KR102226987B1 - Photo-post-curing resin composition - Google Patents

Abstract

It is an object of the present invention to provide a light post-curable resin composition that can suppress outgassing and is excellent in transparency and reliability.
The present invention is an optical post-curable resin composition containing a cation-curable resin, a photo-cationic polymerization initiator, and a compound having an amino group and a cation-polymerizable functional group.

Description

Light post-curable resin composition {PHOTO-POST-CURING RESIN COMPOSITION}

The present invention relates to a light post-curing resin composition that can suppress outgassing and is excellent in transparency and reliability.

In recent years, research on organic optical devices using organic thin-film elements such as organic electroluminescence (organic EL) display elements and organic thin-film solar cell elements has been conducted. Since the organic thin-film device can be manufactured simply by vacuum evaporation, solution coating, or the like, it is also excellent in productivity.

An organic EL display device has a thin film structure in which an organic light emitting material layer is sandwiched between a pair of electrodes facing each other. When electrons are injected from one electrode and holes are injected from the other electrode into the organic light emitting material layer, electrons and holes are combined in the organic light emitting material layer to perform self-emission. Compared with a liquid crystal display device that requires a backlight, it has the advantage that visibility is good, it is possible to be thinner, and it is possible to drive a direct current low voltage.

However, such an organic EL display device has a problem that when the organic light-emitting material layer or electrode is exposed to outside air, its light-emitting characteristics are rapidly deteriorated and its lifespan is shortened. Therefore, for the purpose of improving the stability and durability of the organic EL display device, in the organic EL display device, a sealing technique for blocking the organic light emitting material layer or electrode from moisture or oxygen in the atmosphere is becoming indispensable.

Patent Document 1 discloses a method of filling a photocurable adhesive between substrates of an organic EL display device and sealing by irradiating light in a top-emitting type organic EL display device or the like. However, in the case of using a photocurable adhesive in this way, there is a problem in that outgas is generated during light irradiation and is filled in the device, thereby promoting deterioration of the device.

Japanese Patent Laid-Open Publication No. 2001-357973

It is an object of the present invention to provide a light post-curable resin composition that can suppress outgassing and is excellent in transparency and reliability.

The present invention is a photo-post-curable resin composition containing a cation-curable resin, a photo-cationic polymerization initiator, and a compound having an amino group and a cation-polymerizable functional group.

The present invention is described in detail below.

The present inventors believe that the cause of outgassing when a photocurable adhesive is used for encapsulation of an organic EL display device, etc., is particularly cured made of a compound having an ether bond such as crown ether, which is commonly blended in a light post-curable adhesive. I thought it was in the retarder. That is, it was considered that the curing retardant was decomposed by acid or the like during light irradiation, and thus dioxane or the like was generated as an out gas.

Therefore, the present inventors use a compound having an amino group and a cation polymerizable functional group in place of such a curing retardant, so that the amino group exerts a curing delaying effect and is introduced into the cured product by the cation polymerizable functional group, thereby reducing outgassing. It was found that the occurrence could be suppressed, and the present invention was completed.

The light post-curable resin composition of the present invention contains a compound having an amino group and a cation polymerizable functional group. In the compound having an amino group and a cation-polymerizable functional group, the generation of outgas can be suppressed by introducing the amino group into the cured product by the cation-polymerizable functional group while exhibiting a curing delaying effect.

Further, the compound having an amino group and a cation-polymerizable functional group has a cation-polymerizable functional group, but since it has an amino group, the cation polymerization property is very low.

Examples of the amino group include a primary amino group, a secondary amino group, and a tertiary amino group. When the amino group has a secondary amino group or a tertiary amino group, it is preferable that the nitrogen atom of at least one amino group is bonded to the cation polymerizable functional group directly or via an alkylene group.

It is preferable that the said amino group is a tertiary amino group from a viewpoint of exhibiting an appropriate curing delaying effect.

Examples of the cationic polymerizable functional group include an epoxy group, an oxetane group, a hydroxyl group, a vinyl ether group, an episulfide group, and an ethyleneimine group. Especially, an epoxy group is preferable from a viewpoint of making it easy to introduce into a hardened|cured material.

In addition, it is preferable that the compound having an amino group and a cation polymerizable functional group has two or more of the cation polymerizable functional groups in one molecule from the viewpoint of being easily introduced into a cured product.

