WO2012141299A1 - Curable composition - Google Patents

Curable composition Download PDF

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Publication number
WO2012141299A1
WO2012141299A1 PCT/JP2012/060155 JP2012060155W WO2012141299A1 WO 2012141299 A1 WO2012141299 A1 WO 2012141299A1 JP 2012060155 W JP2012060155 W JP 2012060155W WO 2012141299 A1 WO2012141299 A1 WO 2012141299A1
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Prior art keywords
meth
acrylate
component
curable composition
mass
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PCT/JP2012/060155
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French (fr)
Japanese (ja)
Inventor
淳一郎 武間
慶次 後藤
公彦 依田
Original Assignee
電気化学工業株式会社
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Application filed by 電気化学工業株式会社 filed Critical 電気化学工業株式会社
Priority to JP2013509983A priority Critical patent/JP6106080B2/en
Priority to CN2012800181985A priority patent/CN103459445A/en
Publication of WO2012141299A1 publication Critical patent/WO2012141299A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • C08F290/048—Polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J119/00—Adhesives based on rubbers, not provided for in groups C09J107/00 - C09J117/00
    • C09J119/006—Rubber characterised by functional groups, e.g. telechelic diene polymers

Definitions

  • the present invention relates to a curable composition, an adhesive using the same, and a cured product.
  • optical pickup devices used for reproducing and recording optical recording media such as Blu-ray discs and HD-DVDs that support CDs, DVDs, and blue semiconductor lasers, displays such as liquid crystals and organic electroluminescence, CCDs, CMOSs, etc.
  • electronics field including device packages used in image sensors and semiconductor components, etc., as electronic components become more sophisticated, glass-to-glass, glass-to-metal, glass-to-ceramic, glass-to-plastic, plastic-to-plastic, plastic-to-metal, There are an increasing number of cases in which materials having different light transmission properties are bonded as adherends, such as plastics, ceramics, and metals. And the adhesive agent which fixes with high precision between such materials is calculated
  • the protruding part in bonding between materials that do not transmit light, the protruding part can be cured with light, but the part that does not reach light needs to be cured with something other than light.
  • adhesives to be combined is desired.
  • curable resin compositions having both photocurability and thermosetting properties have been proposed.
  • Patent Document 1 describes a curable resin composition containing a photosensitive resin obtained by reacting a reaction product of a novolak-type epoxy compound and an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride. ing.
  • Patent Document 2 discloses a one-component curability containing a photopolymerization initiator that generates radicals by absorbing light having a wavelength of 380 to 1500 nm and a thermal polymerization initiator having a 10-hour half-life temperature of 50 to 120 ° C. A resin composition is described.
  • Patent Document 3 describes a curable resin composition having a vinyl polymer having a (meth) acryloyl group at a molecular end, a photo radical initiator, and a thermal radical initiator.
  • Patent Documents 4 to 8 describe curable compositions containing (meth) acrylate.
  • the curable resin composition tends to thicken or gel with time and lacks storage stability. Therefore, the main component mainly composed of a photosensitive resin and a thermosetting component are included. It is commercially available as a two-component type with a main curing agent, and these main agents and curing agents are mixed and used at the time of use. This curable resin composition has a problem that it takes time to handle.
  • the curable resin composition described in Patent Document 2 solves the problems described in Patent Document 1, but in addition to workability, the thermal polymerization initiator has a low half-life temperature (decomposition temperature). Specifically, since a thermal polymerization initiator having a half-life temperature of 50 ° C. is used, there is a problem that adhesion is small while it is excellent in low-temperature curability.
  • Patent Document 3 a curable resin composition having excellent curability, oil resistance, heat resistance, and weather resistance has been studied, but the adhesion to satisfy further requirements has been even studied. There wasn't.
  • the present invention has been made in order to solve the problems of the above-described conventional technology.
  • the main purpose is to provide a curable composition having excellent adhesion as an adhesive, and an adhesive and a cured product using the same.
  • the present inventor has (A) one or more (meth) acryloyl groups at the terminal or side chain of the molecule, polybutadiene, polyisoprene, and these (Meth) acryl-modified oligomer, (B) carboxyl group-containing (meth) acrylate, (C) thermal radical polymerization initiator, (D) photoradical polymerization initiator, which is one or more selected from the group consisting of (E) It discovered that the curable composition containing antioxidant could achieve the said objective, and came to this invention.
  • the present invention is as follows. (1) (A) One or more kinds selected from the group consisting of polybutadiene, polyisoprene, and hydrogenated products thereof having one or more (meth) acryloyl groups at the terminal or side chain of the molecule ( (Meth) acrylic modified oligomer, component (A), and optionally contained (F) polyfunctional (meth) acrylate, optionally contained (G) monofunctional (saturated alicyclic hydrocarbon group) ) Acrylate and (H) hydroxyl group-containing (meth) acrylate in total of 100 parts by mass, (B) carboxyl group-containing (meth) acrylate 1 to 10 parts by mass, (C) thermal radical polymerization initiation A curable composition containing 0.01 to 3.5 parts by weight of an agent, (D) 0.01 to 15 parts by weight of a radical photopolymerization initiator, and (E) 0.01 to 5 parts by weight of an antioxidant.
  • the component (G) is at least one selected from the group consisting of isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and 2-methyl-2-adamantyl (meth) acrylate (8)
  • the curable composition according to 1. 10
  • the curable composition of the present invention can be cured by energy rays or heat.
  • the curable composition of the present invention is characterized by high adhesion.
  • the component (A) of the present invention has at least one (meth) acryloyl group at the end or side chain of the molecule, and is one or more selected from the group consisting of polybutadiene, polyisoprene, and hydrogenated products thereof. This is a (meth) acryl-modified oligomer.
  • the main chain skeleton of the (meth) acryl-modified oligomer of the component (A) is preferably at least one selected from the group consisting of polybutadiene, polyisoprene, a hydrogenated polybutadiene, and a hydrogenated polyisoprene.
  • One or more members selected from the group consisting of hydrogenated polybutadienes are more preferred, and polybutadiene is most preferred.
  • the (meth) acrylic modified oligomer of component (A) has at least one (meth) acryloyl group at the end or side chain of the main chain skeleton.
  • those having (meth) acryloyl groups at both ends of the main chain skeleton are preferable.
  • the molecular weight of the component (A) (meth) acryl-modified oligomer is preferably 500 to 50,000, more preferably 800 to 38,000.
  • a molecular weight here, the number average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC) is used preferably.
  • GPC gel permeation chromatography
  • the molecular weight is 500 or more, the hardness of the cured product obtained by irradiating the curable composition of the present invention with energy rays increases, and the adhesive layer is easily formed.
  • the molecular weight is 50,000 or less, the viscosity of the resulting resin composition becomes low, and the workability in mixing during the production process and the workability when using the curable composition in practical applications are improved.
  • (A) Component (meth) acrylic modified oligomers include Nippon Soda Co., Ltd. NISSO-PB TEAI-1000 (Both-end acrylate-modified hydrogenated butadiene oligomer), Nippon Soda Co., Ltd. NISSO-PB TE-2000 (Both-end methacrylate) Modified butadiene oligomer).
  • (B) component is a carboxyl group-containing (meth) acrylate.
  • the carboxyl group-containing (meth) acrylate refers to a monofunctional (meth) acrylate monomer having at least one carboxyl group in the molecule.
  • carboxyl group-containing (meth) acrylates examples include 2- (meth) acryloyloxyethyl succinic acid monoester, 2- (meth) acryloyloxyethyl phthalic acid monoester, 2- (meth) acryloyloxyethyl hexahydrophthalic acid monoester 2- (meth) acryloyloxyethyl dicarboxylic acid monoester such as ⁇ -carboxy-polycaprolactone mono (meth) acrylate and other polycaprolactone modified (meth) acrylic acid ester, (meth) acrylic acid dimer, (meth) acrylic acid Trimers and (meth) acrylic acid tetramers. These can be used alone or in combination of two or more. As the carboxyl group-containing (meth) acrylate, it is preferable to remove (meth) acrylic acid.
  • 2- (meth) acryloyloxyethyl dicarboxylic acid monoester is preferable, and the group consisting of 2- (meth) acryloyloxyethyl succinic acid monoester and 2- (meth) acryloyloxyethyl hexahydrophthalic acid monoester One or more of these are more preferred.
  • Examples of 2- (meth) acryloyloxyethyl succinic acid monoester include 2-methacryloyloxyethyl succinic acid.
  • Examples of 2- (meth) acryloyloxyethyl hexahydrophthalic acid monoester include 2-methacryloyloxyethyl hexahydrophthalic acid.
  • (C) component is a thermal radical polymerization initiator.
  • the thermal radical polymerization initiator an organic peroxide is preferable.
  • the one-hour half-life temperature of the thermal radical polymerization initiator is preferably 127 ° C. or less, more preferably 104 to 127 ° C., and most preferably 106 to 127 ° C.
  • the one-hour half-life temperature is preferably 127 ° C. or less, more preferably 104 to 127 ° C., and most preferably 106 to 127 ° C.
  • 1 hour half-life temperature is measured by the following method.
  • the thermal radical polymerization initiator whose half-life temperature is to be measured is dissolved in a predetermined solvent and adjusted to a predetermined concentration.
  • the obtained solution is sealed in a container, and the thermal radical polymerization initiator is thermally decomposed while maintaining the solution at a predetermined temperature.
  • the one-hour half-life temperature is determined by measuring the relationship between the time at this time and the concentration change of the thermal radical polymerization initiator.
  • Equation (1) a K d value is obtained from Equation (1), and this is substituted into Equation (2) to obtain a half-life temperature.
  • Formula (1): ln (Co / Ct) K d t (In the formula, Co: initial concentration of thermal radical polymerization initiator, Ct: thermal radical polymerization initiator concentration in t-time thermal decomposition term, K d : thermal decomposition rate constant, t: time)
  • Formula (2): t 1/2 ln 2 / K d ( Where t 1/2 is the half-life)
  • the 1-hour half-life temperature is determined by calculating the temperature at which the obtained half-life is 1 hour.
  • the maximum storage temperature of the thermal radical polymerization initiator is preferably 26 to 40 ° C, more preferably 30 to 40 ° C, and most preferably 30 to 38 ° C.
  • the maximum storage temperature is preferably 26 to 40 ° C, more preferably 30 to 40 ° C, and most preferably 30 to 38 ° C.
  • the maximum storage temperature was measured by the following method.
  • the thermal radical polymerization initiator is preferably an organic peroxide that is liquid at 25 ° C. Since it is liquid at 25 ° C., it is not necessary to perform a heating step during production, and self-polymerization due to temperature rise is prevented.
  • Organic peroxides that are liquid at 1 hour half-life temperature of 127 ° C. or less, maximum storage temperature of 26 to 40 ° C., and 25 ° C. include t-butyl peroxyacetate (1 hour half-life temperature of 120 to 123 ° C., Maximum storage temperature 30-38 ° C, liquid at 25 ° C), t-butylperoxy 3,5,5-trimethylhexanoate (1 hour half-life temperature 119 ° C, maximum storage temperature 35 ° C, liquid at 25 ° C) ), T-butyl peroxybenzoate (1 hour half-life temperature 125 ° C., maximum storage temperature 30-38 ° C., liquid at 25 ° C.), t-butyl peroxyisopropyl carbonate (1 hour half-life temperature 116-118 ° C., Maximum storage temperature 30 to 38 ° C, liquid at 25 ° C), t-butylperoxy 2-ethylhexyl carbonate (1 hour half-life temperature 117 ° C, maximum
  • t-butyl peroxy 2-ethylhexyl carbonate, t-amyl peroxy 2-ethylhexyl carbonate, t-butyl peroxy 3,5,5-trimethylhexanoate, t-amyl peroxy 3,5,5 One or more members selected from the group consisting of 5-trimethylhexanoate are preferable, and one or more members selected from the group consisting of t-butylperoxy 2-ethylhexyl carbonate and t-amylperoxy 2-ethylhexyl carbonate are more preferable.
  • thermal radical polymerization initiator examples include di (2-ethylhexyl) peroxydicarbonate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and the like.
  • (D) component is a radical photopolymerization initiator.
  • the radical photopolymerization initiator include an ultraviolet polymerization initiator and a visible light polymerization initiator, both of which are used without limitation.
  • the ultraviolet polymerization initiator include benzoin, benzophenone, and acetophenone.
  • visible light polymerization initiators include acylphosphine oxides, thioxanthones, and quinones.
  • photo radical polymerization initiators examples include benzophenone, 4-phenylbenzophenone, benzoylbenzoic acid, 2,2-diethoxyacetophenone, bisdiethylaminobenzophenone, benzyl, benzoin, benzoylisopropyl ether, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, Thioxanthone, 1- (4-Isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy-2-methyl-1-propane- 1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, camphorquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) Phenylphosphine oxide, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan
  • one or more members selected from the group consisting of 1-hydroxycyclohexyl phenyl ketone and benzyl dimethyl ketal are preferable.
