Polymerizable composition, encapsulation material, image display device, and method for manufacturing an image display device

Abstract

The polymerizable composition comprises a cationic polymerizable compound, a photocationic polymerization initiator, and a tertiary amine. The proportion of the tertiary amine is 60 parts by mass or more per 100 parts by mass of the photocationic polymerization initiator.

Description

Technology Field

[0001] The present invention relates to a polymerizable composition, a packaging material, an image display device, and a method for manufacturing an image display device. Background Technology

[0002] Recently, an image display device equipped with an optical element, for example, an organic EL display, has been known. In such an image display device, the optical element is encapsulated by an encapsulating material in order to prevent the optical element from deteriorating due to moisture in the atmosphere.

[0003] Encapsulation is commonly achieved by coating the material using inkjet printing and curing via UV light. However, since this method requires precise separation and coating of RGB using the FMM (Fine Metal Frame) technique, there are precision challenges when scaling up to large areas. Therefore, when manufacturing large-area OLED displays, it is common practice to deposit a white OLED and convert the color using a color filter.

[0004] When laminating color filters, a encapsulating agent is sealed in a dispenser or the like and cured, but since the lamination is done with color filters, it is structurally difficult to cure by irradiating with ultraviolet light after lamination. Therefore, a method is known in which ultraviolet light is irradiated before lamination to generate reaction initiating components from a photoinitiator, then lamination is performed, and the reaction is completed by heating (see, for example, Patent Document 1).

[0005] In addition, as such a packaging composition, a cotton-based encapsulant comprising, for example, a curable resin, a cationic polymerization initiator, and an amine compound as a photocuring retardant has been proposed (see, for example, Patent Document 1). Prior art literature

[0006] International Release No. 2013 / 157059 Pamphlet International Release No. 2020 / 149359 Pamphlet The problem to be solved

[0007] Meanwhile, in Patent Document 1, since the encapsulant is cured by heating at 100°C, there may be a problem that the optical element is damaged by heating. In order to suppress such damage, the encapsulant composition requires low-temperature curability.

[0008] In addition, such a packaging composition requires a pot life after UV irradiation. Specifically, after UV irradiation of the cotton-based packaging material, it is laminated using, for example, a color filter, and then cured by heating; however, if the viscosity becomes sufficiently high during lamination, the fluidity of the cotton-based packaging material decreases, making it impossible to laminate with accurate dimensions. Therefore, it is necessary to maintain a state where the viscosity is somewhat low after UV irradiation.

[0009] The present invention provides a polymerizable composition that achieves the compatibility of low-temperature curability and low-thickness after light irradiation by using a tertiary amine as a curing retardant, thereby allowing acid to be easily dissociated by heating while maintaining the trapping performance of active species after light irradiation; a packaging material comprising a cured product of the polymerizable composition; an image display device having the packaging material; and a method for manufacturing an image display device. means of solving the problem

[0010] The present invention [1] is a polymerizable composition comprising a cationic polymerizable compound, a photocationic polymerization initiator, and a tertiary amine, wherein the ratio of the tertiary amine is 60 parts by mass or more per 100 parts by mass of the photocationic polymerization initiator.

[0011] The present invention [2] includes the polymerizable composition described in [1], wherein the viscosity measured at 25°C and 100 rpm using an E-type viscometer is 100 mPa·s or higher.

[0012] The present invention [3] comprises a polymerizable composition described in [1] or [2], wherein the tertiary amine has a hindered structure.

[0013] The present invention [4] comprises a polymerizable composition described in any one of claims [1] to [3], wherein the tertiary amine is a 2-function tertiary amine.

[0014] The present invention [5] comprises a polymerizable composition described in any one of claims [1] to [4], wherein the tertiary amine has a NO bond.

[0015] The present invention [6] comprises a polymerizable composition described in any one of claims [1] to [5], wherein the tertiary amine has a NOC bond.

[0016] The present invention [7] comprises a polymerizable composition described in any one of claims [1] to [6], wherein the characteristic measured by the following test is liquid.

[0017] Test: Using Bar Coater No. 6, a 10 μm thick film is prepared on a 0.7 mm thick alkali-free glass substrate using the polymerizable composition. This film is left at room temperature (25°C) for 3 minutes while purging with nitrogen. Afterward, ultraviolet light (integrated light intensity of 1500 mJ / cm² using a UV-LED with a wavelength of 395 nm) is applied to this film. 2 ) investigate. Next, tilt the coated alkali-free glass at 70 degrees and wait 5 minutes, and determine that if the coating film drips down from the bottom of the alkali-free glass, it is liquid.

[0018] The present invention [8] comprises a polymerizable composition described in any one of claims [1] to [7], which further comprises a sensitizing agent.

[0019] The present invention [9] comprises a packaging material comprising a cured product of a polymerizable composition described in any one of claims [1] to [8].

[0020] The present invention

[10] includes an image display device having an optical element and a sealing material described in [9] that encapsulates the optical element.

[0021] The present invention

[11] includes a method for manufacturing an image display device comprising a first process for preparing an optical element and a second process for encapsulating the optical element with the encapsulating material described in [9]. Effects of the invention

[0022] The polymerizable composition of the present invention comprises a cationic polymerizable compound, a photocationic polymerization initiator, and a tertiary amine. In addition, the proportion of the tertiary amine is 60 parts by mass or more with respect to 100 parts by mass of the photocationic polymerization initiator.