Since the compound having an amino group and a cation-polymerizable functional group is particularly excellent in compatibility between the curing delaying effect and the effect of suppressing outgassing introduced into the cured product, it is composed of compounds represented by the following formulas (1) to (7). It is preferable that it is at least 1 type selected from the group.

[Formula 1]

In formula (1), R ¹ represents an alkylene group having 1 to 3 carbon atoms. Each R ¹ may be the same or different.

[Formula 2]

In formula (2), R ² represents a C1-C3 alkylene group. Each R ² may be the same or different.

[Formula 3]

In formula (3), R ³ represents an alkylene group having 1 to 3 carbon atoms. Each R ³ may be the same or different.

[Formula 4]

In formula (4), R ⁴ represents an alkylene group having 1 to 3 carbon atoms. Each R ⁴ may be the same or different. R ⁵ is either a methyl group, an ethyl group, an ethylene group, or a propyl group.

[Formula 5]

In formula (5), R ⁶ represents an alkylene group having 1 to 3 carbon atoms. Each R ⁶ may be the same or different. R ⁷ is either a methyl group, an ethyl group, an ethylene group, or a propyl group, and each R ⁷ may be the same or different.

[Formula 6]

In formula (6), R ⁸ represents an alkylene group having 1 to 3 carbon atoms. Each R ⁸ may be the same or different.

[Formula 7]

In formula (7), R ⁹ represents an alkylene group having 1 to 3 carbon atoms. Each R ⁹ may be the same or different.

In the formula (1), R ¹ is preferably a methylene group, in the formula (2), R ² is preferably a methylene group, in the formula (3), R ³ is preferably a methylene group, and the formula In (4), R ⁴ is preferably a methylene group, R ⁵ is preferably a propyl group, in the formula (5), R ⁶ is preferably a methylene group, R ⁷ is preferably a propyl group, and the formula In (6), R ⁸ is preferably a methylene group, and in formula (7), R ⁹ is preferably a methylene group.

The preferred lower limit of the weight average molecular weight of the compound having an amino group and a cation polymerizable functional group is 200, and a preferred upper limit is 1000. If the weight average molecular weight of the compound having the amino group and the cation polymerizable functional group is less than 200, the compound having the amino group and the cation polymerizable functional group remaining without being introduced into the cured product may cause outgassing. . When the weight average molecular weight of the compound having an amino group and a cation-polymerizable functional group exceeds 1000, the viscosity of the resulting photo-post-curable resin composition may become too high and coatability and the like may deteriorate. A more preferable lower limit of the weight average molecular weight of the compound having an amino group and a cationically polymerizable functional group is 300, and a more preferable upper limit is 800.

In addition, in this specification, the said weight average molecular weight is a value measured by gel permeation chromatography (GPC) and calculated|required by polystyrene conversion. As a column for measuring the weight average molecular weight in terms of polystyrene by GPC, Shodex LF-804 (made by Showa Electric Corporation), etc. are mentioned, for example.

Among the compounds having an amino group and a cation-polymerizable functional group, commercially available compounds include, for example, TEPIC (manufactured by Nissan Chemical Corporation), jER604, jER630 (all manufactured by Mitsubishi Chemical Corporation), and the like.

The content of the compound having an amino group and a cation-polymerizable functional group is preferably 0.01 parts by weight, and a preferable upper limit is 20 parts by weight, based on 100 parts by weight of the cation-curable resin. When the content of the compound having the amino group and the cation polymerizable functional group is less than 0.01 parts by weight, the curing delaying effect may not be sufficiently exhibited. When the content of the compound having an amino group and a cation-polymerizable functional group exceeds 20 parts by weight, the resulting photo-post-curable resin composition may have poor curability. A more preferable lower limit of the content of the compound having an amino group and a cationically polymerizable functional group is 0.05 parts by weight, a more preferable upper limit is 15 parts by weight, a more preferable lower limit is 0.1 parts by weight, and a further preferable upper limit is 10 parts by weight.

The light post-curable resin composition of the present invention contains a cation curable resin.

The cation-curable resin is not particularly limited as long as it is a compound having at least one cation-polymerizable functional group in its molecule and rich in cation-polymerization property.

Examples of the cationic polymerizable functional group include an epoxy group, an oxetane group, a hydroxyl group, a vinyl ether group, an episulfide group, and an ethyleneimine group. Especially, it is preferable that the said cation-curable resin contains an epoxy resin from the point which expresses high adhesiveness and durability after hardening.

