight or less.

In addition, the curable resin composition of the present invention may optionally contain various known additives such as curing retarders, reinforcing agents, softeners, plasticizers, viscosity modifiers, ultraviolet absorbers, and antioxidants.

The curable resin composition of the present invention uses an E-type viscometer. The preferred lower limit of the viscosity measured at 25°C is 0.1 Pa·s, and the preferred upper limit is 5000 Pa·s. By making the said viscosity into this range, the curable resin composition obtained becomes what is excellent in applicability. A more preferable lower limit of the above-mentioned viscosity is 0.2 Pa·s, and a more preferable upper limit is 2000 Pa·s. The above-mentioned viscosity can be measured at 1.0 rpm using, for example, VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.) as an E-type viscometer with a No. 7 rotor.

The preferred lower limit of the refractive index of the cured product of the curable resin composition of the present invention at 25°C at the sodium D line is 1.6. By making the above-mentioned refractive index 1.6 or more, when it is used as a sealant used in display elements such as organic EL display elements, the difference in refractive index with electrodes or passivation films is small, and the resulting display is The device was excellent in light extraction efficiency. A more preferable lower limit of the above-mentioned refractive index is 1.61. The preferable upper limit of the above-mentioned refractive index is not particularly limited, and the practical upper limit is 1.9. The above "refractive index of sodium D line" can be measured using an Abbe's refractometer. In addition, as a cured product for measuring the above-mentioned refractive index, for example, a measuring piece having a length of 20 mm, a width of 10 mm, and a thickness of 100 μm can be used. Regarding the cured product for measuring the above-mentioned refractive index, if it is a photocurable resin composition, it can be obtained by irradiating ultraviolet light at about 1500 mJ/cm ² , and if it is a thermosetting resin composition, it can be obtained by It can be obtained by heating at 150°C for 10 minutes, and if it is a photothermal curable resin composition, it can be obtained by heating at 150°C for 10 minutes after irradiating ultraviolet rays of about 1500 mJ/cm ² .

The curable resin composition of the present invention preferably has a curing shrinkage rate of 7.0% or less. The curable resin composition of the present invention can prevent warpage or peeling of the adherend by making the above curing shrinkage rate 7.0% or less. A more preferable upper limit of the above curing shrinkage rate is 5.0%, a more preferable upper limit is 4.0%, a particularly preferable upper limit is 3.5%, and the most preferable upper limit is 2.5%. Moreover, the preferable lower limit of the above-mentioned curing shrinkage rate is not particularly limited, and the lower limit is substantially 1.0%. In addition, in this specification, the above-mentioned "hardening shrinkage rate" refers to the density of the curable resin composition before curing at 25°C as D _A and the density of the hardened product of the curable resin composition at 25°C as D A . In the case of _DB , the value calculated by the following formula. Curing shrinkage (%) = (( _DB - D _A )/D _B ) × 100 Regarding the cured product used in the measurement of the above density, if it is a photocurable resin composition, it can be irradiated with 1500 mJ /cm ² of ultraviolet light, if it is a thermosetting resin composition, it can be obtained by heating at 150°C for 10 minutes, if it is a photothermosetting resin composition, it can be obtained by irradiating 1500 mJ/cm It is obtained by heating at 150°C for 10 minutes after about ² ultraviolet rays.

The curable resin composition of the present invention is suitably used as a sealant for display elements, especially as a sealant for organic EL display elements. The sealant for display elements and the sealant for organic EL display elements containing the curable resin composition of this invention are also one of this invention.

The sealing agent for organic EL display elements of this invention is suitable especially as an in-plane sealing agent which coats and seals the laminated body which has an organic light emitting material layer. Moreover, the sealing compound for organic electroluminescent display elements of this invention is suitable for sealing of the organic electroluminescent display element of a top emission type.

As a method of sealing an organic EL display element using the sealant for an organic EL display element of the present invention, for example, a method having the steps of applying the organic EL display element of the present invention by printing, dispensing, inkjet, etc. The sealant for display elements is coated on the substrate; and the applied sealant for organic EL display elements is hardened by at least one of heating and light irradiation.