  • Component is an antioxidant.
  • the antioxidant include a phenol type and a hydroquinone type. Among these, a phenol type is preferable.
  • Antioxidants include ⁇ -naphthoquinone, 2-methoxy-1,4-naphthoquinone, methylhydroquinone, hydroquinone, 2,2-methylene-bis (4-methyl-6-tertiarybutylphenol), catechol, hydroquinone monomethyl ether, mono Tertiary butyl hydroquinone, 2,5-ditertiary butyl hydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-ditertiary butyl-p-benzoquinone, picric acid, citric acid, phenothiazine, tertiary Examples thereof include butyl catechol, 2-butyl-4-hydroxyanisole, and 2,6-ditertiary butyl-p-cresol.
  • Phenols include 2,2-methylene-bis (4-methyl-6-tertiary butylphenol), catechol, picric acid, tertiary butyl catechol, 2-butyl-4-hydroxyanisole and 2,6-ditertiary butyl. -P-cresol and the like.
  • the curable composition of the present invention contains the components (A) to (E) as essential components.
  • the composition containing the components (A) to (E) has an effect that the light-shielding area can be cured by heat in addition to being cured by irradiation with energy rays, and has high adhesiveness. .
  • the curable composition of the present invention can contain polyfunctional (meth) acrylate as the component (F) in terms of improving heat resistance.
  • the polyfunctional (meth) acrylate refers to a compound having two or more (meth) acryloyl groups in the molecule.
  • polyfunctional (meth) acrylates polyfunctional methacrylate is preferable.
  • polyfunctional (meth) acrylate examples include polyfunctional (meth) acrylate having an alicyclic structure such as dimethylol-tricyclodecane di (meth) acrylate, dimethylol-cyclohexanedi (meth) acrylate, and ethylene oxide-added bisphenol A di (meth) )
  • Polyfunctional (meth) acrylate having an aromatic ring structure such as acrylate, ethylene oxide-added bisphenol F di (meth) acrylate, propylene oxide-added bisphenol A di (meth) acrylate, propylene oxide-added bisphenol F di (meth) acrylate, tri
  • polyfunctional (meth) acrylates having an aliphatic branched structure such as methylolpropane tri (meth) acrylate. These can be used alone or in combination of two or more.
  • polyfunctional (meth) acrylates having an alicyclic structure polyfunctional (meth) acrylates having an alicyclic structure having 6 to 12 carbon atoms are preferable.
  • polyfunctional (meth) acrylates having an alicyclic structure having 6 to 12 carbon atoms dimethylol-tricyclodecane di (meth) acrylate is preferable.
  • polyfunctional (meth) acrylates having an aliphatic branched structure trimethylolpropane tri (meth) acrylate is preferred.
  • At least one of the group consisting of a polyfunctional (meth) acrylate having an alicyclic structure and a polyfunctional (meth) acrylate having an aliphatic branched structure is preferable, and a polyfunctional having an alicyclic structure is preferable.
  • (Meth) acrylate is more preferred.
  • the curable composition of the present invention can contain a monofunctional (meth) acrylate having a saturated alicyclic hydrocarbon group as the component (G) in terms of improving heat resistance.
  • the monofunctional (meth) acrylate having a saturated alicyclic hydrocarbon group is a monofunctional (meth) acrylate having a saturated alicyclic hydrocarbon group via an ester bond.
  • monofunctional (meth) acrylates having a saturated alicyclic hydrocarbon group having 9 to 12 carbon atoms are preferable.
  • the saturated alicyclic hydrocarbon group having 9 to 12 carbon atoms include dicyclopentanyl group, isobornyl group, adamantyl group and the like. In these, 1 or more types in the group which consists of a dicyclopentanyl group and an isobornyl group are preferable, and an isobornyl group is more preferable.
  • methacrylate is preferable.
  • Examples of the monofunctional (meth) acrylate having a saturated alicyclic hydrocarbon group having 9 to 12 carbon atoms include 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, isobornyl ( And (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and the like. These can be used alone or in combination of two or more.
  • At least one member selected from the group consisting of isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and 2-methyl-2-adamantyl (meth) acrylate is preferable, and isobornyl (meth) acrylate is more preferable. preferable.
  • the curable composition of the present invention can contain a hydroxyl group-containing (meth) acrylate as the component (H) in terms of improving the adhesion to the glass surface.
  • the hydroxyl group-containing (meth) acrylate refers to a monofunctional (meth) acrylate having at least one hydroxyl group in the molecule.
  • monofunctional methacrylate is preferable.
  • hydroxyl group-containing (meth) acrylate examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2 -(Meth) acryloyloxyethyl-2-hydroxypropyl phthalate, glycerol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, 4-hydroxycyclohexyl (meth) Examples thereof include acrylate and 1,4-butanediol mono (meth) acrylate. These can be used alone or in combination of two or more.
  • one or more members selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate are preferable, and 2-hydroxyethyl (meth) Acrylate is more preferred.
  • the curable composition of the present invention can contain a silane coupling agent as component (I) in terms of improving the adhesion to the glass surface.
  • Silane coupling agents include ⁇ -chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris ( ⁇ -methoxyethoxy) silane, ⁇ - (meth) acryloxypropyltrimethoxy.
  • Silane ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, N- ⁇ - (aminoethyl) ) - ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, and ⁇ -ureidopropyltriethoxysilane. These can be used alone or in combination of two or more.
  • ⁇ - (meth) acryloxypropyltrimethoxysilane is preferred.
  • the amount of the curable composition of the present invention used is as follows.
  • (A) component Content of (A) component is (A) component, (F) component contained as needed, (G) component contained as needed, (H) component contained as needed 100 mass in total.
  • 10 parts by mass or more are preferable, 10 to 90 parts by mass are more preferable, and 30 to 70 parts by mass are most preferable.
  • Content of (F) component is 100 mass in total of (A) component, (F) component contained as needed, (G) component contained as needed, and (H) component contained as needed.
  • the amount is preferably 50 parts by mass or less, more preferably 5 to 50 parts by mass, and most preferably 10 to 25 parts by mass.
  • Content of (G) component is 100 mass in total of (A) component, (F) component contained as needed, (G) component contained as needed, and (H) component contained as needed. In part, 50 parts by mass or less is preferable, 5 to 50 parts by mass is more preferable, and 10 to 35 parts by mass is most preferable.
  • Content of (H) component is 100 mass in total of (A) component, (F) component contained as needed, (G) component contained as needed, and (H) component contained as needed.
  • the amount is preferably 40 parts by mass or less, more preferably 3 to 40 parts by mass, most preferably 5 to 20 parts by mass, and still more preferably 10 to 20 parts by mass.
  • the amount of component (B) used is a total of 100 masses of component (A), component (F) contained if necessary, component (G) contained if necessary, and component (H) contained if necessary.
  • the amount is preferably 1 to 10 parts by mass and more preferably 2 to 4 parts by mass with respect to parts.
  • the amount of component (C) used is a total of 100 masses of component (A), component (F) contained if necessary, component (G) contained if necessary, and component (H) contained if necessary.
  • the amount is preferably 0.01 to 3.5 parts by weight, more preferably 0.1 to 1.5 parts by weight with respect to parts.
  • the amount of component (D) used is a total of 100 masses of component (A), component (F) contained if necessary, component (G) contained if necessary, and component (H) contained if necessary.
  • the amount is preferably 0.01 to 15 parts by weight, more preferably 0.5 to 10 parts by weight with respect to parts.
  • the amount of component (E) used is a total of 100 masses of component (A), component (F) contained if necessary, component (G) contained if necessary, and component (H) contained if necessary.
  • the amount is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass with respect to parts.
  • the usage-amount of (I) component is (A) component, (F) component contained as needed, (G) component contained as needed, as needed 1 to 10 parts by mass is preferable and 3 to 8 parts by mass is more preferable with respect to 100 parts by mass in total of the component (H) to be contained.
  • the curable composition of the present invention includes various commonly used elastomers such as acrylic rubber and urethane rubber, methyl methacrylate-butadiene-styrene graft copolymer, and acrylonitrile-butadiene as long as the object of the present invention is not impaired.
  • elastomers such as acrylic rubber and urethane rubber, methyl methacrylate-butadiene-styrene graft copolymer, and acrylonitrile-butadiene as long as the object of the present invention is not impaired.
  • -Graft copolymers such as styrene-based graft copolymers, solvents, extenders, reinforcing materials, plasticizers, thickeners, dyes, pigments, flame retardants, surfactants and fillers can be used.
  • the curable composition of the present invention may be cured by heat in addition to being cured by irradiating with energy rays to form a cured product.
  • the curable composition of the present invention can be suitably used as an adhesive.
  • This adhesive is an optical pickup device used for reproducing and recording optical recording media such as CD, DVD, blue semiconductor laser, Blu-ray disc, HD-DVD, etc., display components such as liquid crystal and organic electroluminescence, CCD It can be suitably used for electronic parts such as electronic components such as image sensors such as CMOS, semiconductor packages, etc., and bonding with solar cell module members.
  • the curable composition of the present invention is also a suitable adhesive for optical elements used for craft glass pedestals, plate fixing applications, lenses, prisms, cameras, binoculars, microscopes, and the like.
  • the curable composition may be cured by irradiation with energy rays using the following light source.
  • the light source used for curing and bonding the curable composition includes a halogen lamp, a metal halide lamp, a high-power metal halide lamp (containing indium, etc.), a low-pressure mercury lamp, a high-pressure mercury lamp, and an ultra-high pressure.
  • LED light emitting diode
  • the light source is appropriately selected depending on the reaction wavelength of the photo-radical polymerization initiator because the radiation wavelength and energy distribution are different. Natural light (sunlight) can also be a reaction initiation light source. You may perform direct irradiation, condensing irradiation by a reflective mirror, condensing irradiation by a fiber, etc. with the said light source. A low wavelength cut filter, a heat ray cut filter, a cold mirror, or the like can also be used.
  • A-1) Both-end methacrylate modified butadiene oligomer (“TE-2000” manufactured by Nippon Soda Co., Ltd., terminal acrylic-modified polybutadiene) (number average molecular weight 2100 in terms of polystyrene by GPC)
  • A-2) Both-end acrylate-modified hydrogenated butadiene oligomer (“TEAI-1000” manufactured by Nippon Soda Co., Ltd., terminal acrylic-modified hydrogenated polybutadiene) (Number average molecular weight 2250 in terms of polystyrene by GPC)
  • component (B) The following was used as the carboxyl group-containing (meth) acrylate of component (B).
  • component (C) (C-1) t-butylperoxy 2-ethylhexyl carbonate (“Trigonox 117” manufactured by Kayaku Akzo Co., Ltd., liquid at 1 hour half-life temperature of 117 ° C., maximum storage temperature of 35 ° C.
  • component (D) 1-hydroxycyclohexyl phenyl ketone (“IRGACURE184” manufactured by Ciba Specialty Chemicals)
  • component (D-2) Benzyldimethyl ketal (“IRGACURE651” manufactured by Ciba Specialty Chemicals)
  • (F) The following was used as the polyfunctional (meth) acrylate.
  • (F-1) Dimethylol-tricyclodecane diacrylate (“Light acrylate DCP-A” manufactured by Kyoeisha Chemical Co., Ltd.)
  • (F-2) Trimethylolpropane trimethacrylate (“Kyoeisha Chemical Co., Ltd.“ Light Ester TMP ”)
  • G The following was used as a monofunctional (meth) acrylate having a saturated alicyclic hydrocarbon group.
  • G-1 Isobornyl methacrylate (Kyoeisha Chemical Co., Ltd. “Light Ester IBX”)
  • G-2) Dicyclopentanyl methacrylate (“Fancryl FA-513M” manufactured by Hitachi Chemical Co., Ltd.)
  • G-3) 2-Methyl-2-adamantyl methacrylate (“Adamantate MM” manufactured by Idemitsu Kosan Co., Ltd.)
  • H The following was used as the hydroxyl group-containing (meth) acrylate.