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, resorcinol type An epoxy resin having an aromatic ring such as an epoxy resin, an epoxy resin having an aliphatic ring such as a hydrogenated bisphenol A type epoxy resin and a hydrogenated bisphenol F type epoxy resin, and an alicyclic epoxy resin. Among them, it is preferable to contain an alicyclic epoxy resin from the viewpoint of suppressing outgassing. These epoxy resins may be used alone or in combination of two or more.

As the alicyclic epoxy resin, for example, 1,2:8,9-diepoxylimonene, 4-vinylcyclohexene monooxide, vinylcyclohexene dioxide, methylated vinylcyclohexene dioxide, (3,4-epoxycyclo Hexyl)methyl-3,4-epoxycyclohexylcarboxylate, bis-(3,4-epoxycyclohexyl)adipate, bis-(3,4-epoxycyclohexylmethylene)adipate, bis-(2,3 -Epoxycyclopentyl) ether, (2,3-epoxy-6-methylcyclohexylmethyl) adipate, dicyclopentadiene dioxide, etc. are mentioned. Among them, (3,4-epoxycyclohexyl)methyl-3,4-epoxycyclohexylcarboxylate is preferable. These alicyclic epoxy resins may be used alone or in combination of two or more.

The optical post-curable resin composition of the present invention contains a photocationic polymerization initiator.

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

As the ionic photoacid generation type photocationic polymerization initiator, for example, the cation moiety is aromatic sulfonium, aromatic iodonium, aromatic diazonium, aromatic ammonium, or (2,4-cyclopentadiene-1- One) ((1-methylethyl)benzene)-Fe cation, and the anion moiety is BF ^4- , PF ^6- , SbF ^6- , or (BX ₄ ) ^- (However, X is at least two or more fluorine or And an onium salt composed of (representing a phenyl group substituted with a trifluoromethyl group).

As the aromatic sulfonium salt, for example, bis(4-(diphenylsulfonio)phenyl)sulfidebishexafluorophosphate, bis(4-(diphenylsulfonio)phenyl)sulfidebishexafluoro Roantimonate, bis(4-(diphenylsulfonio)phenyl)sulfidebistetrafluoroborate, bis(4-(diphenylsulfonio)phenyl)sulfidetetrakis(pentafluorophenyl)borate , Diphenyl-4-(phenylthio)phenylsulfoniumhexafluorophosphate, diphenyl-4-(phenylthio)phenylsulfoniumhexafluoroantimonate, diphenyl-4-(phenylthio)phenylsulfoniumtetra Fluoroborate, diphenyl-4-(phenylthio)phenylsulfonium tetrakis(pentafluorophenyl)borate, triphenylsulfoniumhexafluorophosphate, triphenylsulfoniumhexafluoroantimonate, triphenylsulfonium Tetrafluoroborate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, bis(4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl)sulfidebishexafluoro Phosphate, bis(4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl)sulfidebishexafluoroantimonate, bis(4-(di(4-(2-hydro)) Oxyethoxy))phenylsulfonio)phenyl)sulfidebistetrafluoroborate, bis(4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl)sulfidetetrakis( Pentafluorophenyl) borate, and the like.

Examples of the aromatic iodonium salt include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluoro Phenyl) borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) ) Iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluorophosphate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluoro Roantimonate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrafluoroborate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrakis(pentafluorophenyl)borate, etc. Can be mentioned.

As the aromatic diazonium salt, for example, phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, phenyldiazonium tetrakis (pentafluorophenyl) borate And the like.

Examples of the aromatic ammonium salt include 1-benzyl-2-cyanopyridiniumhexafluorophosphate, 1-benzyl-2-cyanopyridiniumhexafluoroantimonate, and 1-benzyl-2-cyano Pyridinium tetrafluoroborate, 1-benzyl-2-cyanopyridinium tetrakis(pentafluorophenyl)borate, 1-(naphthylmethyl)-2-cyanopyridiniumhexafluorophosphate, 1-(naph) Tylmethyl)-2-cyanopyridiniumhexafluoroantimonate, 1-(naphthylmethyl)-2-cyanopyridiniumtetrafluoroborate, 1-(naphthylmethyl)-2-cyanopyridinium Tetrakis (pentafluorophenyl) borate, etc. are mentioned.