In the step of applying the sealant for organic EL display elements of the present invention to the substrate, the sealant for organic EL display elements of the present invention may be applied to the entire surface of the substrate or to a part of the substrate . The shape of the sealing portion of the sealant for organic EL display element of the present invention formed by coating is not particularly limited as long as it can protect the laminate having the organic light-emitting material layer from the external atmosphere. In order to completely cover the shape of the laminate, a closed pattern may be formed on the periphery of the laminate, or a pattern in the shape of a part of openings may be formed on the periphery of the laminate.

When the above-mentioned sealant for an organic EL display element is cured by heating, it is preferably at least 50°C and not more than 120°C from the viewpoint of reducing damage to the laminate having the organic light-emitting material layer and sufficiently curing for heating.

When the sealing agent for organic EL display elements of the present invention is cured by light irradiation, the sealing agent for organic EL display elements of the present invention can be appropriately cured by irradiating with a wavelength of 300 nm to 400 nm And 300 mJ/cm ² or more and 3000 mJ/cm ² or less cumulative light.

Examples of light sources used for the above light irradiation include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, excimer lasers, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, sodium lamps, and halogen lamps. lamps, xenon lamps, LED lamps, fluorescent lamps, sunlight, electron beam irradiation devices, etc. These light sources may be used alone or in combination of two or more. These light sources can be appropriately selected according to the absorption wavelength of the above-mentioned cationic photopolymerization initiator.

As the means of irradiating light to the sealant for organic EL display elements of the present invention, for example, simultaneous irradiation of various light sources, sequential irradiation with time difference, combined irradiation of simultaneous irradiation and sequential irradiation, etc. can be mentioned, and any irradiation means can be used.

The above-mentioned sealing agent for organic EL display elements is cured by at least one of heating and light irradiation, and the cured product obtained in this step may be further coated with an inorganic material film. As the inorganic material constituting the above-mentioned inorganic material film, conventionally known ones can be used, for example, silicon nitride (SiN _x ) or silicon oxide (SiO _x ) can be used. The above-mentioned inorganic material film may be one layer, or may be obtained by laminating a plurality of layers. Moreover, the said laminated body can also be covered alternately and repeatedly with the said inorganic material film and the resin film which consists of the sealing compound for organic electroluminescence display elements of this invention.

The method for manufacturing the above-mentioned organic EL display element may also have the following steps: a base material (hereinafter, also referred to as "a base material") coated with the sealant for an organic EL display element of the present invention and another base material are bonded. combine. The above-mentioned one substrate may be a substrate on which a layered body having an organic light-emitting material layer is formed, or may be a substrate on which the layered body is not formed. In the case where the above-mentioned one substrate is a substrate on which the above-mentioned laminate is not formed, the organic EL display of the present invention can be displayed in such a manner that the above-mentioned laminate can be protected from the influence of the external atmosphere when the above-mentioned other substrate is bonded. The encapsulant for components can be coated on the above-mentioned one base material. That is, when pasting another base material, it may be coated on the entire surface of the position of the above-mentioned laminate; or when pasting another base material, the position of the above-mentioned laminate may be completely coated. The shape incorporated into it forms the encapsulant portion of the closed pattern. In addition, as a method of sealing the above-mentioned organic EL display element, a method of so-called dam and fill sealing can also be used. That is, first, a curable paste is applied on the substrate of the organic EL display element so as to surround the periphery of the display portion. Then, the sealant for organic EL display element of the present invention is coated on the inner side of the applied curable paste, and the sealant is prevented from overflowing by the curable paste on the periphery, and the facing sealing substrate is bonded. Thereafter, a method of curing the curable paste on the periphery and the sealant for an organic EL display element of the present invention spread inside by at least one of heating and light irradiation can be used.