  • H-1 2-hydroxyethyl methacrylate (Kyoeisha Chemical Co., Ltd. “Light Ester HO”)
  • H-2) 2-hydroxybutyl methacrylate (Kyoeisha Chemical Co., Ltd. “Light Ester HOB”)
  • Tensile shear bond strength measured in accordance with JIS K 6850. Specifically, using a heat-resistant glass (trade name “heat-resistant Pyrex (registered trademark) glass”, width 25 mm ⁇ length 25 mm ⁇ thickness 2.0 mm) as an adherend, the adhesion site is a circle having a diameter of 8 mm, Two heat-resistant glasses are bonded to each other with the prepared composition, and a UV irradiator is used, and the integrated light quantity is 3000 mJ / cm 2 (365 nm illuminance: 150 mW / cm 2 , “EXECURE 3000 (mercury xenon lamp mounted) manufactured by Hoyacadeo Optronics. Curing was performed under the conditions of the UV curing apparatus))) to prepare a tensile strength test piece. The produced test piece was measured for tensile shear bond strength in an environment of 23 ° C. and humidity of 50% using
  • Tensile shear bond strength measured in accordance with JIS K 6850. Specifically, using a heat-resistant glass (trade name “heat-resistant Pyrex (registered trademark) glass”, width 25 mm ⁇ length 25 mm ⁇ thickness 2.0 mm) as an adherend, the adhesion site is a circle having a diameter of 8 mm, Two sheets of heat-resistant glass were bonded together with the prepared composition, and cured using a dryer at 150 ° C. for 10 minutes to prepare a tensile strength test piece. The produced test piece was measured for tensile shear bond strength in an environment of 23 ° C. and humidity of 50% using a universal testing machine.
  • the viscosity of the composition was measured using an E-type viscometer at a temperature of 25 ° C.
  • the curable composition of the present example can be cured by heat in addition to being cured by irradiation with energy rays.
  • the curable composition of this example has high adhesion.
  • the one-hour half-life temperature of the thermal radical polymerization initiator By setting the one-hour half-life temperature of the thermal radical polymerization initiator to 127 ° C. or less, the adhesion is further improved.
  • the maximum storage temperature of the thermal radical polymerization initiator By setting the maximum storage temperature of the thermal radical polymerization initiator to 26 to 40 ° C., the storage stability is excellent.
  • the maximum storage temperature is outside the range of 26 to 40 ° C., but the adhesion is excellent.
  • the 1-hour half-life temperature of the component (C) exceeds 127 ° C., but the adhesion is excellent.
  • the curable composition of the present invention can be cured by irradiating energy rays, and in addition, the light shielding area can be cured by heat.
  • the curable composition of the present invention is an adhesive that has excellent storage stability, good workability, and high adhesiveness even if it is a one-component type by setting the half-life temperature for 1 hour and the maximum storage temperature. Can be provided.
  • the curable composition of the present invention has storage stability that can be used as a one-part composition, and has excellent adhesion as an adhesive that fixes materials having different light transmission properties. Very useful.

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Abstract

The purpose of the present invention is to provide a curable composition which is cured by an energy ray or heat and exhibits high adhesion. This curable composition contains (A) one or more kinds of (meth)acrylic modified oligomers which have one or more (meth)acryloyl groups at an end or in a side chain of each molecule and are selected from the group consisting of polybutadienes, polyisoprenes and hydrogenated products of these compounds, as well as (B) 1-10 parts by mass a carboxyl group-containing (meth)acrylate, (C) 0.01-3.5 parts by mass of a radical thermal polymerization initiator, (D) 0.01-15 parts by mass of a radical photopolymerization initiator and (E) 0.01-5 parts by mass of an antioxidant, respectively per 100 parts by mass of the total of the component (A), (F) a polyfunctional (meth)acrylate that is contained if necessary, (G) a monofunctional (meth)acrylate having a saturated alicyclic hydrocarbon group that is contained if necessary and (H) a hydroxyl group-containing (meth)acrylate that is contained if necessary. It is preferable that the component (C) has a 1-hour half-life temperature of 127°C or less and a maximum storage temperature of 26-40°C, while being in a liquid state at 25°C.

Description

硬化性組成物Curable composition
　本願発明は、硬化性組成物とそれを用いた接着剤及び硬化体に関する。 The present invention relates to a curable composition, an adhesive using the same, and a cured product.
　近年、ＣＤ、ＤＶＤ、青色半導体レーザに対応したＢｌｕ－ｒａｙディスク、ＨＤ－ＤＶＤ等の光記録媒体の再生・記録に用いられる光ピックアップ装置、液晶、有機エレクトロルミネッセンス等のディスプレイ、ＣＣＤ、ＣＭＯＳ等のイメージセンサー、半導体部品等で用いられる素子パッケージをはじめとするエレクトロニクス分野では、電子部品の高機能化に伴い、ガラス同士、ガラスと金属、ガラスとセラミック、ガラスとプラスチック、プラスチック同士、プラスチックと金属、プラスチックとセラミック、及び、金属同士等、被着体として、光の透過性が異なる材料間を接着するケースが増えている。そして、このような材料間において、高い精度で固定する接着剤が求められている。特に、光が透過しない材料間の接着において、はみ出し部分は光で硬化可能であるが、光が届かない部分は光以外で硬化する必要性があるため、光硬化に加え、その他の硬化機能を併せ持つ接着剤の開発が望まれている。このような技術の潮流の中で、光硬化性と熱硬化性を併せ持つ硬化性樹脂組成物が提案されている。 In recent years, optical pickup devices used for reproducing and recording optical recording media such as Blu-ray discs and HD-DVDs that support CDs, DVDs, and blue semiconductor lasers, displays such as liquid crystals and organic electroluminescence, CCDs, CMOSs, etc. In the electronics field, including device packages used in image sensors and semiconductor components, etc., as electronic components become more sophisticated, glass-to-glass, glass-to-metal, glass-to-ceramic, glass-to-plastic, plastic-to-plastic, plastic-to-metal, There are an increasing number of cases in which materials having different light transmission properties are bonded as adherends, such as plastics, ceramics, and metals. And the adhesive agent which fixes with high precision between such materials is calculated | required. In particular, in bonding between materials that do not transmit light, the protruding part can be cured with light, but the part that does not reach light needs to be cured with something other than light. The development of adhesives to be combined is desired. In the trend of such technology, curable resin compositions having both photocurability and thermosetting properties have been proposed.
　特許文献１には、ノボラック型エポキシ化合物と不飽和モノカルボン酸との反応物に飽和又は不飽和多塩基酸無水物を反応させて得られる感光性樹脂を含有する硬化性樹脂組成物が記載されている。 Patent Document 1 describes a curable resin composition containing a photosensitive resin obtained by reacting a reaction product of a novolak-type epoxy compound and an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride. ing.
　特許文献２には、波長３８０～１５００ｎｍの光を吸収することによりラジカルを発生する光重合開始剤と１０時間半減期温度５０～１２０℃である熱重合開始剤を含有する１液型の硬化性樹脂組成物が記載されている。 Patent Document 2 discloses a one-component curability containing a photopolymerization initiator that generates radicals by absorbing light having a wavelength of 380 to 1500 nm and a thermal polymerization initiator having a 10-hour half-life temperature of 50 to 120 ° C. A resin composition is described.
　特許文献３には、分子末端に（メタ）アクリロイル系基を有するビニル重合体、光ラジカル開始剤、熱ラジカル開始剤を有する硬化性樹脂組成物が記載されている。 Patent Document 3 describes a curable resin composition having a vinyl polymer having a (meth) acryloyl group at a molecular end, a photo radical initiator, and a thermal radical initiator.
　特許文献４～８には、（メタ）アクリレートを含有する硬化性組成物が記載されている。 Patent Documents 4 to 8 describe curable compositions containing (meth) acrylate.
特公平１－５４３９０号公報Japanese Patent Publication No. 1-54390 特開２００７－２６２１９４号公報JP 2007-262194 A 国際公開第２００７／０７７９００号パンフレットInternational Publication No. 2007/077900 Pamphlet 特開２０１０－１３２８９１号公報JP 2010-132891 A 国際公開第２０１０／０５０５２７号パンフレットInternational Publication No. 2010/050527 Pamphlet 特開２００９－２３５２０５号公報JP 2009-235205 A 特開２００８－１０１１５１号公報JP 2008-101151 A 特開２００８－１０１１０６号公報JP 2008-101106 A
　ところで、特許文献１の記載によれば、硬化性樹脂組成物は、経時的に増粘又はゲル化し易く、保存安定性に欠けることから、感光性樹脂を主体とした主剤と熱硬化性成分を主体とした硬化剤との２液型として市販され、使用時にこれら主剤と硬化剤を混合して用いられる。この硬化性樹脂組成物は、取り扱いにおいて、手間がかかるといった問題があった。 By the way, according to the description of Patent Document 1, the curable resin composition tends to thicken or gel with time and lacks storage stability. Therefore, the main component mainly composed of a photosensitive resin and a thermosetting component are included. It is commercially available as a two-component type with a main curing agent, and these main agents and curing agents are mixed and used at the time of use. This curable resin composition has a problem that it takes time to handle.
　また、特許文献２に記載された硬化性樹脂組成物は、特許文献１に記載の問題点を解決するものであるが、作業性に加え、半減期温度（分解温度）の低い熱重合開始剤、具体的には半減期温度が５０℃の熱重合開始剤を用いることから、低温硬化性に優れている反面、密着性が小さいといった問題があった。 Further, the curable resin composition described in Patent Document 2 solves the problems described in Patent Document 1, but in addition to workability, the thermal polymerization initiator has a low half-life temperature (decomposition temperature). Specifically, since a thermal polymerization initiator having a half-life temperature of 50 ° C. is used, there is a problem that adhesion is small while it is excellent in low-temperature curability.
　特許文献３においては、確かに硬化性、耐油性、耐熱性、耐候性に優れた硬化性樹脂組成物について検討されてはいるが、さらなる要求を満たすような、密着性については検討すらされていなかった。 In Patent Document 3, a curable resin composition having excellent curability, oil resistance, heat resistance, and weather resistance has been studied, but the adhesion to satisfy further requirements has been even studied. There wasn't.
　本発明は、上記従来技術が抱える問題を解決する為になされたものである。その主な目的は、接着剤として、密着性に優れる硬化性組成物とそれを用いた接着剤及び硬化体を提供することにある。 The present invention has been made in order to solve the problems of the above-described conventional technology. The main purpose is to provide a curable composition having excellent adhesion as an adhesive, and an adhesive and a cured product using the same.
　本発明者は、前記の課題を解決するべく鋭意研究を重ねた結果、（Ａ）分子の末端又は側鎖に１個以上の（メタ）アクリロイル基を有し、ポリブタジエン、ポリイソプレン、及び、これらの水素添加物からなる群から選ばれる１種以上である（メタ）アクリル変性オリゴマー、（Ｂ）カルボキシル基含有（メタ）アクリレート、（Ｃ）熱ラジカル重合開始剤、（Ｄ）光ラジカル重合開始剤、（Ｅ）酸化防止剤を含有する硬化性組成物が、前記の目的を達成し得ることを見いだし、本発明に至ったものである。 As a result of intensive studies to solve the above problems, the present inventor has (A) one or more (meth) acryloyl groups at the terminal or side chain of the molecule, polybutadiene, polyisoprene, and these (Meth) acryl-modified oligomer, (B) carboxyl group-containing (meth) acrylate, (C) thermal radical polymerization initiator, (D) photoradical polymerization initiator, which is one or more selected from the group consisting of (E) It discovered that the curable composition containing antioxidant could achieve the said objective, and came to this invention.
　本発明は、以下のとおりである。
（１）（Ａ）分子の末端又は側鎖に１個以上の（メタ）アクリロイル基を有し、ポリブタジエン、ポリイソプレン、及び、これらの水素添加物からなる群から選ばれる１種以上である（メタ）アクリル変性オリゴマー、（Ａ）成分、および必要に応じて含有する（Ｆ）多官能（メタ）アクリレート、必要に応じて含有する（Ｇ）飽和脂環式炭化水素基を有する単官能（メタ）アクリレートならびに必要に応じて含有する（Ｈ）水酸基含有（メタ）アクリレートの合計１００質量部に対して、（Ｂ）カルボキシル基含有（メタ）アクリレート１～１０質量部、（Ｃ）熱ラジカル重合開始剤０．０１～３．５質量部、（Ｄ）光ラジカル重合開始剤０．０１～１５質量部、および（Ｅ）酸化防止剤０．０１～５質量部を含有する硬化性組成物。
（２）前記（Ｃ）成分が１時間半減期温度１２７℃以下である（１）に記載の硬化性組成物。
（３）前記（Ｃ）成分が貯蔵最高温度２６～４０℃である（１）又は（２）に記載の硬化性組成物。
（４）前記（Ｃ）成分が２５℃にて液状である（１）～（３）のいずれかに記載の硬化性組成物。
（５）前記（Ｂ）成分が２－（メタ）アクリロイルオキシエチルジカルボン酸モノエステルを含有する（１）～（４）のいずれかに記載の硬化性組成物。
（６）更に（Ｆ）多官能（メタ）アクリレートを含有する（１）～（５）のいずれかに記載の硬化性組成物。
（７）前記（Ｆ）成分が脂環式構造を有する多官能（メタ）アクリレートである（６）に記載の硬化性組成物。
（８）更に（Ｇ）飽和脂環式炭化水素基を有する単官能（メタ）アクリレートを含有する（１）～（７）のいずれかに記載の硬化性組成物。
（９）前記（Ｇ）成分がイソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、２－メチル－２－アダマンチル（メタ）アクリレートからなる群から選択される少なくとも１種である（８）に記載の硬化性組成物。
（１０）更に（Ｈ）水酸基含有（メタ）アクリレートを含有する（１）～（９）のいずれかに記載の硬化性組成物。
（１１）更に（Ｉ）シランカップリング剤を含有する（１）～（１０）のいずれかに記載の硬化性組成物。
（１２）（１）～（１１）のいずれかに記載の硬化性組成物からなる接着剤。
（１３）（１２）に記載の接着剤を用いてなる接合体。
（１４）（１）～（１１）のいずれかに記載の硬化性組成物を硬化してなる硬化体。 The present invention is as follows.