[0023] First, when light is irradiated onto such a polymerizable composition, an acid is generated from a photocationic polymerization initiator. Subsequently, this acid is captured by a sufficient amount of a tertiary amine. Then, when this polymerizable composition is heated at a low temperature, the acid is detached, and the polymerizable composition is polymerized (cured). Therefore, this polymerizable composition has excellent low-temperature curability.

[0024] In addition, the polymerizable composition has excellent low viscosity after light irradiation because polymerization (curing) caused by light irradiation is suppressed by a sufficient amount of tertiary amine. Specific details for implementing the invention

[0025] The polymerizable composition comprises a cationic polymerizable compound, a photocationic polymerization initiator, and a tertiary amine.

[0026] <Cationic Polymerizable Compounds>

[0027] Examples of cationic polymerizable compounds include epoxy compounds and oxetane compounds. Preferably, epoxy compounds and oxetane compounds are used in combination as cationic polymerizable compounds. More preferably, the cationic polymerizable compound consists of an epoxy compound and an oxetane compound.

[0028] [Epoxy Compounds]

[0029] Examples of epoxy compounds include aliphatic epoxy resins, alicyclic epoxy resins, and aromatic epoxy resins, and preferably, alicyclic epoxy resins.

[0030] A cycloaliphatic epoxy resin is a curable resin (photocurable resin, preferably a UV-curable resin) having epoxy groups and an aliphatic ring (cycloaliphatic backbone) and not having an aromatic ring.

[0031] Examples of cycloaliphatic epoxy resins include glycidyl group-containing cycloaliphatic epoxy resins, glycidyl ether group-containing cycloaliphatic epoxy resins, and epoxycyclostructure-containing epoxy resins.

[0032] (Glycidyl group-containing cycloaliphatic epoxy resin)

[0033] A glycidyl group-containing alicyclic epoxy resin has, for example, a glycidyl group bonded to an aliphatic ring. Such a glycidyl group-containing alicyclic epoxy resin is, for example, represented by the following general formula (1).

[0034] [Chemical Formula 1]

[0035]

[0036] In equation (1), R 1 represents a monovalent organic group, and n represents the degree of polymerization. Additionally, a substituent such as an alkyl group may be bonded to the carbon atoms constituting the cyclohexane ring.

[0037] As a glycidyl group-containing alicyclic epoxy resin represented by the above general formula (1), specifically, a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol may be used.

[0038] A glycidyl group-containing cycloaliphatic epoxy resin represented by the above general formula (1) may be commercially available. As a commercially available product of a glycidyl group-containing cycloaliphatic epoxy resin represented by the above general formula (1), for example, EHPE3150 (epoxy equivalent 170-190 g / eq., manufactured by Daicel Co.).

[0039] (Glycidyl ether-containing alicyclic epoxy resin)

[0040] A glycidyl ether-containing alicyclic epoxy resin has glycidyl ether units bonded to an aliphatic ring. Preferably, the glycidyl ether-containing alicyclic epoxy resin is a polyglycidyl ether-containing alicyclic epoxy resin having a plurality of glycidyl ether units bonded to an aliphatic ring.

[0041] Examples of glycidyl ether-containing alicyclic epoxy resins include difunctional glycidyl ether-containing alicyclic epoxy resins. Examples of difunctional glycidyl ether-containing alicyclic epoxy resins include hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, and hexahydrophthalic acid diglycidyl ester.

[0042] (Epoxycyclostructure-containing epoxy resin)

[0043] An epoxy resin containing an epoxycyclo structure has an epoxycyclo structure having an epoxy group composed of two adjacent carbon atoms forming an aliphatic ring and one oxygen atom bonded to the two carbon atoms.

[0044] As an example of an epoxy cyclo structure-containing epoxy resin, an epoxy cyclohexane structure-containing epoxy resin (hereinafter referred to as an ECH structure-containing epoxy resin) may be cited.

[0045] Examples of epoxy resins containing an ECH structure include an epoxy resin containing one ECH structure represented by the following chemical formula (2), an epoxy resin containing one ECH structure represented by the following chemical formula (3), an epoxy resin containing two ECH structures represented by the following general formula (4), and modified products thereof.

[0046] [Chemical Formula 2]

[0047]

[0048] [Chemical Formula 3]

[0049]

[0050] [Chemical Formula 4]

[0051]

[0052] In formula (4), X represents a linker (a divalent group having one or more atoms). R 2 represents one atom or substituent selected from the group consisting of a hydrogen atom, a fluorine atom, an alkyl group, a fluoroalkyl group, an aryl group, a furyl group, and a thienoyl group. Two Rs in Formula (4). 2 They may be identical or different from each other.

[0053] An epoxy resin containing two ECH structures represented by the above general formula (4) (hereinafter referred to as an epoxy resin containing an ECH structure represented by the general formula (4)) has an ECH structure (epoxycyclohexyl group) at both ends of the molecule, and two epoxycyclohexyl groups are bonded by interposing linkers. Meanwhile, the epoxycyclohexyl group is a functional group comprising an epoxy group composed of a cyclohexane ring, two adjacent carbon atoms forming the cyclohexane ring, and one oxygen atom bonded to those two carbon atoms.

[0054] In the above general formula (4), R 2 Examples of alkyl groups represented by are straight-chain or branched-chain alkyl groups having 1 to 6 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, etc.).

[0055] In the above general formula (4), R 2 Examples of fluoroalkyl groups represented by are straight-chain or branched-chain fluoroalkyl groups having 1 to 6 carbon atoms (e.g., perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, etc.).