As the (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe salt, for example, (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-cyclopentadien-1-yl)((1-methylethyl) )Benzene)-Fe(II)tetrakis(pentafluorophenyl)borate, etc. are mentioned.

Examples of the nonionic photoacid-generating photocationic polymerization initiator include nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenol sulfonic acid ester, diazonaphthoquinone, N-hydroxyimide sulfonate, and the like. .

Among the above photocationic polymerization initiators, commercially available ones include, for example, DTS-200 (manufactured by Midori Chemical), UVI6990, UVI6974 (all manufactured by Union Carbide), SP-150, SP-170 (all manufactured by ADEKA). , FC-508, FC-512 (all manufactured by 3M), Irgacure 261 (manufactured by BASF Japan), PI2074 (manufactured by Rhodia), and the like.

As for the content of the photocationic polymerization initiator, the preferred lower limit is 0.1 parts by weight and the preferred upper limit is 10 parts by weight based on 100 parts by weight of the cationic curable resin. If the content of the photocationic polymerization initiator is less than 0.1 part by weight, the cation polymerization may not sufficiently proceed or the curing reaction may be too slow. If the content of the photocationic polymerization initiator exceeds 10 parts by weight, the curing reaction of the photo-post-curable resin composition to be obtained becomes too fast, workability decreases, or the cured product of the photo-post-curable resin composition to be obtained may become uneven. have. A more preferable lower limit of the content of the photocationic polymerization initiator is 0.5 parts by weight, and a more preferable upper limit is 5 parts by weight.

The light post-curable resin composition of the present invention may contain a sensitizer. The sensitizer has a role of further improving the polymerization initiation efficiency of the cation polymerization initiator and further accelerating the curing reaction of the light post-curable resin composition of the present invention.

Examples of the sensitizer include thioxanthone compounds such as 2,4-diethyl thioxanthone, 2,2-dimethoxy-1,2-diphenylethan-1-one, benzophenone, and 2 ,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4'-bis(dimethylamino)benzophenone, 4-benzoyl-4'methyldiphenyl sulfide, and the like.

The content of the sensitizer is, with respect to 100 parts by weight of the cation-curable resin, a preferable lower limit is 0.05 parts by weight, and a preferable upper limit is 3 parts by weight. When the content of the sensitizer is less than 0.05 parts by weight, the sensitizing effect may not be sufficiently obtained. When the content of the sensitizer exceeds 3 parts by weight, absorption may become too large and light may not be transmitted to the deep part. A more preferable lower limit of the content of the sensitizer is 0.1 parts by weight, and a more preferable upper limit is 1 part by weight.

The light post-curable resin composition of the present invention may contain a silane coupling agent. The silane coupling agent has a role of improving the adhesion between the light post-curable resin composition of the present invention and a substrate.

Examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-isocyanate propyltrimethoxysilane. Can be mentioned. These silane coupling agents may be used alone or in combination of two or more.

As for the content of the silane coupling agent, a preferable lower limit is 0.1 parts by weight and a preferable upper limit is 10 parts by weight based on 100 parts by weight of the cation-curable resin. When the content of the silane coupling agent is less than 0.1 part by weight, the effect of improving the adhesiveness of the obtained photo-post-curable resin composition may not be sufficiently exhibited. When the content of the silane coupling agent exceeds 10 parts by weight, excess silane coupling agent may bleed out. A more preferable lower limit of the content of the silane coupling agent is 0.5 parts by weight, and a more preferable upper limit is 5 parts by weight.

The light post-curable resin composition of the present invention may further contain a thermosetting agent within a range that does not impair the object of the present invention. By containing the said thermosetting agent, thermosetting can be imparted to the photo-post-curable resin composition of this invention.

The thermosetting agent is not particularly limited, and examples thereof include hydrazide compounds, imidazole derivatives, acid anhydrides, dicyandiamides, guanidine derivatives, modified aliphatic polyamines, addition products of various amines and epoxy resins.

Examples of the hydrazide compound include 1,3-bis (hydrazinocarbonoethyl-5-isopropylhydantoin) and the like.

Examples of the imidazole derivatives include 1-cyanoethyl-2-phenylimidazole, N-(2-(2-methyl-1-imidazolyl)ethyl)urea, 2,4-diamino -6-(2'-methylimidazolyl-(1'))-ethyl-s-triazine, N,N'-bis(2-methyl-1-imidazolylethyl)urea, N,N'- (2-methyl-1-imidazolylethyl)-adipoamide, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, etc. Can be mentioned.