(1) (A) One or more kinds selected from the group consisting of polybutadiene, polyisoprene, and hydrogenated products thereof having one or more (meth) acryloyl groups at the terminal or side chain of the molecule ( (Meth) acrylic modified oligomer, component (A), and optionally contained (F) polyfunctional (meth) acrylate, optionally contained (G) monofunctional (saturated alicyclic hydrocarbon group) ) Acrylate and (H) hydroxyl group-containing (meth) acrylate in total of 100 parts by mass, (B) carboxyl group-containing (meth) acrylate 1 to 10 parts by mass, (C) thermal radical polymerization initiation A curable composition containing 0.01 to 3.5 parts by weight of an agent, (D) 0.01 to 15 parts by weight of a radical photopolymerization initiator, and (E) 0.01 to 5 parts by weight of an antioxidant.
(2) The curable composition according to (1), wherein the component (C) has a one-hour half-life temperature of 127 ° C. or lower.
(3) The curable composition according to (1) or (2), wherein the component (C) has a maximum storage temperature of 26 to 40 ° C.
(4) The curable composition according to any one of (1) to (3), wherein the component (C) is liquid at 25 ° C.
(5) The curable composition according to any one of (1) to (4), wherein the component (B) contains 2- (meth) acryloyloxyethyldicarboxylic acid monoester.
(6) The curable composition according to any one of (1) to (5), further comprising (F) a polyfunctional (meth) acrylate.
(7) The curable composition according to (6), wherein the component (F) is a polyfunctional (meth) acrylate having an alicyclic structure.
(8) The curable composition according to any one of (1) to (7), further comprising (G) a monofunctional (meth) acrylate having a saturated alicyclic hydrocarbon group.
(9) The component (G) is at least one selected from the group consisting of isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and 2-methyl-2-adamantyl (meth) acrylate (8) The curable composition according to 1.
(10) The curable composition according to any one of (1) to (9), further comprising (H) a hydroxyl group-containing (meth) acrylate.
(11) The curable composition according to any one of (1) to (10), further comprising (I) a silane coupling agent.
(12) An adhesive comprising the curable composition according to any one of (1) to (11).
(13) A joined body using the adhesive according to (12).
(14) A cured product obtained by curing the curable composition according to any one of (1) to (11).
　本発明の硬化性組成物は、エネルギー線や熱により硬化することが可能である。本発明の硬化性組成物は、密着性が高いという特徴を有する。 The curable composition of the present invention can be cured by energy rays or heat. The curable composition of the present invention is characterized by high adhesion.
　本発明の（Ａ）成分は、分子の末端又は側鎖に１個以上の（メタ）アクリロイル基を有し、ポリブタジエン、ポリイソプレン、及び、これらの水素添加物からなる群から選ばれる１種以上である（メタ）アクリル変性オリゴマーである。 The component (A) of the present invention has at least one (meth) acryloyl group at the end or side chain of the molecule, and is one or more selected from the group consisting of polybutadiene, polyisoprene, and hydrogenated products thereof. This is a (meth) acryl-modified oligomer.
　（Ａ）成分の（メタ）アクリル変性オリゴマーの主鎖骨格は、ポリブタジエン、ポリイソプレン、ポリブタジエンの水素添加物、及び、ポリイソプレンの水素添加物からなる群から選ばれる少なくとも１種が好ましく、ポリブタジエン及びポリブタジエンの水素添加物からなる群のうちの１種以上がより好ましく、ポリブタジエンが最も好ましい。 The main chain skeleton of the (meth) acryl-modified oligomer of the component (A) is preferably at least one selected from the group consisting of polybutadiene, polyisoprene, a hydrogenated polybutadiene, and a hydrogenated polyisoprene. One or more members selected from the group consisting of hydrogenated polybutadienes are more preferred, and polybutadiene is most preferred.
　（Ａ）成分の（メタ）アクリル変性オリゴマーは、上記主鎖骨格の末端又は側鎖に少なくとも１個の（メタ）アクリロイル基を有する。これらの中では、主鎖骨格の両末端に（メタ）アクリロイル基を有するものが好ましい。 The (meth) acrylic modified oligomer of component (A) has at least one (meth) acryloyl group at the end or side chain of the main chain skeleton. Among these, those having (meth) acryloyl groups at both ends of the main chain skeleton are preferable.
　（Ａ）成分の（メタ）アクリル変性オリゴマーの分子量は５００～５０,０００が好ましく、８００～３８,０００がより好ましい。ここでいう分子量としては、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定されるポリスチレン換算の数平均分子量が好ましく用いられる。分子量が５００以上である場合、本発明の硬化性組成物にエネルギー線を照射して得られる硬化体の硬度が大きくなり、接着剤層が形成し易くなる。分子量が５０,０００以下である場合、得られる樹脂組成物の粘度が低くなり、製造過程での混合等における作業性、実用用途において当該硬化性組成物を用いる際の作業性が良好になる。 The molecular weight of the component (A) (meth) acryl-modified oligomer is preferably 500 to 50,000, more preferably 800 to 38,000. As a molecular weight here, the number average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC) is used preferably. When the molecular weight is 500 or more, the hardness of the cured product obtained by irradiating the curable composition of the present invention with energy rays increases, and the adhesive layer is easily formed. When the molecular weight is 50,000 or less, the viscosity of the resulting resin composition becomes low, and the workability in mixing during the production process and the workability when using the curable composition in practical applications are improved.
　（Ａ）成分の（メタ）アクリル変性オリゴマーとしては、日本曹達社製ＮＩＳＳＯ－ＰＢ　ＴＥＡＩ－１０００（両末端アクリレート変性水素添加ブタジエン系オリゴマー）、日本曹達社製ＮＩＳＳＯ－ＰＢ　ＴＥ－２０００（両末端メタクリレート変性ブタジエン系オリゴマー）等が挙げられる。 (A) Component (meth) acrylic modified oligomers include Nippon Soda Co., Ltd. NISSO-PB TEAI-1000 (Both-end acrylate-modified hydrogenated butadiene oligomer), Nippon Soda Co., Ltd. NISSO-PB TE-2000 (Both-end methacrylate) Modified butadiene oligomer).
　（Ｂ）成分は、カルボキシル基含有（メタ）アクリレートである。カルボキシル基含有（メタ）アクリレートは分子内にカルボキシル基を少なくとも一つ以上有する単官能（メタ）アクリレートモノマーをいう。 (B) component is a carboxyl group-containing (meth) acrylate. The carboxyl group-containing (meth) acrylate refers to a monofunctional (meth) acrylate monomer having at least one carboxyl group in the molecule.
　カルボキシル基含有（メタ）アクリレートとしては、２－（メタ）アクリロイルオキシエチルコハク酸モノエステル、２－（メタ）アクリロイルオキシエチルフタル酸モノエステル、２－（メタ）アクリロイルオキシエチルヘキサヒドロフタル酸モノエステル等の２－（メタ）アクリロイルオキシエチルジカルボン酸モノエステル、ω－カルボキシ－ポリカプロラクトンモノ（メタ）アクリレート等のポリカプロラクトン変性（メタ）アクリル酸エステル、（メタ）アクリル酸ダイマー、（メタ）アクリル酸トリマー、（メタ）アクリル酸テトラマーが挙げられる。これらは１種又は２種以上を組み合わせて用いることができる。カルボキシル基含有（メタ）アクリレートとしては、（メタ）アクリル酸を除くことが好ましい。 Examples of carboxyl group-containing (meth) acrylates include 2- (meth) acryloyloxyethyl succinic acid monoester, 2- (meth) acryloyloxyethyl phthalic acid monoester, 2- (meth) acryloyloxyethyl hexahydrophthalic acid monoester 2- (meth) acryloyloxyethyl dicarboxylic acid monoester such as ω-carboxy-polycaprolactone mono (meth) acrylate and other polycaprolactone modified (meth) acrylic acid ester, (meth) acrylic acid dimer, (meth) acrylic acid Trimers and (meth) acrylic acid tetramers. These can be used alone or in combination of two or more. As the carboxyl group-containing (meth) acrylate, it is preferable to remove (meth) acrylic acid.
　これらの中では、２－（メタ）アクリロイルオキシエチルジカルボン酸モノエステルが好ましく、２－（メタ）アクリロイルオキシエチルコハク酸モノエステル、２－（メタ）アクリロイルオキシエチルヘキサヒドロフタル酸モノエステルからなる群のうちの１種以上がより好ましい。２－（メタ）アクリロイルオキシエチルコハク酸モノエステルとしては、２－メタクリロイルオキシエチルコハク酸等が挙げられる。２－（メタ）アクリロイルオキシエチルヘキサヒドロフタル酸モノエステルとしては、２－メタクリロイルオキシエチルヘキサヒドロフタル酸等が挙げられる。 Of these, 2- (meth) acryloyloxyethyl dicarboxylic acid monoester is preferable, and the group consisting of 2- (meth) acryloyloxyethyl succinic acid monoester and 2- (meth) acryloyloxyethyl hexahydrophthalic acid monoester One or more of these are more preferred. Examples of 2- (meth) acryloyloxyethyl succinic acid monoester include 2-methacryloyloxyethyl succinic acid. Examples of 2- (meth) acryloyloxyethyl hexahydrophthalic acid monoester include 2-methacryloyloxyethyl hexahydrophthalic acid.
　（Ｃ）成分は、熱ラジカル重合開始剤である。熱ラジカル重合開始剤としては、有機過酸化物が好ましい。 (C) component is a thermal radical polymerization initiator. As the thermal radical polymerization initiator, an organic peroxide is preferable.
〔１時間半減期温度〕
　熱ラジカル重合開始剤の１時間半減期温度は１２７℃以下が好ましく、１０４～１２７℃がより好ましく、１０６～１２７℃が最も好ましい。１時間半減期温度を１２７℃以下にすることにより、低温硬化性が高くなるといった効果を有する。１時間半減期温度を１０４℃以上にすることにより、貯蔵安定性が高くなるといった効果を有する。 [1 hour half-life temperature]
The one-hour half-life temperature of the thermal radical polymerization initiator is preferably 127 ° C. or less, more preferably 104 to 127 ° C., and most preferably 106 to 127 ° C. By setting the one-hour half-life temperature to 127 ° C. or lower, there is an effect that the low-temperature curability is increased. By setting the one-hour half-life temperature to 104 ° C. or higher, there is an effect that the storage stability is increased.
　１時間半減期温度は、以下の方法により測定する。 1 hour half-life temperature is measured by the following method.
　半減期温度測定対象の熱ラジカル重合開始剤を所定の溶剤で溶解し、所定の濃度に調整する。得られた溶液を容器に密封し、溶液を所定の温度に保持して熱ラジカル重合開始剤を熱分解する。この際の時間と熱ラジカル重合開始剤の濃度変化との関係を測定することにより１時間半減期温度を求める。 ¡The thermal radical polymerization initiator whose half-life temperature is to be measured is dissolved in a predetermined solvent and adjusted to a predetermined concentration. The obtained solution is sealed in a container, and the thermal radical polymerization initiator is thermally decomposed while maintaining the solution at a predetermined temperature. The one-hour half-life temperature is determined by measuring the relationship between the time at this time and the concentration change of the thermal radical polymerization initiator.
　具体的には、まず、所定の温度において、式（１）よりＫd値を求めて、これを式（２）に代入して半減期温度を求める。 Specifically, first, at a predetermined temperature, a K d value is obtained from Equation (1), and this is substituted into Equation (2) to obtain a half-life temperature.
　式（１）：ｌｎ（Ｃｏ／Ｃｔ）＝Ｋdｔ
（式中、Ｃｏ：熱ラジカル重合開始剤の初期濃度、Ｃｔ：ｔ時間熱分解語の熱ラジカル重合開始剤濃度、Ｋd：熱分解速度定数、ｔ：時間）
式（２）：ｔ1／2＝ｌｎ２／Ｋd
（式中、ｔ1／2：半減期） Formula (1): ln (Co / Ct) = K d t
(In the formula, Co: initial concentration of thermal radical polymerization initiator, Ct: thermal radical polymerization initiator concentration in t-time thermal decomposition term, K d : thermal decomposition rate constant, t: time)
Formula (2): t 1/2 = ln 2 / K d
( Where t 1/2 is the half-life)
　得られた半減期が１時間となる温度を算出することで、１時間半減期温度が求められる。 The 1-hour half-life temperature is determined by calculating the temperature at which the obtained half-life is 1 hour.