[0056] In the above general formula (4), R 2 Examples of aryl groups represented by can be aryl groups having 6 to 18 carbon atoms (e.g., phenyl group, naphthyl group, etc.).

[0057] Examples of the linkers indicated by X in the above general formula (4) include oxygen atoms, sulfur atoms, divalent hydrocarbon groups, polyoxyalkylene groups, carbonyl groups, ether groups, thioether groups, ester groups, carbonate groups, amide groups, and groups connected thereto.

[0058] Examples of divalent hydrocarbon groups include straight-chain or branched-chain alkylene groups having 1 to 20 carbon atoms (e.g., methylene group, methylmethylene group, dimethylmethylene group, ethylene group, propylene group, trimethylene group, butylene group, etc.), straight-chain or branched-chain unsaturated hydrocarbon groups having 1 to 20 carbon atoms (e.g., propenylene group, methylpropenylene group, butenylene group, etc.).

[0059] Examples of polyoxyalkylene groups include straight-chain or branched-chain polyoxyalkylene groups having 1 to 120 carbon atoms (e.g., polyoxyethylene groups, polyoxypropylene groups, etc.).

[0060] As an epoxy resin containing an ECH structure represented by the general formula (4), specifically, bis(3,4-epoxycyclohexylmethyl)ether, 1,2-bis(3,4-epoxycyclohexane-1-yl)ethane, 2,2-bis(3,4-epoxycyclohexane-1-yl)propane, 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexane carboxylate, and ε-caprolactone modified 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, and preferably, 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexane carboxylate.

[0061] In addition, commercially available epoxy resins containing an ECH structure represented by the above general formula (4) may be used. Examples of commercially available epoxy resins containing an ECH structure represented by the above general formula (4) include celoxide 8010, celoxide 2021P (epoxy equivalent 128-145 g / eq.), and celoxide 2081 (all manufactured by Daicel Co.).

[0062] As an ECH structure-containing epoxy resin, preferably, an ECH structure-containing epoxy resin represented by the general formula (4) above may be used.

[0063] In addition, as a cycloaliphatic epoxy resin, preferably a glycidyl group-containing cycloaliphatic epoxy resin and an epoxy cyclostructure-containing epoxy resin may be used, and preferably, the epoxy cyclostructure-containing epoxy resin may be used alone and the glycidyl group-containing cycloaliphatic epoxy resin and the epoxy cyclostructure-containing epoxy resin may be used in combination.

[0064] When a glycidyl group-containing alicyclic epoxy resin and an epoxy cyclostructure-containing epoxy resin are used in combination, the mixing ratio of the glycidyl group-containing alicyclic epoxy resin is, for example, 1 part by mass or more, preferably 5 parts by mass or more, and, for example, 20 parts by mass or less, preferably 10 parts by mass or less, with respect to 100 parts by mass of the total amount of the glycidyl group-containing alicyclic epoxy resin and the epoxy cyclostructure-containing epoxy resin. In addition, the mixing ratio of the glycidyl group-containing alicyclic epoxy resin is, for example, 1% by mass or more, preferably 3% by mass or more, with respect to the cationic polymerizable compound, and, for example, 15% by mass or less, preferably 8% by mass or less.

[0065] In addition, the blending ratio of the epoxy cyclostructure-containing epoxy resin is, for example, 80 parts by mass or more, preferably 90 parts by mass or more, with respect to 100 parts by mass of the total amount of the glycidyl group-containing alicyclic epoxy resin and the epoxy cyclostructure-containing epoxy resin, and also, for example, 99 parts by mass or less, preferably 95 parts by mass or less. In addition, the blending ratio of the epoxy cyclostructure-containing epoxy resin is, for example, 60% by mass or more, preferably 70% by mass or more, with respect to the cationic polymerizable compound, and also, for example, 90% by mass or less, preferably 80% by mass or less.

[0066] The weight average molecular weight of the alicyclic epoxy resin is, for example, 200 or more, for example, 1000 or less, preferably 500 or less. The weight average molecular weight (Mw) can be determined by gel permeation chromatography (GPC) using polystyrene as a standard material.

[0067] In addition, the epoxy equivalent in the cycloaliphatic epoxy resin is, for example, 90 g / eq. or more, preferably 100 g / eq. or more, for example, 250 g / eq. or less, preferably 190 g / eq. or less. The epoxy equivalent can be measured in accordance with JIS K7236:2001.

[0068] Epoxy compounds can be used alone or in combination of two or more types.

[0069] And, the mixing ratio of the epoxy compound is, for example, 65 mass% or more, preferably 75 mass% or more, with respect to the cationic polymerizable compound, and also, for example, 95 mass% or less, preferably 85 mass% or less.

[0070] [Oxetane Compound]

[0071] Oxetane compounds contain, for example, 1 to 5 oxetane rings.

[0072] Examples of oxetane compounds include monofunctional oxetane compounds having one oxetane ring, difunctional oxetane compounds having two oxetane rings, and trifunctional or more oxetane compounds having three or more oxetane rings.

[0073] Examples of monofunctional oxetane compounds include 3-ethyl-3-hydroxymethyloxetane, 3-(meth)allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy)methylbenzene, 2-ethylhexyl(3-ethyl-3-oxetanylmethyl)ether, ethyldiethylene glycol(3-ethyl-3-oxetanylmethyl)ether, and 3-cyclohexylmethyl-3-ethyl-oxetane.