Examples of the acid anhydride include tetrahydrophthalic anhydride and ethylene glycol-bis (anhydrotrimelitate).

These thermosetting agents may be used alone or in combination of two or more.

The content of the thermosetting agent is preferably 0.5 parts by weight, and the upper limit is 30 parts by weight, based on 100 parts by weight of the cation curable resin. When the content of the thermosetting agent is less than 0.5 parts by weight, sufficient thermosetting properties may not be imparted to the obtained photo-post-curable resin composition. When the content of the thermosetting agent exceeds 30 parts by weight, the storage stability of the obtained photo-post-curable resin composition may be insufficient, or the moisture resistance of the cured product of the obtained photo-post-curable resin composition may deteriorate. A more preferable lower limit of the content of the thermosetting agent is 1 part by weight, and a more preferable upper limit is 15 parts by weight.

The light post-curable resin composition of the present invention may contain a surface modifier within a range that does not impair the object of the present invention. By containing the surface modifier, it is possible to impart flatness of the coating film to the photo-post-curable resin composition of the present invention.

Examples of the surface modifier include surfactants and leveling agents.

Examples of the surfactant and leveling agent include silicone-based, acrylic-based, and fluorine-based surfactants.

Among the surfactants and leveling agents that are commercially available, for example, BYK-345 (manufactured by BIC Chemie Japan), BYK-340 (manufactured by BIC Chemie Japan), and Suflon S-611 (AGC Corporation) Already manufactured by Chemical Co.), etc. are mentioned.

The photo-post-curable resin composition of the present invention may contain a compound that reacts with an acid generated in the photo-post-curable resin composition or an ion exchange resin in order to improve the durability of the device electrode within a range that does not impair the transparency of the cured product.

Examples of the compound reacting with the generated acid include a substance neutralized with an acid, for example, an alkali metal carbonate or hydrogen carbonate, or an alkaline earth metal carbonate or hydrogen carbonate. Specifically, for example, calcium carbonate, calcium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, and the like are used.

As the ion exchange resin, any of a cation exchange type, an anion exchange type, and a zwitterion exchange type can be used. In particular, a cation exchange type or a zwitterion exchange type capable of adsorbing chloride ions is preferable.

Further, the light post-curable resin composition of the present invention may contain various known additives such as a reinforcing agent, a softening agent, a plasticizer, a viscosity modifier, an ultraviolet absorber, and an antioxidant, as necessary.

As a method for producing the light post-curable resin composition of the present invention, for example, a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a mixer such as three rolls are used, and a cationic curable resin And a method of mixing an additive such as a photocationic polymerization initiator, a compound having an amino group and a cationically polymerizable functional group, and a silane coupling agent added as needed.

ADVANTAGE OF THE INVENTION According to this invention, generation|occurrence|production of outgas can be suppressed and the light post-curable resin composition excellent in transparency and reliability can be provided.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited only to these examples.

(Example 1)

As a cation-curable resin, 50 parts by weight of bisphenol F type epoxy resin (manufactured by DIC, 「EPICLON EXA-830LVP」) 50 parts by weight, hydrogenated bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, 「jER YL8034」) 25 parts by weight, and hydrogen 25 parts by weight of an added bisphenol F-type epoxy resin (manufactured by Mitsubishi Chemical Corporation, 「jER YL6753」), 1.0 parts by weight of an aromatic sulfonium salt (manufactured by Midori Chemical Co., Ltd., 「DTS-200」) as a photocationic polymerization initiator, and a tertiary amino group And triglycidyl isocyanurate (manufactured by Nissan Chemical Co., Ltd., ``TEPIC'') 5 parts by weight as a compound having a cation polymerizable functional group, and 2,4-diethylthioxanthone (manufactured by Nippon Explosives Co., Ltd., `` DETX-S") 0.01 parts by weight and 1 part by weight of γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone, "KBM-403") as a silane coupling agent, and a fluorine-based leveling agent (AGC Seimi Chemical) Manufacturing, "Suplon S-611") 1 part by weight of mixing and heating to 80 °C, then using a homodisper type stirring mixer (Primix Co., "Homodisper L type") at a stirring speed of 3000 rpm The mixture was uniformly stirred and mixed to prepare a light post-curable resin composition.