〔貯蔵最高温度〕
　熱ラジカル重合開始剤の貯蔵最高温度は２６～４０℃が好ましく、３０～４０℃がより好ましく、３０～３８℃が最も好ましい。貯蔵最高温度を２６℃以上にすることにより、貯蔵安定性が高くなるといった効果を有する。貯蔵最高温度を４０℃以下にすることにより、低温硬化性が高くなるといった効果を有する。 [Maximum storage temperature]
The maximum storage temperature of the thermal radical polymerization initiator is preferably 26 to 40 ° C, more preferably 30 to 40 ° C, and most preferably 30 to 38 ° C. By setting the maximum storage temperature to 26 ° C. or higher, there is an effect that the storage stability is increased. By setting the maximum storage temperature to 40 ° C. or lower, there is an effect that the low-temperature curability is increased.
　貯蔵最高温度は、以下の方法により測定した。 The maximum storage temperature was measured by the following method.
　所定の温度に設定したオーブン内に所定量の熱ラジカル重合開始剤を入れた容器を一定期間保持し、定期的に熱ラジカル重合開始剤の純度（活性酸素量）を測定する。一定期間内に品質上、問題ない範囲で低下しない最高温度を求めて貯蔵最高温度とした。 * Hold a container with a predetermined amount of thermal radical polymerization initiator in an oven set at a predetermined temperature for a certain period, and periodically measure the purity (active oxygen amount) of the thermal radical polymerization initiator. The maximum temperature that does not decrease within a certain period in terms of quality within a certain period of time was determined and used as the maximum storage temperature.
　熱ラジカル重合開始剤は２５℃にて液状である有機過酸化物が好ましい。２５℃にて液状であることにより、製造時に加熱工程を行う必要がなく、温度上昇による自己重合を防止するといった効果を有する。 The thermal radical polymerization initiator is preferably an organic peroxide that is liquid at 25 ° C. Since it is liquid at 25 ° C., it is not necessary to perform a heating step during production, and self-polymerization due to temperature rise is prevented.
　１時間半減期温度１２７℃以下、貯蔵最高温度２６～４０℃、かつ、２５℃にて液状である有機過酸化物としては、ｔ－ブチルパーオキシアセテート（１時間半減期温度１２０～１２３℃、貯蔵最高温度３０～３８℃、２５℃にて液状）、ｔ－ブチルパーオキシ３,５,５－トリメチルヘキサノエート（１時間半減期温度１１９℃、貯蔵最高温度３５℃、２５℃にて液状）、ｔ－ブチルパーオキシベンゾエート（１時間半減期温度１２５℃、貯蔵最高温度３０～３８℃、２５℃にて液状）、ｔ－ブチルパーオキシイソプロピルカーボネート（１時間半減期温度１１６～１１８℃、貯蔵最高温度３０～３８℃、２５℃にて液状）、ｔ－ブチルパーオキシ２－エチルヘキシルカーボネート（１時間半減期温度１１７℃、貯蔵最高温度３０～３８℃、２５℃にて液状）、１，１－ジ（ｔ－ブチルパーオキシ）シクロヘキサン（１時間半減期温度１１１～１１６℃、貯蔵最高温度３０～３８℃、２５℃にて液状）、２，２－ジ（ｔ－ブチルパーオキシ）ブタン（１時間半減期温度１１９～１２７℃、貯蔵最高温度３０～３８℃、２５℃にて液状）、１，６－ビス（ｔ－ブチルパーオキシカルボニロキシ）ヘキサン（１時間半減期温度１１５℃、貯蔵最高温度３５℃、２５℃にて液状）、２，２－ビス（４，４－ジ－ｔ－ブチルパーオキシシクロヘキシ）プロパン（１時間半減期温度１０９～１１４℃、貯蔵最高温度３０～３５℃、２５℃にて液状）、ｎ－ブチル４，４－ジ－（ｔ－ブチルパーオキシ）バレレート（１時間半減期温度１２７℃、貯蔵最高温度３０℃、２５℃にて液状）、ｔ－ブチルパーオキシラウレート（１時間半減期温度１１８℃、貯蔵最高温度３０℃、２５℃にて液状）、ｔ－アミルパーオキシアセテート（１時間半減期温度１２０℃、貯蔵最高温度３８℃、２５℃にて液状）、ｔ－アミルパーオキシ３,５,５－トリメチルヘキサノエート（１時間半減期温度１１４℃、貯蔵最高温度３０～３５℃、２５℃にて液状）、ｔ－アミルパーオキシベンゾエート（１時間半減期温度１２２℃、貯蔵最高温度３８℃、２５℃にて液状）、ｔ－アミルパーオキシイソプロピルカーボネート（１時間半減期温度１１５℃、貯蔵最高温度３８℃、２５℃にて液状）、ｔ－アミルパーオキシ２－エチルヘキシルカーボネート（１時間半減期温度１１７℃、貯蔵最高温度３８℃、２５℃にて液状）、２，２－ジ－（ｔ－アミルパーオキシ）ブタン（１時間半減期温度１１５℃、貯蔵最高温度３５℃、２５℃にて液状）、１，１－ジ（ｔ－アミルパーオキシ）シクロヘキサン（１時間半減期温度１１２℃、貯蔵最高温度３８℃、２５℃にて液状）、１，１－ジ（ｔ－ヘキシルパーオキシ）－３,５,５－トリメチルシクロヘキサン（１時間半減期温度１０６℃、貯蔵最高温度３０℃、２５℃にて液状）、１，１－ジ（ｔ－ヘキシルパーオキシ）シクロヘキサン（１時間半減期温度１０７℃、貯蔵最高温度３０℃、２５℃にて液状）等が挙げられる。これらは１種又は２種以上を組み合わせて用いることができる。 Organic peroxides that are liquid at 1 hour half-life temperature of 127 ° C. or less, maximum storage temperature of 26 to 40 ° C., and 25 ° C. include t-butyl peroxyacetate (1 hour half-life temperature of 120 to 123 ° C., Maximum storage temperature 30-38 ° C, liquid at 25 ° C), t-butylperoxy 3,5,5-trimethylhexanoate (1 hour half-life temperature 119 ° C, maximum storage temperature 35 ° C, liquid at 25 ° C) ), T-butyl peroxybenzoate (1 hour half-life temperature 125 ° C., maximum storage temperature 30-38 ° C., liquid at 25 ° C.), t-butyl peroxyisopropyl carbonate (1 hour half-life temperature 116-118 ° C., Maximum storage temperature 30 to 38 ° C, liquid at 25 ° C), t-butylperoxy 2-ethylhexyl carbonate (1 hour half-life temperature 117 ° C, maximum storage temperature 30 to 38 ° C) Liquid at 25 ° C.), 1,1-di (t-butylperoxy) cyclohexane (1 hour half-life temperature 111-116 ° C., maximum storage temperature 30-38 ° C., liquid at 25 ° C.), 2,2- Di (t-butylperoxy) butane (1 hour half-life temperature 119-127 ° C, maximum storage temperature 30-38 ° C, liquid at 25 ° C), 1,6-bis (t-butylperoxycarbonyloxy) Hexane (1 hour half-life temperature 115 ° C, maximum storage temperature 35 ° C, liquid at 25 ° C), 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane (1 hour half-life temperature 109-114 ° C, maximum storage temperature 30-35 ° C, liquid at 25 ° C), n-butyl 4,4-di- (t-butylperoxy) valerate (1 hour half-life temperature 127 ° C, maximum storage temperature 30 Liquid at ℃ and 25 ℃), t-bu Chilperoxylaurate (1 hour half-life temperature 118 ° C, maximum storage temperature 30 ° C, liquid at 25 ° C), t-amyl peroxyacetate (1 hour half-life temperature 120 ° C, maximum storage temperature 38 ° C, 25 ° C) Liquid), t-amylperoxy 3,5,5-trimethylhexanoate (1 hour half-life temperature 114 ° C, maximum storage temperature 30-35 ° C, liquid at 25 ° C), t-amylperoxybenzoate (Liquid at 1 hour half-life temperature 122 ° C, maximum storage temperature 38 ° C, 25 ° C), t-amyl peroxyisopropyl carbonate (1 hour half-life temperature 115 ° C, storage maximum temperature 38 ° C, liquid at 25 ° C) , T-amylperoxy 2-ethylhexyl carbonate (1 hour half-life temperature 117 ° C, maximum storage temperature 38 ° C, liquid at 25 ° C), 2,2-di- (t-amylpero B) Butane (liquid at 1 hour half-life temperature 115 ° C, maximum storage temperature 35 ° C, 25 ° C), 1,1-di (t-amylperoxy) cyclohexane (1 hour half-life temperature 112 ° C, maximum storage temperature Liquid at 38 ° C and 25 ° C), 1,1-di (t-hexylperoxy) -3,5,5-trimethylcyclohexane (1 hour half-life temperature 106 ° C, maximum storage temperature 30 ° C, 25 ° C) Liquid), 1,1-di (t-hexylperoxy) cyclohexane (liquid at 1 hour half-life temperature of 107 ° C., maximum storage temperature of 30 ° C. and 25 ° C.), and the like. These can be used alone or in combination of two or more.
　これらの中では、ｔ－ブチルパーオキシ２－エチルヘキシルカーボネート、ｔ－アミルパーオキシ２－エチルヘキシルカーボネート、ｔ－ブチルパーオキシ３，５，５－トリメチルヘキサノエート、ｔ－アミルパーオキシ３，５，５－トリメチルヘキサノエートからなる群のうちの１種以上が好ましく、ｔ－ブチルパーオキシ２－エチルヘキシルカーボネート、ｔ－アミルパーオキシ２－エチルヘキシルカーボネートからなる群のうちの１種以上がより好ましい。 Among these, t-butyl peroxy 2-ethylhexyl carbonate, t-amyl peroxy 2-ethylhexyl carbonate, t-butyl peroxy 3,5,5-trimethylhexanoate, t-amyl peroxy 3,5,5 One or more members selected from the group consisting of 5-trimethylhexanoate are preferable, and one or more members selected from the group consisting of t-butylperoxy 2-ethylhexyl carbonate and t-amylperoxy 2-ethylhexyl carbonate are more preferable.
　熱ラジカル重合開始剤としては、ジ（２－エチルヘキシル）パーオキシジカーボネート、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキサン等も挙げられる。 Examples of the thermal radical polymerization initiator include di (2-ethylhexyl) peroxydicarbonate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and the like.
　（Ｄ）成分は、光ラジカル重合開始剤である。光ラジカル重合開始剤には紫外線重合開始剤や可視光重合開始剤等があるが、どちらも制限無く用いられる。紫外線重合開始剤としては、ベンゾイン系、ベンゾフェノン系、アセトフェノン系等が挙げられる。可視光重合開始剤としては、アシルホスフィンオキサイド系、チオキサントン系、キノン系等が挙げられる。 (D) component is a radical photopolymerization initiator. Examples of the radical photopolymerization initiator include an ultraviolet polymerization initiator and a visible light polymerization initiator, both of which are used without limitation. Examples of the ultraviolet polymerization initiator include benzoin, benzophenone, and acetophenone. Examples of visible light polymerization initiators include acylphosphine oxides, thioxanthones, and quinones.
　光ラジカル重合開始剤としては、ベンゾフェノン、４－フェニルベンゾフェノン、ベンゾイル安息香酸、２，２－ジエトキシアセトフェノン、ビスジエチルアミノベンゾフェノン、ベンジル、ベンゾイン、ベンゾイルイソプロピルエーテル、ベンジルジメチルケタール、１－ヒドロキシシクロヘキシルフェニルケトン、チオキサントン、１－（４－イソプロピルフェニル）２－ヒドロキシ－２－メチルプロパン－１－オン、１－（４－（２－ヒドロキシエトキシ）－フェニル）－２－ヒドロキシ－２－メチル－１―プロパン－１－オン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、カンファーキノン、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）―フェニルホスフィンオキサイド、２－メチル―１―（４－（メチルチオ）フェニル）―２－モルフォリノプロパン－１－オン、２－ベンジル―２－ジメチルアミノ－１―（４－モルフォリノフェニル）―１－ブタノン－１、ビス（２，６－ジメトキシベンゾイル）―２，４，４―トリメチル－ペンチルホスフィンオキサイド等が挙げられる。これらは１種又は２種以上を組み合わせて用いることができる。 Examples of photo radical polymerization initiators include benzophenone, 4-phenylbenzophenone, benzoylbenzoic acid, 2,2-diethoxyacetophenone, bisdiethylaminobenzophenone, benzyl, benzoin, benzoylisopropyl ether, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, Thioxanthone, 1- (4-Isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy-2-methyl-1-propane- 1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, camphorquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) Phenylphosphine oxide, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1- Examples include butanone-1, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide. These can be used alone or in combination of two or more.