[0074] As a bifunctional oxetane compound, for example, 1,4-bis{〔(3-ethyl-3-oxetanyl)methoxy〕methyl}benzene, 3,3'-(oxybismethylene)bis(3-ethyloxetane), 1,4-bis〔(3-ethyl-3-oxetanyl)methoxy〕benzene, 1,3-bis〔(3-ethyl-3-oxetanyl)methoxy〕benzene, 3,7-bis(3-oxetanyl)-5-oxanonein, 1,4-bis〔(3-ethyl-3-oxetanylmethoxy)methyl〕benzene, 1,2-bis〔(3-ethyl-3-oxetanylmethoxy)methyl〕ethane, 1,2-bis〔(3-ethyl-3-oxetanylmethoxy)methyl〕propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, Examples include dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl)ether, and preferably 3,3'-(oxybismethylene)bis(3-ethyloxetane).

[0075] Examples of oxetane compounds with three or more functions include trimethylolpropane tris(3-ethyl-3-oxetanylmethyl)ether, pentaerythritol tris(3-ethyl-3-oxetanylmethyl)ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl)ether, and dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl)ether.

[0076] Commercially available oxetane compounds may also be used. Examples of commercially available oxetane compounds include Aaron Oxetane OXT-221 (3,3'-(oxybismethylene)bis(3-ethyloxetane)) and Aaron Oxetane OXT-121 (both manufactured by Doagosei Chemical Co., Ltd.).

[0077] As an oxetane compound, preferably a two-function oxetane compound may be cited.

[0078] Oxetane compounds can be used alone or in combination of two or more types.

[0079] The proportion of the oxetane compound is, for example, 5 mass% or more, preferably 15 mass% or more, with respect to the cationic polymerizable compound, and also, for example, 60 mass% or less, preferably 50 mass% or less, more preferably 40 mass% or less, even more preferably 35 mass% or less, and particularly preferably 25 mass% or less.

[0080] In addition, the proportion of the cationic polymerizable compound is, for example, 80 mass% or more, preferably 85 mass% or more, more preferably 90 mass% or more, and also, for example, 98 mass% or less, with respect to the polymerizable composition.

[0081] <Photocationic Polymerization Initiator>

[0082] A photocationic polymerization initiator is, for example, a photoacid generator that generates acid upon light irradiation.

[0083] The photocationic polymerization initiator is not particularly limited, and known photocationic polymerization initiators may be used.

[0084] Examples of photocationic polymerization initiators include, specifically, aromatic sulfonium salts, aromatic iodonium salts, aromatic diazonium salts, and aromatic ammonium salts. The anionic portion of these salts is, for example, BF 4- , PF 6- , SbF 6- , or BY 4- (Y is a phenyl group substituted with at least two fluorine or trifluoromethyl groups.)

[0085] Examples of aromatic sulfonium salts include bis[4-(diphenylsulfonio)phenyl]sulfide bishexafluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfide bishexafluoroantimonate, bis[4-(diphenylsulfonio)phenyl]sulfide bistetrafluoroborate, bis[4-(diphenylsulfonio)phenyl]sulfide tetrakis(pentafluorophenyl)borate, diphenyl-4-(phenylthio)phenylsulfonium hexafluorophosphate, diphenyl-4-(phenylthio)phenylsulfonium hexafluoroantimonate, and diphenyl-4-(phenylthio)phenylsulfonium tetrafluoroborate.

[0086] Examples of aromatic iodium salts include diphenyl-iodonium hexafluorophosphate, diphenyl-iodonium hexafluoroantimonate, diphenyl-iodonium tetrafluoroborate, diphenyl-iodonium tetrakis(pentafluorophenyl)borate, bis(dodecylphenyl)iodonium hexafluorophosphate, bis(dodecylphenyl)iodonium hexafluoroantimonate, bis(dodecylphenyl)iodonium tetrafluoroborate, and bis(dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate.

[0087] Examples of aromatic diazonium salts include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis(pentafluorophenyl)borate.

[0088] Examples of aromatic ammonium salts include 1-benzyl-2-cyanopyridinium hexafluorophosphate and 1-benzyl-2-cyanopyridinium hexafluoroantimonate.

[0089] In addition, commercially available photocationic polymerization initiators may be used. Specifically, examples include Irgacure250, Irgacure270, Irgacure290 (all manufactured by BASF), CPI-100P, CPI-101A, CPI-200K, CPI-310B, CPI-400PG (all manufactured by San Afro), SP-150, SP-170, SP-171, SP-056, SP-066, SP-130, SP-140, SP-601, SP-606, SP-701 (all manufactured by ADEKA).

[0090] Photocationic polymerization initiators can be used alone or in combination of two or more types.

[0091] The mixing ratio of the photocationic polymerization initiator is, for example, 0.25 parts by weight or more, preferably 0.5 parts by weight or more, more preferably 0.8 parts by weight or more, even more preferably 1.0 parts by weight or more, particularly preferably 1.3 parts by weight or more, with respect to 100 parts by weight of the cationic polymerizable compound. Also, for example, 5.0 parts by weight or less, preferably 4.0 parts by weight or less, more preferably 3.0 parts by weight or less, even more preferably 2.5 parts by weight or less, and particularly preferably 2.0 parts by weight or less.

[0092] <Tertiary Amine>

[0093] Tertiary amines capture acid generated from a photocationic polymerization initiator by light irradiation.

[0094] As tertiary amines, examples include a monofunctional tertiary amine having one amino group, a difunctional tertiary amine having two amino groups, and a tertiary amine with three or more amino groups. Preferably, from the perspective of high acid trapping efficiency, a difunctional tertiary amine and a tertiary amine with three or more functions may be cited. More preferably, from the perspective of maintaining good compatibility with epoxy compounds, a difunctional tertiary amine may be cited. Even more preferably, from the perspective of ease of acid dissociation upon heating, a difunctional tertiary amine having a NO bond, and particularly preferably, a difunctional tertiary amine having a NOC bond may be cited.