The step of hardening the sealant for an organic EL display element by at least one of heating and light irradiation may be performed before the step of bonding the one base material and the other base material, or may be performed. It is carried out after the step of laminating the above-mentioned one base material and the above-mentioned another base material. When the step of hardening the above-mentioned sealant for organic EL display elements by at least one of heating and light irradiation is performed before the step of bonding the above-mentioned one substrate and the above-mentioned other substrate, the organic EL of the present invention In the sealing agent for display elements, it is preferable that the application time after performing at least any one of heating and light irradiation until hardening reaction progresses and becomes unbonded is 1 minute or more. By making the above-mentioned pot time 1 minute or more, hardening does not progress excessively until the said one base material and the said other base material are bonded together, and higher adhesive strength can be obtained.

In the step of bonding the above-mentioned one base material to the above-mentioned another base material, the method of bonding the above-mentioned one base material to the above-mentioned another base material is not particularly limited, and it is preferable to carry out the bonding under a reduced pressure environment. combine. The preferable lower limit of the degree of vacuum under the above-mentioned decompression environment is 0.01 kPa, and the preferable upper limit is 10 kPa. By setting the degree of vacuum in the decompressed environment within this range, it does not take a long time to reach a vacuum state from the airtightness of the vacuum device or the capability of the vacuum pump, and it is possible to more efficiently remove the above-mentioned one substrate and the above-mentioned other substrate. Bubbles in the sealant for organic EL display elements of the present invention when one substrate is bonded.

The curable resin composition of the present invention is also suitably used as an optical adhesive. An optical adhesive containing the curable resin composition of the present invention is also one of the present invention.

Examples of the adherend of the optical adhesive of the present invention include optical members such as lenses for optics, optical sheets, filters, diffraction gratings, gratings, and optical fibers. The optical adhesive agent of the present invention is preferably used for bonding optical components such as optical lenses, optical sheets, filters, diffraction gratings, gratings, and optical fibers.

The cured product of the curable resin composition of the present invention is also suitably used as an optical member. An optical member including a cured product of the curable resin composition of the present invention is also one of the present invention.

The optical member of the present invention is preferably a molded body. As an optical member of this invention, an optical lens, an optical device member, a display device member, etc. are mentioned, for example. [Effect of Invention]

According to the present invention, it is possible to provide a curable resin composition having excellent curability and a cured product having a high refractive index. Moreover, according to this invention, the sealing compound for display elements containing this curable resin composition, and the sealing compound for organic electroluminescence display elements can be provided. Furthermore, according to the present invention, an optical adhesive containing the curable resin composition and an optical member containing a cured product of the curable resin composition can be provided.

Hereinafter, examples are disclosed to describe the present invention in more detail, but the present invention is not limited to these examples.

(Examples 1-10, Comparative Examples 1-3) According to the blending ratios recorded in Tables 1 and 2, use a stirring mixer to stir and mix each material at a stirring speed of 2000 rpm, thereby preparing the curable resin compositions of Examples 1-10 and Comparative Examples 1-3 things. As the stirring mixer, AR-250 (manufactured by Thinky Corporation) was used.

＜Evaluation＞ The following evaluations were performed on each curable resin composition obtained in Examples and Comparative Examples. The results are shown in Tables 1 and 2.

(viscosity and storage stability) The viscosity (initial viscosity) at 25° C. and 1.0 rpm was measured for each curable resin composition obtained in Examples and Comparative Examples using an E-type viscometer. As the E-type viscometer, VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.) was used, and as the rotor, No. 7 rotor was used. Also, the viscosity of each curable resin composition obtained in Examples and Comparative Examples after storage at 40° C. for 72 hours was measured in the same manner as the initial viscosity, and ((viscosity after storage at 40° C. for 72 hours) − (Initial Viscosity))/(Initial Viscosity) is derived as the rate of change of viscosity. The case where the viscosity change rate is less than 1.10 is set as "○", the case where it is more than 1.10 and less than 2.00 is set as "Δ", and the case where it is more than 2.00 or gelled is set as "X", In this way, the storage stability was evaluated.