　これらの中では、１－ヒドロキシシクロヘキシルフェニルケトン、ベンジルジメチルケタールからなる群のうちの１種以上が好ましい。 Of these, one or more members selected from the group consisting of 1-hydroxycyclohexyl phenyl ketone and benzyl dimethyl ketal are preferable.
　（Ｅ）成分は酸化防止剤である。酸化防止剤としては、フェノール系、ハイドロキノン系等が挙げられる。これらの中では、フェノール系が好ましい。 (E) Component is an antioxidant. Examples of the antioxidant include a phenol type and a hydroquinone type. Among these, a phenol type is preferable.
　酸化防止剤としては、β―ナフトキノン、２－メトキシー１，４－ナフトキノン、メチルハイドロキノン、ハイドロキノン、２，２－メチレン－ビス（４－メチル－６－ターシャリーブチルフェノール）、カテコール、ハイドロキノンモノメチルエーテル、モノターシャリーブチルハイドロキノン、２，５－ジターシャリーブチルハイドロキノン、ｐ－ベンゾキノン、２，５－ジフェニル－ｐ－ベンゾキノン、２，５－ジターシャリーブチル－ｐ－ベンゾキノン、ピクリン酸、クエン酸、フェノチアジン、ターシャリーブチルカテコール、２－ブチル－４－ヒドロキシアニソール及び２，６－ジターシャリーブチル－ｐ－クレゾール等が挙げられる。これらは１種又は２種以上を組み合わせて用いることができる。フェノール系としては、２，２－メチレン－ビス（４－メチル－６－ターシャリーブチルフェノール）、カテコール、ピクリン酸、ターシャリーブチルカテコール、２－ブチル－４－ヒドロキシアニソール及び２，６－ジターシャリーブチル－ｐ－クレゾール等が挙げられる。 Antioxidants include β-naphthoquinone, 2-methoxy-1,4-naphthoquinone, methylhydroquinone, hydroquinone, 2,2-methylene-bis (4-methyl-6-tertiarybutylphenol), catechol, hydroquinone monomethyl ether, mono Tertiary butyl hydroquinone, 2,5-ditertiary butyl hydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-ditertiary butyl-p-benzoquinone, picric acid, citric acid, phenothiazine, tertiary Examples thereof include butyl catechol, 2-butyl-4-hydroxyanisole, and 2,6-ditertiary butyl-p-cresol. These can be used alone or in combination of two or more. Phenols include 2,2-methylene-bis (4-methyl-6-tertiary butylphenol), catechol, picric acid, tertiary butyl catechol, 2-butyl-4-hydroxyanisole and 2,6-ditertiary butyl. -P-cresol and the like.
　これらの中では、２，２－メチレン－ビス（４－メチル－６－ターシャリーブチルフェノール）が好ましい。 Of these, 2,2-methylene-bis (4-methyl-6-tertiary butylphenol) is preferable.
　本発明の硬化性組成物は、前記（Ａ）～（Ｅ）成分を必須成分として含有する。
　前記（Ａ）～（Ｅ）成分を含有する組成物は、エネルギー線を照射することにより硬化することに加え、遮光エリアを熱により硬化することが可能であり、密着性が高いといった効果を有する。 The curable composition of the present invention contains the components (A) to (E) as essential components.
The composition containing the components (A) to (E) has an effect that the light-shielding area can be cured by heat in addition to being cured by irradiation with energy rays, and has high adhesiveness. .
　本発明の硬化性組成物は、耐熱性向上の点で、（Ｆ）成分として、多官能（メタ）アクリレートを含有することができる。多官能（メタ）アクリレートとは、分子内に（メタ）アクリロイル基を２個以上有する化合物をいう。多官能（メタ）アクリレートの中では、多官能メタクリレートが好ましい。 The curable composition of the present invention can contain polyfunctional (meth) acrylate as the component (F) in terms of improving heat resistance. The polyfunctional (meth) acrylate refers to a compound having two or more (meth) acryloyl groups in the molecule. Among polyfunctional (meth) acrylates, polyfunctional methacrylate is preferable.
　多官能（メタ）アクリレートとしては、ジメチロール－トリシクロデカンジ（メタ）アクリレート、ジメチロール－シクロヘキサンジ（メタ）アクリレート等の脂環式構造を有する多官能（メタ）アクリレート、エチレンオキシド付加ビスフェノールＡジ（メタ）アクリレート、エチレンオキシド付加ビスフェノールＦジ（メタ）アクリレート、プロピレンオキシド付加ビスフェノールＡジ（メタ）アクリレート、プロピレンオキシド付加ビスフェノールＦジ（メタ）アクリレート等の芳香族環構造を有する多官能（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート等の脂肪族分岐構造を有する多官能（メタ）アクリレート等が挙げられる。これらは１種又は２種以上を組み合わせて用いることができる。 Examples of the polyfunctional (meth) acrylate include polyfunctional (meth) acrylate having an alicyclic structure such as dimethylol-tricyclodecane di (meth) acrylate, dimethylol-cyclohexanedi (meth) acrylate, and ethylene oxide-added bisphenol A di (meth) ) Polyfunctional (meth) acrylate having an aromatic ring structure such as acrylate, ethylene oxide-added bisphenol F di (meth) acrylate, propylene oxide-added bisphenol A di (meth) acrylate, propylene oxide-added bisphenol F di (meth) acrylate, tri Examples include polyfunctional (meth) acrylates having an aliphatic branched structure such as methylolpropane tri (meth) acrylate. These can be used alone or in combination of two or more.
　脂環式構造を有する多官能（メタ）アクリレートの中では、炭素数６～１２の脂環式構造を有する多官能（メタ）アクリレートが好ましい。炭素数６～１２の脂環式構造を有する多官能（メタ）アクリレートの中では、ジメチロール－トリシクロデカンジ（メタ）アクリレートが好ましい。脂肪族分岐構造を有する多官能（メタ）アクリレートの中では、トリメチロールプロパントリ（メタ）アクリレートが好ましい。 Among polyfunctional (meth) acrylates having an alicyclic structure, polyfunctional (meth) acrylates having an alicyclic structure having 6 to 12 carbon atoms are preferable. Among polyfunctional (meth) acrylates having an alicyclic structure having 6 to 12 carbon atoms, dimethylol-tricyclodecane di (meth) acrylate is preferable. Among polyfunctional (meth) acrylates having an aliphatic branched structure, trimethylolpropane tri (meth) acrylate is preferred.
　これらの中では、脂環式構造を有する多官能（メタ）アクリレート、脂肪族分岐構造を有する多官能（メタ）アクリレートからなる群のうちの１種以上が好ましく、脂環式構造を有する多官能（メタ）アクリレートがより好ましい。 Among these, at least one of the group consisting of a polyfunctional (meth) acrylate having an alicyclic structure and a polyfunctional (meth) acrylate having an aliphatic branched structure is preferable, and a polyfunctional having an alicyclic structure is preferable. (Meth) acrylate is more preferred.
　本発明の硬化性組成物は、耐熱性向上の点で、（Ｇ）成分として、飽和脂環式炭化水素基を有する単官能（メタ）アクリレートを含有することができる。飽和脂環式炭化水素基を有する単官能（メタ）アクリレートは、エステル結合を介することにより、飽和脂環式炭化水素基を有する単官能（メタ）アクリレートである。 The curable composition of the present invention can contain a monofunctional (meth) acrylate having a saturated alicyclic hydrocarbon group as the component (G) in terms of improving heat resistance. The monofunctional (meth) acrylate having a saturated alicyclic hydrocarbon group is a monofunctional (meth) acrylate having a saturated alicyclic hydrocarbon group via an ester bond.
　（Ｇ）成分の中では、炭素数９～１２の飽和脂環式炭化水素基を有する単官能（メタ）アクリレートが好ましい。炭素数９～１２の飽和脂環式炭化水素基としては、ジシクロペンタニル基、イソボルニル基、アダマンチル基等が挙げられる。これらの中では、ジシクロペンタニル基、イソボルニル基からなる群のうちの１種以上が好ましく、イソボルニル基がより好ましい。（Ｇ）成分の単官能（メタ）アクリレートの中では、メタクリレートが好ましい。 Among the components (G), monofunctional (meth) acrylates having a saturated alicyclic hydrocarbon group having 9 to 12 carbon atoms are preferable. Examples of the saturated alicyclic hydrocarbon group having 9 to 12 carbon atoms include dicyclopentanyl group, isobornyl group, adamantyl group and the like. In these, 1 or more types in the group which consists of a dicyclopentanyl group and an isobornyl group are preferable, and an isobornyl group is more preferable. Among the monofunctional (meth) acrylates of component (G), methacrylate is preferable.
　炭素数９～１２の飽和脂環式炭化水素基を有する単官能（メタ）アクリレートとしては、２－メチル－２－アダマンチル（メタ）アクリレート、２－エチル－２－アダマンチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニルオキシエチル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート等が挙げられる。これらは１種又は２種以上を組み合わせて用いることができる。 Examples of the monofunctional (meth) acrylate having a saturated alicyclic hydrocarbon group having 9 to 12 carbon atoms include 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, isobornyl ( And (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and the like. These can be used alone or in combination of two or more.
　これらの中では、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、２－メチル－２－アダマンチル（メタ）アクリレートからなる群のうちの１種以上が好ましく、イソボルニル（メタ）アクリレートがより好ましい。 Among these, at least one member selected from the group consisting of isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and 2-methyl-2-adamantyl (meth) acrylate is preferable, and isobornyl (meth) acrylate is more preferable. preferable.
　本発明の硬化性組成物は、ガラス面への密着性向上の点で、（Ｈ）成分として、水酸基含有（メタ）アクリレート含有することができる。水酸基含有（メタ）アクリレートは、分子内に水酸基を少なくとも一つ以上有する単官能（メタ）アクリレートをいう。（Ｈ）成分の中では、単官能メタクリレートが好ましい。 The curable composition of the present invention can contain a hydroxyl group-containing (meth) acrylate as the component (H) in terms of improving the adhesion to the glass surface. The hydroxyl group-containing (meth) acrylate refers to a monofunctional (meth) acrylate having at least one hydroxyl group in the molecule. Among the components (H), monofunctional methacrylate is preferable.
　水酸基含有（メタ）アクリレートとしては、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、２－（メタ）アクリロイルオキシエチル－２－ヒドロキシプロピルフタレート、グリセロールモノ（メタ）アクリレート、１，６－へキサンジオールモノ（メタ）アクリレート、ネオペンチルグリコールモノ（メタ）アクリレート、４－ヒドロキシシクロヘキシル（メタ）アクリレート、１，４－ブタンジオールモノ（メタ）アクリレート等が挙げられる。これらは１種又は２種以上を組み合わせて用いることができる。 Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2 -(Meth) acryloyloxyethyl-2-hydroxypropyl phthalate, glycerol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, 4-hydroxycyclohexyl (meth) Examples thereof include acrylate and 1,4-butanediol mono (meth) acrylate. These can be used alone or in combination of two or more.
　これらの中では、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレートからなる群のうちの１種以上が好ましく、２－ヒドロキシエチル（メタ）アクリレートがより好ましい。 Among these, one or more members selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate are preferable, and 2-hydroxyethyl (meth) Acrylate is more preferred.
　本発明の硬化性組成物は、ガラス面への密着性向上の点で、（Ｉ）成分として、シランカップリング剤を含有することができる。 The curable composition of the present invention can contain a silane coupling agent as component (I) in terms of improving the adhesion to the glass surface.
　シランカップリング剤としては、γ－クロロプロピルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリクロルシラン、ビニルトリエトキシシラン、ビニル－トリス（β－メトキシエトキシ）シラン、γ－（メタ）アクリロキシプロピルトリメトキシシラン、β－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－メルカプトプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン、Ｎ－β－（アミノエチル）－γ－アミノプロピルトリメトキシシラン、Ｎ－β－（アミノエチル）－γ－アミノプロピルメチルジメトキシシラン及びγ－ユレイドプロピルトリエトキシシラン等が挙げられる。これらは１種又は２種以上を組み合わせて用いることができる。 Silane coupling agents include γ-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane, γ- (meth) acryloxypropyltrimethoxy. Silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) ) -Γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, and γ-ureidopropyltriethoxysilane. These can be used alone or in combination of two or more.