[0095] In addition, the tertiary amine preferably has a hindered structure. Examples of hindered structures include, for instance, a structure having steric hindrance such as 2,2,6,6-tetramethylpiperidine.

[0096] The tertiary amine is preferably a binary tertiary amine having a hindered structure. That is, the tertiary amine preferably has two 2,2,6,6-tetramethylpiperidine structures.

[0097] Examples of such tertiary amines include compounds represented by the following general formula (5) and compounds represented by the following general formula (6).

[0098] [Chemical Formula 5]

[0099]

[0100] In equation (5), R 3 Silver represents an alkyl group having 1 to 20 carbon atoms. Examples of straight-chain or branched-chain alkyl groups having 1 to 20 carbon atoms include butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and eicosyl groups. Two Rs in formula (5). 3 They may be identical or different from each other.

[0101] [Chemical Formula 6]

[0102]

[0103] In equation (6), R 4 represents a straight-chain or branched-chain alkyl group having 1 to 20 carbon atoms. Examples of straight-chain or branched-chain alkyl groups having 4 to 20 carbon atoms include butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and eicosyl groups. Two Rs in formula (5) 4 They may be identical or different from each other. R 5 represents an alkylene group having 1 to 8 carbon atoms. Examples of alkylene groups having 1 to 8 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, and an octylene group.

[0104] A compound represented by the above general formula (5), preferably a compound represented by the following general formula (7) (in the above general formula (5), R 3 This represents the undesilgi.) can be cited.

[0105] [Chemical Formula 7]

[0106]

[0107] In addition, as a compound represented by the above general formula (6), preferably, a compound represented by the following general formula (8) (in the above general formula (6), R 4 a, representing an octyl group, and R 5 (a, represents an octylene group.) can be cited.

[0108] [Chemical Formula 8]

[0109]

[0110] Commercially available tertiary amines may be used. Examples of commercially available tertiary amines include ADEKA STAP LA-81 (a compound represented by the above general formula (7), manufactured by ADEKA Corporation) and Tinuvin 123 (a compound represented by the above general formula (8), manufactured by BASF Japan Corporation).

[0111] The proportion of the tertiary amine is, in terms of capture ability for acid generated from the photocationic polymerization initiator, 60 parts by mass or more, preferably 70 parts by mass or more, more preferably 80 parts by mass or more, even more preferably 90 parts by mass or more, and particularly preferably 100 parts by mass or more, with respect to 100 parts by mass of the photocationic polymerization initiator.

[0112] Tertiary amines may be used alone or in combination of two or more types.

[0113] In addition, the proportion of the tertiary amine is, for example, 1 part by mass or more, preferably 1.3 parts by mass or more, with respect to 100 parts by mass of the cationic polymerizable compound, and, for example, 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less.

[0114] In addition, the proportion of the tertiary amine is, for example, 0.6 mass% or more, preferably 1 mass% or more, with respect to the polymerizable composition, and, for example, 10 mass% or less, preferably 5 mass% or less.

[0115] Preparation of Polymerizable Compositions

[0116] To prepare a polymerizable composition, a cationic polymerizable compound, a photocationic polymerization initiator, and a tertiary amine are mixed. By doing so, a polymerizable composition is prepared.

[0117] [Increase / Decrease System]

[0118] In the above formulation, preferably, a sensitizer is incorporated. That is, the polymerizable composition preferably includes a sensitizer.

[0119] Examples of sensitizers include carbazoles, acetophenones, benzophenones, naphthalenes, phenols, biacetyl, eosin, rose bengal, pyrenes, anthracenes (e.g., 9,10-di(capryloyloxy)anthracene), and phenothiazines, and preferably, anthracenes.

[0120] The mixing ratio of the sensitizer is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, with respect to 100 parts by mass of the cationic polymerizable compound, and also, for example, 5 parts by mass or less, preferably 2 parts by mass or less, more preferably 1 part by mass or less.

[0121] In addition, the mixing ratio of the sensitizer with respect to the polymerizable composition is, for example, 0.1 mass% or more, preferably 0.2 mass% or more, more preferably 0.3 mass% or more, even more preferably 0.5 mass% or more, and also, for example, 5 mass% or less, preferably 2 mass% or less, more preferably 1 mass% or less.

[0122] Sensitizers may be used alone or in combination of two or more types.

[0123] [Tackifier]

[0124] In the above formulation, a tackifier may be added as needed. That is, the polymerizable composition may include a tackifier.

[0125] Examples of tackifiers include natural rosin, modified rosin, polyterpene resin, synthetic petroleum resin, coumarone resin, phenolic resin, xylene resin, styrene resin (e.g., styrene polymer), and isoprene resin, and preferably, styrene resin.

[0126] The mixing ratio of the tackifier is, for example, 1 part by mass or more, preferably 3 parts by mass or more, and also, for example, 10 parts by mass or less, with respect to 100 parts by mass of the cationic polymerizable compound.

[0127] In addition, the mixing ratio of the tackifier is, for example, 1 mass% or more, preferably 3 mass% or more, and, for example, 10 mass% or less, with respect to the polymerizable composition.

[0128] Tackifiers can be used alone or in combination of two or more types.