(Curability) 0.3 g of each curable resin composition obtained in Examples and Comparative Examples was dropped on a glass substrate. Next, for the curable resin compositions obtained in Examples 1-4, 8-10 and Comparative Examples 1-3, heat at 100° C. for 30 minutes, and for the curable resin compositions obtained in Examples 5-7 , using UV-LED to irradiate 1500 mJ/cm ² of ultraviolet light with a wavelength of 365 nm. For the curable resin composition after heating or light irradiation, check whether it is cured, and whether it has surface stickiness or adhesiveness. If it is hardened and does not have surface stickiness or adhesiveness, it is set as "○", if it is hardened but has surface stickiness or stickiness, it is set as "Δ", and if it is not hardened, it is set as "×". , to evaluate the hardenability.

(Curing Shrinkage) The density of each curable resin composition and cured product obtained in Examples and Comparative Examples was measured using a dry density meter (“AccuPyc II 1345” manufactured by Shimadzu Corporation). Furthermore, for the curable resin compositions obtained in Examples 1-4, 8-10 and Comparative Examples 1-3, heat at 150° C. for 10 minutes, and for the curable resin compositions obtained in Examples 5-7 The object was irradiated with 1500 mJ/cm ² of ultraviolet rays with a wavelength of 365 nm using a UV-LED to obtain a hardened object. From each obtained density, the hardening shrinkage rate was calculated by the above-mentioned formula.

(Low outgassing property) 300 mg of each curable resin composition obtained in Examples and Comparative Examples was measured and sealed in a small glass bottle, and then cured. For the curable resin compositions obtained in Examples 1-4, 8-10 and Comparative Examples 1-3, they were cured by heating at 100°C for 30 minutes, and for the curable resin compositions obtained in Examples 5-7 The composition was hardened by irradiating ultraviolet light with a wavelength of 365 nm at 1500 mJ/cm ² using a UV-LED. Next, the outgassing amount in the vial was measured in terms of toluene using a gas chromatography-mass spectrometer. As the gas chromatography mass spectrometer, JMS-Q1050 (manufactured by JEOL Ltd.) was used. The case where the outgassing amount is less than 100 ppm is set as "○○", the case where it is more than 100 ppm and less than 200 ppm is set as "○", and the case where it is more than 200 ppm and less than 400 ppm is set as "Δ ", the case of 400 ppm or more will be set as "×" to evaluate the low outgassing property.

(Refractive Index) A silicone rubber sheet with a thickness of 100 μm was dug into a rectangle with a length of 20 mm and a width of 10 mm to make a mold. Place the mold on the release PET film, fill the mold with each of the curable resin compositions obtained in Examples and Comparative Examples, and then overlap another release PET film so that no air bubbles remain to obtain a laminate. body. The obtained laminate was sandwiched between two glass plates and fixed to harden the curable resin composition. For the curable resin compositions obtained in Examples 1 to 4, 8 to 10 and Comparative Examples 1 to 3, they were cured by heating at 150°C for 10 minutes, and for the curable resin compositions obtained in Examples 5 to 7 The composition was hardened by irradiating ultraviolet light with a wavelength of 365 nm at 1500 mJ/cm ² using a UV-LED. Thereafter, the PET film was peeled off, and the cured product of the sealant was taken out from the silicone rubber sheet to obtain a test piece with a length of 20 mm, a width of 10 mm, and a thickness of 100 μm. About the obtained test piece, the refractive index of the sodium D line of 25 degreeC was measured using the Abbe's refractometer. As the Abbe refractometer, NAR-4T (manufactured by Atago Corporation) was used. The refractive index was evaluated by setting "○" when the refractive index was 1.60 or more, "Δ" when it was 1.58 or more and less than 1.60, and "x" when it was less than 1.58.

(Discoloration resistance) A mold made of a PET film with a thickness of 100 μm was placed on a glass substrate, and each curable resin composition obtained in Examples and Comparative Examples was filled in the mold so that no air bubbles remained. The test piece was obtained by superimposing another glass substrate and curing the curable resin composition. For the curable resin compositions obtained in Examples 1-4, 8-10 and Comparative Examples 1-3, they were cured by heating at 100°C for 30 minutes, and for the curable resin compositions obtained in Examples 5-7 The composition was hardened by irradiating ultraviolet light with a wavelength of 365 nm at 1500 mJ/cm ² using a UV-LED. For the obtained test piece, the transmittance at a wavelength of 430 nm was measured at 25° C. using a spectrophotometer (manufactured by Hitachi High-Tech Science, Inc., “U-3900”). The case where the penetration rate is above 97% is set as "○", the case where the penetration rate is above 92% and less than 97% is set as "Δ", and the case where the penetration rate is less than 92% is set as "×". The anti-discoloration property was evaluated.