　これらの中では、γ－（メタ）アクリロキシプロピルトリメトキシシランが好ましい。 Of these, γ- (meth) acryloxypropyltrimethoxysilane is preferred.
　本発明の硬化性組成物の使用量は、以下の通りである。 The amount of the curable composition of the present invention used is as follows.
　（Ａ）成分の含有量は、（Ａ）成分、必要に応じて含有する（Ｆ）成分、必要に応じて含有する（Ｇ）成分、必要に応じて含有する（Ｈ）成分の合計１００質量部中、１０質量部以上が好ましく、１０～９０質量部がより好ましく、３０～７０質量部が最も好ましい。 Content of (A) component is (A) component, (F) component contained as needed, (G) component contained as needed, (H) component contained as needed 100 mass in total. Of these, 10 parts by mass or more are preferable, 10 to 90 parts by mass are more preferable, and 30 to 70 parts by mass are most preferable.
　（Ｆ）成分の含有量は、（Ａ）成分、必要に応じて含有する（Ｆ）成分、必要に応じて含有する（Ｇ）成分ならびに必要に応じて含有する（Ｈ）成分の合計１００質量部中、５０質量部以下が好ましく、５～５０質量部がより好ましく、１０～２５質量部が最も好ましい。 Content of (F) component is 100 mass in total of (A) component, (F) component contained as needed, (G) component contained as needed, and (H) component contained as needed. The amount is preferably 50 parts by mass or less, more preferably 5 to 50 parts by mass, and most preferably 10 to 25 parts by mass.
　（Ｇ）成分の含有量は、（Ａ）成分、必要に応じて含有する（Ｆ）成分、必要に応じて含有する（Ｇ）成分ならびに必要に応じて含有する（Ｈ）成分の合計１００質量部中、５０質量部以下が好ましく、５～５０質量部がより好ましく、１０～３５質量部が最も好ましい。 Content of (G) component is 100 mass in total of (A) component, (F) component contained as needed, (G) component contained as needed, and (H) component contained as needed. In part, 50 parts by mass or less is preferable, 5 to 50 parts by mass is more preferable, and 10 to 35 parts by mass is most preferable.
　（Ｈ）成分の含有量は、（Ａ）成分、必要に応じて含有する（Ｆ）成分、必要に応じて含有する（Ｇ）成分ならびに必要に応じて含有する（Ｈ）成分の合計１００質量部中、４０質量部以下が好ましく、３～４０質量部がより好ましく、５～２０質量部が最も好ましく、１０～２０質量部が更に好ましい。 Content of (H) component is 100 mass in total of (A) component, (F) component contained as needed, (G) component contained as needed, and (H) component contained as needed. The amount is preferably 40 parts by mass or less, more preferably 3 to 40 parts by mass, most preferably 5 to 20 parts by mass, and still more preferably 10 to 20 parts by mass.
　（Ａ）成分と、（Ｆ）成分、（Ｇ）成分、（Ｈ）成分の全てとを含む場合、（Ａ）成分、（Ｆ）成分、（Ｇ）成分、（Ｈ）成分の使用量は、（Ａ）成分、（Ｆ）成分、（Ｇ）成分、（Ｈ）成分の合計１００質量部中、（Ａ）成分：（Ｆ）成分：（Ｇ）成分：（Ｈ）成分（単位は質量部）＝３０～７０：５～５０：５～５０：２～３０が好ましく、４０～７０：１０～４０：１０～４０：４～２０がより好ましい。 When (A) component and all of (F) component, (G) component, and (H) component are included, the usage amount of (A) component, (F) component, (G) component, (H) component is , (A) component, (F) component, (G) component, (H) component in total 100 parts by mass, (A) component: (F) component: (G) component: (H) component (unit is mass) Part) = 30 to 70: 5 to 50: 5 to 50: 2 to 30 is preferable, and 40 to 70:10 to 40:10 to 40: 4 to 20 is more preferable.
　（Ｂ）成分の使用量は、（Ａ）成分、必要に応じて含有する（Ｆ）成分、必要に応じて含有する（Ｇ）成分、必要に応じて含有する（Ｈ）成分の合計１００質量部に対して、１～１０質量部が好ましく、２～４質量部がより好ましい。 The amount of component (B) used is a total of 100 masses of component (A), component (F) contained if necessary, component (G) contained if necessary, and component (H) contained if necessary. The amount is preferably 1 to 10 parts by mass and more preferably 2 to 4 parts by mass with respect to parts.
　（Ｃ）成分の使用量は、（Ａ）成分、必要に応じて含有する（Ｆ）成分、必要に応じて含有する（Ｇ）成分、必要に応じて含有する（Ｈ）成分の合計１００質量部に対して、０．０１～３．５質量部が好ましく、０．１～１．５質量部がより好ましい。 The amount of component (C) used is a total of 100 masses of component (A), component (F) contained if necessary, component (G) contained if necessary, and component (H) contained if necessary. The amount is preferably 0.01 to 3.5 parts by weight, more preferably 0.1 to 1.5 parts by weight with respect to parts.
　（Ｄ）成分の使用量は、（Ａ）成分、必要に応じて含有する（Ｆ）成分、必要に応じて含有する（Ｇ）成分、必要に応じて含有する（Ｈ）成分の合計１００質量部に対して、０．０１～１５質量部が好ましく、０．５～１０質量部がより好ましい。 The amount of component (D) used is a total of 100 masses of component (A), component (F) contained if necessary, component (G) contained if necessary, and component (H) contained if necessary. The amount is preferably 0.01 to 15 parts by weight, more preferably 0.5 to 10 parts by weight with respect to parts.
　（Ｅ）成分の使用量は、（Ａ）成分、必要に応じて含有する（Ｆ）成分、必要に応じて含有する（Ｇ）成分、必要に応じて含有する（Ｈ）成分の合計１００質量部に対して、０．０１～５質量部が好ましく、０．０５～３質量部がより好ましい。 The amount of component (E) used is a total of 100 masses of component (A), component (F) contained if necessary, component (G) contained if necessary, and component (H) contained if necessary. The amount is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass with respect to parts.
　なお、特許文献４～８にはいずれにも、本発明において必須の成分である、（Ｂ）カルボキシル基含有（メタ）アクリレートの含有量、（Ｃ）熱ラジカル重合開始剤の含有量、（Ｄ）光ラジカル重合開始剤の含有量、（Ｅ）酸化防止剤の含有量を特定範囲に設定し、所期の効果を発揮させることについては何ら記載がない。 In all of Patent Documents 4 to 8, the content of (B) carboxyl group-containing (meth) acrylate, which is an essential component in the present invention, (C) the content of thermal radical polymerization initiator, (D There is no description about setting the content of the photo-radical polymerization initiator and the content of the (E) antioxidant within a specific range to exert the desired effect.
　また、（Ｉ）成分を含む場合、（Ｉ）成分の使用量は、（Ａ）成分、必要に応じて含有する（Ｆ）成分、必要に応じて含有する（Ｇ）成分、必要に応じて含有する（Ｈ）成分の合計１００質量部に対して、１～１０質量部が好ましく、３～８質量部がより好ましい。 Moreover, when (I) component is included, the usage-amount of (I) component is (A) component, (F) component contained as needed, (G) component contained as needed, as needed 1 to 10 parts by mass is preferable and 3 to 8 parts by mass is more preferable with respect to 100 parts by mass in total of the component (H) to be contained.
　本発明の硬化性組成物は、本発明の目的を損なわない範囲で、一般に使用されているアクリルゴム、ウレタンゴム等の各種エラストマー、メタクリル酸メチル－ブタジエン－スチレン系グラフト共重合体やアクリロニトリル－ブタジエン－スチレン系グラフト共重合体等のグラフト共重合体、溶剤、増量材、補強材、可塑剤、増粘剤、染料、顔料、難燃剤、界面活性剤及び充填剤等を使用することができる。 The curable composition of the present invention includes various commonly used elastomers such as acrylic rubber and urethane rubber, methyl methacrylate-butadiene-styrene graft copolymer, and acrylonitrile-butadiene as long as the object of the present invention is not impaired. -Graft copolymers such as styrene-based graft copolymers, solvents, extenders, reinforcing materials, plasticizers, thickeners, dyes, pigments, flame retardants, surfactants and fillers can be used.
　本発明の硬化性組成物は、エネルギー線を照射することにより硬化することに加え、熱により硬化させ、硬化体としてもよい。 The curable composition of the present invention may be cured by heat in addition to being cured by irradiating with energy rays to form a cured product.
　本発明の硬化性組成物は接着剤として好適に用いることができる。この接着剤は、ＣＤ、ＤＶＤ、青色半導体レーザに対応したＢｌｕ－ｒａｙディスク、ＨＤ－ＤＶＤ等の光記録媒体の再生・記録に用いられる光ピックアップ装置、液晶、有機エレクトロルミネッセンス等のディスプレイ部品、ＣＣＤ、ＣＭＯＳといったイメージセンサー等の電子部品、半導体部品等で用いられる素子パッケージ等のエレクトロニクス分野、太陽電池モジュールの部材での接着に、好適に用いることができる。本発明の硬化性組成物は、工芸ガラスの台座、皿の固定用途、レンズ、プリズム、カメラ、双眼鏡及び顕微鏡等に用いられる光学素子においても、好適な接着剤となる。 The curable composition of the present invention can be suitably used as an adhesive. This adhesive is an optical pickup device used for reproducing and recording optical recording media such as CD, DVD, blue semiconductor laser, Blu-ray disc, HD-DVD, etc., display components such as liquid crystal and organic electroluminescence, CCD It can be suitably used for electronic parts such as electronic components such as image sensors such as CMOS, semiconductor packages, etc., and bonding with solar cell module members. The curable composition of the present invention is also a suitable adhesive for optical elements used for craft glass pedestals, plate fixing applications, lenses, prisms, cameras, binoculars, microscopes, and the like.
［製造方法］
　本発明の硬化性組成物の製造方法については、組成物が硬化しない程度に過度の熱がかからない条件にて、上記の材料を十分に混合できれば特に制限はない。材料の混合方法としては、プロペラの回転に伴う撹拌力を利用する撹拌法等が挙げられる。これらの混合方法は、低コストで、安定した混合を行えるので好ましい。 [Production method]
About the manufacturing method of the curable composition of this invention, there will be no restriction | limiting in particular if said material is fully mixed on the conditions which do not apply excessive heat to such an extent that a composition does not harden | cure. Examples of the material mixing method include a stirring method using a stirring force accompanying rotation of the propeller. These mixing methods are preferable because stable mixing can be performed at low cost.
　上記の混合を行った後、下記の光源を用いたエネルギー線の照射により硬化性組成物の硬化を行ってもよい。 After the above-mentioned mixing, the curable composition may be cured by irradiation with energy rays using the following light source.
〔光源〕
　本発明の実施形態において、硬化性組成物の硬化、接着に用いられる光源としては、ハロゲンランプ、メタルハライドランプ、ハイパワーメタルハライドランプ（インジウム等を含有する）、低圧水銀ランプ、高圧水銀ランプ、超高圧水銀ランプ、キセノンランプ、キセノンエキシマランプ、キセノンフラッシュランプ、ライトエミッティングダイオード（以下、ＬＥＤという）等が挙げられる。これらの光源は、それぞれの光ラジカル重合開始剤の反応波長に対応したエネルギー線の照射を効率よく行えるので好ましい。 〔light source〕
In the embodiment of the present invention, the light source used for curing and bonding the curable composition includes a halogen lamp, a metal halide lamp, a high-power metal halide lamp (containing indium, etc.), a low-pressure mercury lamp, a high-pressure mercury lamp, and an ultra-high pressure. Examples thereof include a mercury lamp, a xenon lamp, a xenon excimer lamp, a xenon flash lamp, and a light emitting diode (hereinafter referred to as LED). These light sources are preferable because they can efficiently irradiate energy rays corresponding to the reaction wavelengths of the respective radical photopolymerization initiators.
　上記光源は、各々放射波長、エネルギー分布が異なるため、光ラジカル重合開始剤の反応波長等により適宜選択される。自然光（太陽光）も反応開始光源になり得る。上記光源により、直接照射、反射鏡等による集光照射、ファイバー等による集光照射を行ってもよい。低波長カットフィルター、熱線カットフィルター、コールドミラー等も用いることもできる。 The light source is appropriately selected depending on the reaction wavelength of the photo-radical polymerization initiator because the radiation wavelength and energy distribution are different. Natural light (sunlight) can also be a reaction initiation light source. You may perform direct irradiation, condensing irradiation by a reflective mirror, condensing irradiation by a fiber, etc. with the said light source. A low wavelength cut filter, a heat ray cut filter, a cold mirror, or the like can also be used.
　以下に、実験例を挙げて、本発明を更に詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to experimental examples, but the present invention is not limited thereto.
　実験例では、以下の化合物を使用した。 In the experimental example, the following compounds were used.