[0129] [Other ingredients]

[0130] In the above formulation, additives may be incorporated as needed. That is, the polymerizable composition may include additives.

[0131] Examples of additives include antioxidants, polymerization initiators, anti-aging agents, wettability improvers, surfactants, plasticizers, ultraviolet absorbers, preservatives, and antimicrobial agents.

[0132] The mixing ratio of additives is appropriately set according to the use and purpose.

[0133] Additives may be used alone or in combination of two or more types.

[0134] In addition, the polymerizable composition may be diluted with a known organic solvent.

[0135] <Physical properties of polymerizable composition>

[0136] The viscosity of the polymerizable composition, measured using an E-type viscometer at 25°C and 100 rpm, is, for example, 101 mPa·s or more, preferably 106 mPa·s or more, more preferably 111 mPa·s or more, and even more preferably 116 mPa·s or more.

[0137] If the above viscosity is above the above lower limit, the shape retention during application is excellent.

[0138] In addition, the viscosity is, for example, 500 mPa·s or less, preferably 400 mPa·s or less, more preferably 300 mPa·s or less, even more preferably 250 mPa·s or less, and particularly preferably 200 mPa·s or less.

[0139] If the above viscosity is below the above upper limit, the polymerizable composition has excellent fluidity when bonded.

[0140] In addition, the nature of the polymerizable composition is preferably liquid. The method for confirming the nature of the polymerizable composition is described in detail in the evaluation of low viscosity after light irradiation in the examples described below.

[0141] In addition, the cured product of the polymerizable composition preferably has transparency. Specifically, the total light transmittance of the cured product of the polymerizable composition (in accordance with JIS K 7361-1) is, for example, 80% or more, preferably 85% or more, more preferably 90% or more, and also, for example, 100% or less.

[0142] <Effects of Action>

[0143] The polymerizable composition comprises a cationic polymerizable compound, a photocationic polymerization initiator, and a tertiary amine. In addition, the proportion of the tertiary amine is 60 parts by mass or more per 100 parts by mass of the photocationic polymerization initiator.

[0144] First, when light is irradiated onto such a polymerizable composition, an acid is generated from the photocationic polymerization initiator. Subsequently, this acid is captured by a sufficient amount of a tertiary amine (a blending ratio of 60 parts by mass or more per 100 parts by mass of the photocationic polymerization initiator). Then, when this polymerizable composition is heated to a low temperature (e.g., 90°C or lower, preferably 85°C or lower; also, e.g., 40°C or higher, preferably 60°C or higher), the acid is detached, and the polymerizable composition is polymerized (cured). Therefore, this polymerizable composition has excellent low-temperature curability. As a result, for example, when this polymerizable composition is used as an encapsulation for an optical element in an image display device equipped with an optical element, damage to the optical element caused by heat can be suppressed.

[0145] In addition, the polymerizable composition has excellent low viscosity after light irradiation because polymerization (curing) caused by light irradiation is suppressed by a sufficient amount of tertiary amine.

[0146] Bag material

[0147] The encapsulant comprises a cured product of the above-mentioned polymerizable composition. Since the encapsulant comprises a cured product of the above-mentioned polymerizable composition, it exhibits excellent low-temperature curability.

[0148] Image display device

[0149] An image display device comprises an optical element and the encapsulating material that encapsulates the optical element. In the image display device, since the optical element is encapsulated by the encapsulating material, damage to the optical element by heat can be reliably suppressed.

[0150] Method for manufacturing an image display device

[0151] A method for manufacturing an image display device comprises a first process for preparing an optical element and a second process for encapsulating the optical element with the encapsulating material.

[0152] In the first process, an optical element is prepared.

[0153] In the second process, the optical element is encapsulated by an encapsulating material. Specifically, the polymerizable composition is applied to encapsulate the optical element, for example, by inkjet printing, and then the polymerizable composition is cured. By doing so, the optical element is encapsulated by an encapsulating material.

[0154] Examples

[0155] Next, the present invention will be described based on examples and comparative examples, but the present invention is not limited by the following examples. Meanwhile, "parts" and "%" are based on mass unless otherwise specified. Furthermore, specific numerical values ​​such as mixing ratios (content ratios), physical properties, and parameters used in the following description may be replaced with the upper limits (numerical values ​​defined as "less than" or "less than") or lower limits (numerical values ​​defined as "greater than" or "greater than") of the corresponding mixing ratios (content ratios), physical properties, and parameters described in the "Specific Details for Implementing the Invention" above.

[0156] <Ingredient Details>

[0157] The product names and abbreviations of the ingredients used in each example and each comparative example are described in detail.

[0158] EHPE3150: 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, a glycidyl group-containing alicyclic epoxy resin represented by the above general formula (1), epoxy equivalent weight 170-190 g / eq., manufactured by Daicel Co.

[0159] CEL2021P: 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate, epoxy resin containing an ECH structure represented by the above general formula (4), trade name "Celoxide 2021P", molecular weight: 252.3, epoxy equivalent: 128-145 g / eq., manufactured by Daicel Co.

[0160] OXT221: 3,3'-(oxybismethylene)bis(3-ethyloxetane), trade name "Aaron Oxetane OXT-221", manufactured by Doagosei Chemical Co., Ltd.

[0161] LA-81: A compound represented by the above general formula (7), trade name “ADEKA STEP LA-81”, manufactured by ADEKA Corporation)

[0162] Tinuvin 123: A compound represented by the above general formula (8), trade name “Tinuvin 123”, manufactured by BASF Japan Co., Ltd.