]-3',6'-二醇 - - - - - - - - 10 - 陽離子聚合起始劑 陽離子熱聚合起始劑 硼酸鹽系四級銨鹽 （King Industries公司製造，「CXC-1821」） 2 2 2 2 - - - 2 2 2 陽離子光聚合起始劑 硼酸鹽系鋶鹽 （日本綠化學公司製造，「DTS-200」） - - - - 1 1 1 - - - 穩定劑 三乙醇胺 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 評價 黏度（Pa・s） 0.6 1.4 0.4 1.5 350 1.6 430 0.7 0.7 140 黏度變化率 （保存穩定性） 1.01 （○） 1.00 （○） 1.01 （○） 1.02 （○） 1.00 （○） 1.02 （○） 1.01 （○） 1.00 （○） 1.00 （○） 1.02 （○） 硬化性 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ 硬化收縮率 3.8 3.6 3.4 3.7 2.4 3.3 2.2 3.9 3.8 3.2 低釋氣性 ○○ ○ ○ ○ ○ ○○ ○○ ○○ ○○ ○ 折射率 1.62 （○） 1.64 （○） 1.62 （○） 1.64 （○） 1.65 （○） 1.61 （○） 1.64 （○） 1.62 （○） 1.62 （○） 1.60 （○） 防變色性 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ [Table 1] Example 1 2 3 4 5 6 7 8 9 10 Composition (parts by weight) cationic polymerizable compound Compounds with biphenyl skeleton and epoxy group o-Phenylphenol Glycidyl Ether (manufactured by Yokkaichi Gosei Co., Ltd., "OPP-EP") 80 75 90 80 65 55 20 80 80 - Compounds with biphenyl skeleton and oxetanyl Compound represented by formula (3) (manufactured by Ube Industries, Ltd., "ETERNACOLL OXBP") - - - - - - - - - 85 other 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (manufactured by Daicel, "Celloxide 2021P") 10 - - - - 25 - 10 10 - 4,4'-bis(1,2-epoxycyclohexane) (manufactured by Daicel, "Celloxide 8010") - 5 5 - - - 30 - - - Terpene compound Terpene compounds containing phenolic hydroxyl groups 9,9-bis(4-hydroxyphenyl) terpene 10 20 5 20 35 20 50 - - 15 9,9-bis(4-hydroxy-3-methylphenyl) terpine - - - - - - - 10 - - Spiro[茀-9,9'-𠮿

]-3',6'-diol - - - - - - - - 10 - cationic polymerization initiator Cationic Thermal Polymerization Initiator Borate-based quaternary ammonium salt (manufactured by King Industries, "CXC-1821") 2 2 2 2 - - - 2 2 2 Cationic Photopolymerization Initiator Borate-based permeic salt (manufactured by Nippon Midori Chemical Co., Ltd., "DTS-200") - - - - 1 1 1 - - - stabilizer Triethanolamine 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 evaluate Viscosity (Pa・s) 0.6 1.4 0.4 1.5 350 1.6 430 0.7 0.7 140 Viscosity change rate (storage stability) 1.01 (○) 1.00 (○) 1.01 (○) 1.02 (○) 1.00 (○) 1.02 (○) 1.01 (○) 1.00 (○) 1.00 (○) 1.02 (○) sclerosis ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Hardening shrinkage 3.8 3.6 3.4 3.7 2.4 3.3 2.2 3.9 3.8 3.2 low outgassing ○○ ○ ○ ○ ○ ○○ ○○ ○○ ○○ ○ Refractive index 1.62 (○) 1.64 (○) 1.62 (○) 1.64 (○) 1.65 (○) 1.61 (○) 1.64 (○) 1.62 (○) 1.62 (○) 1.60 (○) Anti-tarnish ○ ○ ○ ○ ○ ○ ○ ○ ○ ○