(Examples 2 to 6, Comparative Examples 1 to 3)

Each material described in Table 1 was stirred and mixed in the same manner as in Example 1 according to the blending ratio shown in Table 1 to prepare a light post-curable resin composition.

<Evaluation>

The following evaluation was performed about each light post-curable resin composition obtained in Examples and Comparative Examples. Table 1 shows the results.

(1) viscosity

For each light post-curable resin composition obtained in Examples and Comparative Examples, the viscosity under the conditions of 25°C and 100 rpm was measured using an E-type viscometer (manufactured by Toki Industries, "VISCOMETER TV-22").

(2) curing retardation

The test piece of each light post-curable resin composition obtained in Examples and Comparative Examples was irradiated with an ultraviolet ray of 1500 mJ/cm 2 using an ultraviolet irradiation device (manufactured by Oak Co., Ltd., "JL-4300-3S"). After 10 minutes, the curability was confirmed, and further after that, heating was performed in an oven at 100° C. for 15 minutes to confirm curability. As a result, in the case of uncured after 10 minutes of UV irradiation and cured after heating at 100°C, it is thickened after 10 minutes of UV irradiation and cured after heating at 100°C. When cured within or after heating at 100° C., the curing delay was evaluated as "x".

(3) Transparency of the cured product

Each light post-curable resin composition obtained in Examples and Comparative Examples was formed to a thickness of 10 µm between two glass plates of 75 mm × 25 mm × 1 mm, respectively, and ultraviolet rays having a wavelength of 365 nm were used in a vacuum environment using a high-pressure mercury lamp. Was cured by irradiating so that the irradiation amount was 3000 mJ/cm 2 to obtain a cured product. About the obtained hardened|cured material, the total light transmittance was measured using a spectrophotometer (manufactured by Hitachi High Technologies, "U-2900"). As a result, the transparency of the cured product was evaluated by setting the transmittance of 95 or more as "○", the case of 90 or more and less than 95 as "△", and the case of less than 90 as "x".

(4) Outgassing prevention

After weighing and sealing 300 mg of each light post-curable resin composition obtained in Examples and Comparative Examples in a vial bottle, ultraviolet rays were irradiated at 1500 mJ/cm 2 using an ultraviolet irradiation device (manufactured by Oak Co., Ltd., "JL-4300-3S"). After irradiation, the resin was cured by heating at 100°C for 15 minutes. Further, this vial bottle was heated in a constant temperature oven at 85°C for 100 hours, and the vaporized component in the vial bottle was measured using a gas chromatograph mass spectrometer (manufactured by Nippon Electronics Co., Ltd., "JMS-k9").

Outgassing prevention by using ``◎'' when the amount of the vaporized component is less than 10 ppm, ``○'' when the amount is 10 ppm or more and less than 50 ppm, ``△'' when the amount is less than 50 ppm or more and less than 100 ppm, and ``x'' when it is 100 ppm or more Was evaluated.

(5) Reliability of organic EL display devices

(Manufacture of a substrate on which a laminate having an organic light emitting material layer is disposed)

A film formed by forming an ITO electrode to a thickness of 1000 angstroms on a glass substrate (25 mm in length, 25 mm in width, and 0.7 mm in thickness) was used as a substrate. The substrate was ultrasonically cleaned for 15 minutes each with acetone, aqueous alkali solution, ion-exchanged water, and isopropyl alcohol, followed by cleaning with boiled isopropyl alcohol for 10 minutes, and a UV-ozone cleaner (manufactured by Nippon Laser Electronics Co., Ltd.) , "NL-UV253") was performed immediately before treatment.