[0163] UVS581: 9,10-Di(Capryloyloxy)anthracene, Trade name "Anthracure UVS-581", Manufactured by Kawasaki Kasei Industry Co., Ltd.

[0164] BHT: Dibutylhydroxytoluene

[0165] Preparation of Polymerizable Compositions

[0166] Examples 1 to 8, and Comparative Examples 1 to 4

[0167] Based on the formulation described in Table 1, each component was combined to prepare a polymerizable composition.

[0168] <Evaluation>

[0169] [viscosity]

[0170] The viscosity of the polymerizable compositions of each example and each comparative example was measured. Specifically, an E-type viscometer (TVE-35L type viscometer, manufactured by Toki Sangyo Co., Ltd., rotor name: 3°×R9.7) was used, and the viscosity at 25°C was measured in accordance with the cone plate viscometer method of JIS K5600-2-3 (2014). The rotation speed of the cone plate during measurement was set to 100 rpm.

[0171] [Low vapority after light irradiation]

[0172] For the polymerizable compositions of each example and each comparative example, a coating film with a thickness of 10 μm was prepared on a 0.7 mm thick alkali-free glass using Bar Coater No. 6. This coating film was left at room temperature (25°C) for 3 minutes while purging with nitrogen. Afterward, ultraviolet light (integrated light intensity of 1500 mJ / cm² using a UV-LED with a wavelength of 395 nm) was applied to this coating film. 2 ) was investigated. Next, the alkali-free glass was tilted 70 degrees, and after waiting 5 minutes, it was determined whether the coating film sagged and fell off from the bottom of the alkali-free glass.

[0173] (standard)

[0174] A: The film sagged and fell off from the bottom (the polymerizable composition is liquid).

[0175] B: The film moved to the bottom of the alkali-free glass but did not sag or fall off.

[0176] C: The film did not sag or fall off, and movement of the film could not be confirmed.

[0177] [Low-temperature curable]

[0178] For the polymerizable compositions of each example and each comparative example, a coating film with a thickness of 10 μm was formed on a 0.7 mm thick alkali-free glass using Bar Coater No. 6. This coating film was left at room temperature (25°C) for 3 minutes while purging with nitrogen. Afterward, ultraviolet light (1000 mW, 1500 mJ / cm²) was applied to this coating film in an N2 purging box. 2 ...was investigated. Subsequently, the coating film was heated at 80°C for 30 minutes with the film surface facing upward. After heating, the coating film was touched with a hand wearing protective gear to check its tackiness. Low-temperature curing properties were evaluated based on the following criteria. The results are shown in Table 1.

[0179] (standard)

[0180] A: Taekseong was not observed.

[0181] B: It is hardened overall, but the tackiness was checked.

[0182] C: It is liquid, and liquid gets on the skin when touched.

[0183] [Small Damage]

[0184] (Manufacturing of laminates)

[0185] A substrate was prepared by forming an ITO electrode film on the other side of the glass substrate in the thickness direction. Subsequently, on this substrate, the glass substrate side was treated using a UV-ozone treatment device (manufactured by Sen Special Light Source Co., PL21-200(S) / UVE-200J), and then ultrasonic cleaning was performed for 15 minutes each using an alkaline aqueous solution, pure water, acetone, and isopropyl alcohol, and finally, ultrasonic cleaning was performed for 10 minutes using acetone.

[0186] Next, this substrate was fixed to the substrate folder of the vacuum deposition apparatus. Separately, 200 mg of Dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile (HAT-CN) was added to one pre-fired coil (first coil), and 200 mg of 9-Phenyl-3,6-bis(9-phenyl-9H-carbazol-3-yl)-9H-carbazole (Tris-PCz) was added to another pre-fired coil (second coil). After that, the inside of the vacuum chamber of the vacuum deposition apparatus was 1×10 -4 Depressurized to Pa.

[0187] Next, the first heating element was heated to deposit HAT-CN on the substrate at a deposition rate of 0.4 Å / sec. By doing so, a HAT-CN film (film thickness 100 nm) was formed on the other side (ITO electrode side) in the thickness direction of the substrate.

[0188] Next, the second heating element was heated to deposit Tris-PCz on the substrate at a deposition rate of 1.0 Å / sec. As a result, a Tris-PCz film (film thickness 400 nm) was formed on the other side of the substrate in the thickness direction (HAT-CN film side).

[0189] Next, separately, prepare the first-baked fruit (third fruit), add 200 mg of Tris(8-hydroxyquinolinato)aluminium (Alq3) to it, and place it inside a vacuum chamber again 1 × 10 4 The pressure was reduced to Pa. Then, the third reduction was applied, and Alq3 was deposited on the substrate at a deposition rate of 0.5 Å / sec. As a result, an Alq3 film (film thickness 700 nm) was formed on the other side of the substrate in the thickness direction (Tris-PCz film side).

[0190] Next, prepare a tungsten resistance heating boat (first heating boat), place 200 mg of lithium fluoride into it, and place it inside the vacuum chamber again 1 × 10 4 The pressure was reduced to Pa. Then, the first heating boat was heated, and lithium fluoride was deposited on the substrate at a deposition rate of 0.03 Å / sec. By doing so, a lithium fluoride film (film thickness 5 nm) was formed on the other side of the substrate in the thickness direction (Alq3 film side).