[Table 2] comparative example 1 2 3 Composition (parts by weight) cationic polymerizable compound Compounds with biphenyl skeleton and epoxy group o-Phenylphenol Glycidyl Ether (manufactured by Yokkaichi Gosei Co., Ltd., "OPP-EP") 80 80 50 other 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (manufactured by Daicel, "Celloxide 2021P") - - 50 Terpene compound Terpene compounds containing phenolic hydroxyl groups 9,9-bis(4-hydroxyphenyl) terpene - 20 - Terpene compounds with non-phenolic hydroxyl groups 9,9-bis(4-(2-hydroxyethoxy)phenyl) terpine 20 - - cationic polymerization initiator Cationic Thermal Polymerization Initiator Borate-based quaternary ammonium salt (manufactured by King Industries, "CXC-1821") 2 - - anionic polymerization catalyst 2-Methylimidazole - 2 2 stabilizer Triethanolamine 0.01 0.01 0.01 evaluate Viscosity (Pa・s) 5.4 5.7 0.2 Viscosity change rate (storage stability) 1.00 (○) Gelation (×) 1.11 (Δ) sclerosis x x ○ Hardening shrinkage 3.1 3.8 4.5 low outgassing Δ ○ ○○ Refractive index 1.63 (○) 1.64 (○) 1.57 (×) Anti-tarnish ○ x ○ [Industrial availability]

According to the present invention, it is possible to provide a curable resin composition having excellent curability and a cured product having a high refractive index. Moreover, according to this invention, the sealing compound for display elements containing this curable resin composition, and the sealing compound for organic electroluminescence display elements can be provided. Furthermore, according to the present invention, an optical adhesive containing the curable resin composition and an optical member containing a cured product of the curable resin composition can be provided.

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Claims (11)

A curable resin composition characterized in that it contains a cation polymerizable compound, a cation polymerization initiator, and a terpene compound having a phenolic hydroxyl group in the molecule. The curable resin composition according to claim 1, wherein the fennel compound having a phenolic hydroxyl group in its molecule has two or more phenolic hydroxyl groups in one molecule. The curable resin composition according to claim 1 or 2, wherein the above-mentioned fennel compound having a phenolic hydroxyl group in its molecule is a compound represented by the following formula (1):

In formula (1), R ¹ and R ² are each a hydrogen atom, or are bonded to represent one oxygen atom, and R ³ to R ⁸ each independently represent a hydrogen atom, an alkyl group with 1 to 6 carbons, and a phenyl group , or benzyl. The curable resin composition according to claim 1, 2 or 3, wherein, in 100 parts by weight of the above curable resin composition, the content of the terpene compound having a phenolic hydroxyl group in the molecule is not less than 3 parts by weight and not more than 60 parts by weight . The curable resin composition according to claim 1, 2, 3, or 4, wherein the cationic polymerizable compound includes: a compound having a biphenyl skeleton and an epoxy group, and a compound having a biphenyl skeleton and an oxetanyl group. ) at least any one of the compounds. As for the curable resin composition of claim 1, 2, 3, 4 or 5, the cured product has a refractive index of 1.6 or more at the sodium D line at 25°C. The curable resin composition as claimed in claim 1, 2, 3, 4, 5 or 6 has a viscosity of 0.1 Pa·s to 5000 Pa·s measured at 25°C using an E-type viscometer. A sealant for display elements, which contains the curable resin composition of claim 1, 2, 3, 4, 5, 6 or 7. A sealant for organic EL display elements, which contains the curable resin composition of claim 1, 2, 3, 4, 5, 6 or 7. An optical adhesive containing the curable resin composition of claim 1, 2, 3, 4, 5, 6 or 7. An optical component comprising a cured product of the curable resin composition of claim 1, 2, 3, 4, 5, 6 or 7.