Next, this substrate was fixed to the substrate folder of a vacuum evaporation apparatus, and 200 mg of N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine (α-NPD) was added in an unglazed crucible, 200 mg of tris(8-hydroxyquinolinato)aluminum (Alq ₃ ) was put in another different unglazed crucible, and the vacuum chamber was decompressed ^{to 1 × 10 -4 Pa.} Thereafter, the crucible containing α-NPD was heated, and α-NPD was deposited on the substrate at a deposition rate of 15 Å/s to form a hole transport layer having a thickness of 600 Å. Subsequently, _{a crucible containing Alq 3} was heated, and an organic light emitting material layer having a thickness of 600 Å was formed at a deposition rate of 15 Å/s. Thereafter, the substrate on which the hole transport layer and the organic light emitting material layer were formed was transferred to another vacuum evaporation apparatus, 200 mg of lithium fluoride was placed in a resistance heating boat made of tungsten in the vacuum evaporation apparatus, and 1.0 g of an aluminum wire was placed in another boat made of tungsten. Thereafter, the inside of the vapor deposition apparatus of the vacuum evaporation apparatus ^{was reduced to 2 × 10 -4} Pa, lithium fluoride was formed into a 5 Å film at a deposition rate of 0.2 Å/s, and then aluminum was formed into a 1000 Å film at a rate of 20 Å/s. The inside of the vapor deposition apparatus was returned to normal pressure with nitrogen, and a substrate on which a laminate having a 10 mm x 10 mm organic light-emitting material layer was disposed was taken out.

(Coating with inorganic material film A)

A mask having an opening of 13 mm x 13 mm was provided so as to cover the entire laminate of the substrate on which the obtained laminate was disposed, and an inorganic material film A was formed by the plasma CVD method.

In the plasma CVD method, SiH ₄ gas and nitrogen gas are used as source gases, each flow rate is 10 sccm and 200 sccm, RF power is 10 W (frequency 2.45 GHz), the temperature in the chamber is 100° C., It carried out under the condition of making the pressure 0.9 Torr.

The thickness of the formed inorganic material film A was about 1 µm.

(Formation of resin protective film)

A substrate on which a laminate coated with an inorganic material film A was disposed was installed in a vacuum apparatus, 0.5 g of each light post-curable resin composition obtained in Examples and Comparative Examples was put in a heating boat installed in the vacuum apparatus, and the pressure was reduced to 10 Pa, The light post-curable resin composition was heated at 200°C to a rectangular portion of 11 mm×11 mm including the laminate, and vacuum vapor deposition was performed so that the thickness became 0.5 μm. Thereafter, in a vacuum environment, ultraviolet rays having a wavelength of 365 nm were irradiated with a high-pressure mercury lamp so that the irradiation amount was 3000 mJ/cm 2, and the light post-curable resin composition was cured to form a resin protective film.

(Coating with inorganic material film B)

After the resin protective film was formed, a mask having an opening of 12 mm x 12 mm was provided so as to cover the entire resin protective film, and an inorganic material film B was formed by plasma CVD to obtain an organic EL display device.

In the plasma CVD method, SiH ₄ gas and nitrogen gas are used as source gases, the respective flow rates are SiH ₄ gas 10 sccm and nitrogen gas 200 sccm, RF power 10 W (frequency 2.45 GHz), and the temperature in the chamber. It carried out under the conditions of 100 degreeC and the pressure in the chamber being 0.9 Torr.

The thickness of the formed inorganic material film B was about 1 µm.

(Observation of light emission state of organic EL display device)

After exposing the obtained organic EL display device in an environment of 85°C and 85% humidity for 100 hours, a voltage of 3 V was applied to visually observe the light emission state of the organic EL display device (the presence or absence of dark spots and extinction around pixels). Observed. Reliability of the organic EL display device was evaluated by using "○" for uniform light emission without dark spots or ambient quenching, and "x" for slight dark spots or peripheral quenching.

Industrial applicability

ADVANTAGE OF THE INVENTION According to this invention, generation|occurrence|production of outgas can be suppressed and the light post-curable resin composition excellent in transparency and reliability can be provided.

Claims (7)

It contains a cation curable resin, a photocationic polymerization initiator, and a compound having an amino group and a cationically polymerizable functional group,
A light post-curable resin composition, wherein the content of the compound having an amino group and a cation-polymerizable functional group is 0.01 to 20 parts by weight based on 100 parts by weight of the cation curable resin. The method of claim 1,
A light post-curable resin composition, wherein the amino group is a tertiary amino group. The method according to claim 1 or 2,
A light post-curable resin composition, wherein the compound having an amino group and a cation-polymerizable functional group has two or more cation-polymerizable functional groups in one molecule. The method according to claim 1 or 2,
A light post-curable resin composition, wherein the compound having an amino group and a cation-polymerizable functional group has a weight average molecular weight of 200 to 1000. The method according to claim 1 or 2,
The cation-curable resin contains an epoxy resin, and a light post-curable resin composition. The method of claim 5,
A light post-curable resin composition comprising an alicyclic epoxy resin as the epoxy resin. delete