[0191] Next, prepare another tungsten resistance heating boat (second heating boat), place 1g of magnesium and 200mg of silver into it, and place it inside the vacuum chamber again 1×10 4 The pressure was reduced to Pa. Then, the second heating boat was heated to set the magnesium deposition rate to 0.9 Å / sec and the silver deposition rate to 0.1 Å / sec, thereby depositing magnesium and silver on the substrate such that the ratio of magnesium to silver was 9 / 1. As a result, a film composed of magnesium and silver (film thickness 150 nm) was formed on the other side of the substrate in the thickness direction (the lithium fluoride film side). By doing so, a laminate having an 8 mm × 8 mm organic light-emitting material layer was obtained.

[0192] This laminate was encapsulated with the polymerizable compositions of each example and each comparative example. Specifically, 30 mg of the polymerizable compositions of each example and each comparative example was dropped onto the opposite side of the laminate in the thickness direction (the side of the film made of magnesium and silver), irradiated at 395 nm with 1500 mW, and then heated with a hot plate at 80°C for 30 minutes to cure the polymerizable compositions. By doing so, an organic EL display device was manufactured.

[0193] Next, after exposing this organic EL display element to an environment at a temperature of 85°C for 500 hours, a voltage of 3V was applied, and the luminescence state of the organic EL display element was visually inspected. The element damageability was evaluated based on the following criteria. The results are shown in Table 1.

[0194] A: No damage was observed in the organic EL display element.

[0195] B: Some dark spots occurred.

[0196] C: Dark spots occurred in most areas.

[0197] <Consideration>

[0198] Comparative Examples 1 and 2, which do not contain tertiary amines and contain primary amines, have reduced low-temperature curability. That is, in Comparative Examples 1 and 2, the primary amine first captures the acid generated from the photocationic polymerization initiator by light irradiation, but cannot detach the acid by subsequent low-temperature heating (85°C). Therefore, it can be seen that low-temperature curability is reduced.

[0199] In addition, Comparative Examples 3 and 4, in which the mixing ratio of tertiary amine is less than 60 parts by mass relative to 100 parts by mass of photocationic polymerization initiator, show reduced low viscosity after light irradiation. That is, in Comparative Examples 3 and 4, the amount of tertiary amine required to capture the acid generated from the photocationic polymerization initiator by light irradiation is small, so the acid cannot be reliably captured. Consequently, it can be seen that the polymerizable composition polymerizes (cures) upon light irradiation, causing the viscosity to increase rapidly, and thus the pot life for bonding cannot be secured.

[0200] In contrast, Examples 1 to 8, which contain a tertiary amine and in which the mixing ratio of the tertiary amine is 60 parts by weight or more per 100 parts by weight of the photocationic polymerization initiator, have excellent low viscosity and low temperature curing properties after light irradiation.

[0201] That is, in Examples 1 to 8, since a sufficient amount of tertiary amine is included, the acid generated from the photocationic polymerization initiator can be reliably captured by light irradiation. Therefore, the low viscosity after light irradiation is excellent. In addition, the acid can be removed by low-temperature heating (85°C). Therefore, the low-temperature curing properties are excellent.

[0202]

[0203] Meanwhile, although the above invention has been provided as an exemplary embodiment of the present invention, it is merely an example and should not be interpreted restrictively. Variations of the present invention that are obvious to those skilled in the art are included in the latter claims. Industrial applicability

[0204] The polymerizable composition, encapsulation material, image display device, and method for manufacturing the image display device of the present invention can be suitably used, for example, in the manufacture of an organic EL display.

Claims

Claim 1 A polymerizable composition comprising a cationic polymerizable compound, a photocationic polymerization initiator, and a tertiary amine, wherein the mixing ratio of the tertiary amine is 60 parts by weight or more per 100 parts by weight of the photocationic polymerization initiator, the cationic polymerizable compound comprises an epoxy compound and an oxetane compound, wherein the content ratio of the epoxy compound is 65% by weight or more and 95% by weight or less relative to the cationic polymerizable compound, and the content ratio of the oxetane compound is 5% by weight or more and 35% by weight or less relative to the cationic polymerizable compound. Claim 2 A polymerizable composition according to claim 1, wherein the viscosity measured using an E-type viscometer under conditions of 25°C and 100 rpm is 100 mPa·s or higher. Claim 3 In claim 1, the tertiary amine is a polymerizable composition having a hindered structure. Claim 4 A polymerizable composition according to claim 1, wherein the tertiary amine is a 2-function tertiary amine. Claim 5 In claim 1, the tertiary amine is a polymerizable composition having a NO bond. Claim 6 In claim 1, the tertiary amine is a polymerizable composition having a NOC bond. Claim 7 A polymerizable composition according to claim 1, wherein the properties measured by the following test are in a liquid state. Test: A coating film with a thickness of 10 μm is prepared on a 0.7 mm thick alkali-free glass surface using Bar Coater No. 6 with the polymerizable composition. This coating film is left at room temperature (25°C) for 3 minutes while purging with nitrogen. Thereafter, ultraviolet light (integrated light intensity of 1500 mJ / cm² using a UV-LED with a wavelength of 395 nm) is applied to this coating film. 2 ) investigate. Next, tilt the coated alkali-free glass at 70 degrees and wait 5 minutes, and determine that if the coating film drips down from the bottom of the alkali-free glass, it is liquid. Claim 8 A polymerizable composition according to claim 1, further comprising a sensitizer. Claim 9 A bag material comprising a cured product of the polymerizable composition described in claim 1. Claim 10 An image display device comprising an optical element and a sealing material described in claim 9 for sealing the optical element. Claim 11 A method for manufacturing an image display device comprising a first process for preparing an optical element and a second process for encapsulating the optical element using an encapsulating material described in claim 9.

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