　（Ａ）成分の（メタ）アクリル変性オリゴマーとして下記を用いた。
　（Ａ－１）両末端メタクリレート変性ブタジエン系オリゴマー（日本曹達社製「ＴＥ－２０００」、末端アクリル変性ポリブタジエン）（ＧＰＣによるポリスチレン換算の数平均分子量２１００）
　（Ａ－２）両末端アクリレート変性水素添加ブタジエン系オリゴマー（日本曹達社製「ＴＥＡＩ－１０００」、末端アクリル変性水素添加ポリブタジエン）（ＧＰＣによるポリスチレン換算の数平均分子量２２５０） The following was used as the (meth) acryl-modified oligomer of component (A).
(A-1) Both-end methacrylate modified butadiene oligomer (“TE-2000” manufactured by Nippon Soda Co., Ltd., terminal acrylic-modified polybutadiene) (number average molecular weight 2100 in terms of polystyrene by GPC)
(A-2) Both-end acrylate-modified hydrogenated butadiene oligomer (“TEAI-1000” manufactured by Nippon Soda Co., Ltd., terminal acrylic-modified hydrogenated polybutadiene) (Number average molecular weight 2250 in terms of polystyrene by GPC)
　（Ｂ）成分のカルボキシル基含有（メタ）アクリレートとして下記を用いた。
　（Ｂ－１）２－メタクリロイルオキシエチルコハク酸（共栄社化学社製「ライトエステルＨＯ－ＭＳ」）
　（Ｂ－２）フタル酸モノヒドロキシエチルアクリレート（東亜合成社製「Ｍ－５４００」）
　（Ｂ－３）２－メタクリロイルオキシエチルヘキサヒドロフタル酸（共栄社化学社製「ライトエステルＨＯ－ＨＨ」） The following was used as the carboxyl group-containing (meth) acrylate of component (B).
(B-1) 2-Methacryloyloxyethyl succinic acid (“Light Ester HO-MS” manufactured by Kyoeisha Chemical Co., Ltd.)
(B-2) Monohydroxyethyl acrylate phthalate (“M-5400” manufactured by Toa Gosei Co., Ltd.)
(B-3) 2-Methacryloyloxyethyl hexahydrophthalic acid (“Kyoeisha Chemical Co., Ltd.“ Light Ester HO—HH ”)
　（Ｃ）成分の熱ラジカル重合開始剤として下記を用いた。
　（Ｃ－１）ｔ－ブチルパーオキシ２－エチルヘキシルカーボネート（化薬アクゾ社製「トリゴノックス１１７」、１時間半減期温度１１７℃、貯蔵最高温度３５℃、２５℃にて液状）
　（Ｃ－２）ｔ－アミルパーオキシ２－エチルヘキシルカーボネート（アルケマ吉富社製「ルペロックスＴＡＩＣ」、１時間半減期温度１１７℃、貯蔵最高温度３８℃、２５℃にて液状）
　（Ｃ－３）ｔ－ブチルパーオキシ３，５，５－トリメチルヘキサノエート（化薬アクゾ社製「トリゴノックス４２」、１時間半減期温度１１９℃、貯蔵最高温度３５℃、２５℃にて液状）
　（Ｃ－４）ｔ－アミルパーオキシ３，５，５－トリメチルヘキサノエート（化薬アクゾ社製「カヤエステルＡＮ」、１時間半減期温度１１４℃、貯蔵最高温度３５℃、２５℃にて液状）
比較として、下記の熱ラジカル重合開始剤を用いた。
　（Ｃ－５）ジ（２－エチルヘキシル）パーオキシジカーボネート（アルケマ吉富社製「ルペロックス２２３」、１時間半減期温度６６℃、貯蔵最高温度－１０℃、２５℃にて液状）
　（Ｃ－６）２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキサン（化薬アクゾ社製「カヤヘキサＡＤ」、１時間半減期温度１３８℃、貯蔵最高温度３５℃、２５℃にて液状） The following was used as the thermal radical polymerization initiator of component (C).
(C-1) t-butylperoxy 2-ethylhexyl carbonate (“Trigonox 117” manufactured by Kayaku Akzo Co., Ltd., liquid at 1 hour half-life temperature of 117 ° C., maximum storage temperature of 35 ° C. and 25 ° C.)
(C-2) t-amylperoxy 2-ethylhexyl carbonate (“Lupelox TAIC” manufactured by Arkema Yoshitomi, 1 hour half-life temperature 117 ° C., maximum storage temperature 38 ° C., liquid at 25 ° C.)
(C-3) t-butylperoxy 3,5,5-trimethylhexanoate (“Trigonox 42” manufactured by Kayaku Akzo Co., Ltd.) 1 hour half-life temperature 119 ° C., maximum storage temperature 35 ° C., 25 ° C. )
(C-4) t-amylperoxy 3,5,5-trimethylhexanoate (“Kayaester AN” manufactured by Kayaku Akzo Co., Ltd., 1 hour half-life temperature of 114 ° C., maximum storage temperature of 35 ° C., 25 ° C. Liquid)
For comparison, the following thermal radical polymerization initiator was used.
(C-5) Di (2-ethylhexyl) peroxydicarbonate (“Lupelox 223” manufactured by Arkema Yoshitomi Co., Ltd., liquid at 1 hour half-life temperature of 66 ° C., maximum storage temperature of −10 ° C. and 25 ° C.)
(C-6) 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (“Kayahexa AD” manufactured by Kayaku Akzo Co., Ltd.), 1 hour half-life temperature of 138 ° C., maximum storage temperature of 35 ° C., 25 Liquid at ℃)
　（Ｄ）成分の光ラジカル重合開始剤として下記を用いた。
　（Ｄ－１）１－ヒドロキシシクロヘキシルフェニルケトン（チバ・スペシャルティー・ケミカルズ社製「ＩＲＧＡＣＵＲＥ１８４」）
　（Ｄ－２）ベンジルジメチルケタール（チバ・スペシャルティー・ケミカルズ社製「ＩＲＧＡＣＵＲＥ６５１」） The following was used as the radical photopolymerization initiator of component (D).
(D-1) 1-hydroxycyclohexyl phenyl ketone (“IRGACURE184” manufactured by Ciba Specialty Chemicals)
(D-2) Benzyldimethyl ketal (“IRGACURE651” manufactured by Ciba Specialty Chemicals)
　（Ｅ）酸化防止剤として下記を用いた。
　（Ｅ－１）２，２－メチレン－ビス（４－メチル－６－ターシャリーブチルフェノール）（住友化学社製「スミライザーＭＤＰ－Ｓ」） (E) The following was used as an antioxidant.
(E-1) 2,2-methylene-bis (4-methyl-6-tertiary butylphenol) (“Sumilyzer MDP-S” manufactured by Sumitomo Chemical Co., Ltd.)
　（Ｆ）多官能（メタ）アクリレートとして下記を用いた。
　（Ｆ－１）ジメチロール－トリシクロデカンジアクリレート（共栄社化学社製「ライトアクリレートＤＣＰ－Ａ」）
　（Ｆ－２）トリメチロールプロパントリメタクリレート（共栄社化学社製「ライトエステルＴＭＰ」） (F) The following was used as the polyfunctional (meth) acrylate.
(F-1) Dimethylol-tricyclodecane diacrylate (“Light acrylate DCP-A” manufactured by Kyoeisha Chemical Co., Ltd.)
(F-2) Trimethylolpropane trimethacrylate (“Kyoeisha Chemical Co., Ltd.“ Light Ester TMP ”)
　（Ｇ）飽和脂環式炭化水素基を有する単官能（メタ）アクリレートとして下記を用いた。
　（Ｇ－１）イソボルニルメタクリレート（共栄社化学社製「ライトエステルＩＢＸ」）
　（Ｇ－２）ジシクロペンタニルメタクリレート（日立化成工業社製「ファンクリルＦＡ－５１３Ｍ」）
　（Ｇ－３）２－メチル－２－アダマンチルメタクリレート（出光興産社製「アダマンテートＭＭ」） (G) The following was used as a monofunctional (meth) acrylate having a saturated alicyclic hydrocarbon group.
(G-1) Isobornyl methacrylate (Kyoeisha Chemical Co., Ltd. “Light Ester IBX”)
(G-2) Dicyclopentanyl methacrylate (“Fancryl FA-513M” manufactured by Hitachi Chemical Co., Ltd.)
(G-3) 2-Methyl-2-adamantyl methacrylate (“Adamantate MM” manufactured by Idemitsu Kosan Co., Ltd.)
　（Ｈ）水酸基含有（メタ）アクリレートとして下記を用いた。
　（Ｈ－１）２－ヒドロキシエチルメタクリレート（共栄社化学社製「ライトエステルＨＯ」）
　（Ｈ－２）２－ヒドロキシブチルメタクリレート（共栄社化学社製「ライトエステルＨＯＢ」）」） (H) The following was used as the hydroxyl group-containing (meth) acrylate.
(H-1) 2-hydroxyethyl methacrylate (Kyoeisha Chemical Co., Ltd. “Light Ester HO”)
(H-2) 2-hydroxybutyl methacrylate (Kyoeisha Chemical Co., Ltd. “Light Ester HOB”))
　（Ｉ）シランカップリング剤として下記を用いた。
　（Ｉ－１）３－メタクリロキシプロピルトリメトキシシラン（モメンティブ・パフォーマンス・マテリアル社製「Ａ－１７４」）を使用した。 (I) The following was used as a silane coupling agent.
(I-1) 3-Methacryloxypropyltrimethoxysilane (“A-174” manufactured by Momentive Performance Materials) was used.
（実験例１～２３）
　表１～３に示す種類の原材料を、表１～３に示す組成割合（単位は質量部）で混合し、実験例１～２３の硬化性組成物を調製した。結果を表１～３に示した。 (Experimental Examples 1 to 23)
Raw materials of the types shown in Tables 1 to 3 were mixed in the composition ratios (units are parts by mass) shown in Tables 1 to 3, and curable compositions of Experimental Examples 1 to 23 were prepared. The results are shown in Tables 1-3.
〔光硬化性評価（引張剪断接着強さ）〕
　引張せん断接着強さ：ＪＩＳ　Ｋ　６８５０に従い測定した。具体的には被着体とした耐熱ガラス（商品名「耐熱パイレックス（登録商標）ガラス」、幅２５ｍｍ×長さ２５ｍｍ×厚さ２．０ｍｍ）を用いて、接着部位を直径８ｍｍの円形として、作製した該組成物にて、２枚の耐熱ガラスを張り合わせ、ＵＶ照射器を使用し、積算光量３０００ｍＪ／ｃｍ2（３６５ｎｍの照度：１５０ｍＷ／ｃｍ2、ＨＯＹＡＣＡＮＤＥＯ ＯＰＴＲＯＮＩＣＳ社製「ＥＸＥＣＵＲＥ３０００（水銀キセノンランプ搭載ＵＶ硬化装置）」）の条件にて硬化させ、引張強さ試験片を作製した。作製した試験片は、万能試験機を使用して、２３℃、湿度５０％の環境下、引張せん断接着強さを測定した。 [Photo-curability evaluation (tensile shear bond strength)]
Tensile shear bond strength: measured in accordance with JIS K 6850. Specifically, using a heat-resistant glass (trade name “heat-resistant Pyrex (registered trademark) glass”, width 25 mm × length 25 mm × thickness 2.0 mm) as an adherend, the adhesion site is a circle having a diameter of 8 mm, Two heat-resistant glasses are bonded to each other with the prepared composition, and a UV irradiator is used, and the integrated light quantity is 3000 mJ / cm 2 (365 nm illuminance: 150 mW / cm 2 , “EXECURE 3000 (mercury xenon lamp mounted) manufactured by Hoyacadeo Optronics. Curing was performed under the conditions of the UV curing apparatus))) to prepare a tensile strength test piece. The produced test piece was measured for tensile shear bond strength in an environment of 23 ° C. and humidity of 50% using a universal testing machine.
〔熱硬化性評価（引張剪断接着強さ）〕
　引張せん断接着強さ：ＪＩＳ　Ｋ　６８５０に従い測定した。具体的には被着体とした耐熱ガラス（商品名「耐熱パイレックス（登録商標）ガラス」、幅２５ｍｍ×長さ２５ｍｍ×厚さ２．０ｍｍ）を用いて、接着部位を直径８ｍｍの円形として、作製した該組成物にて、２枚の耐熱ガラスを張り合わせ、乾燥機を使用し、１５０℃、１０分間の条件にて硬化させ、引張強さ試験片を作製した。作製した試験片は、万能試験機を使用して、２３℃、湿度５０％の環境下、引張せん断接着強さを測定した。 [Thermosetting evaluation (tensile shear bond strength)]
Tensile shear bond strength: measured in accordance with JIS K 6850. Specifically, using a heat-resistant glass (trade name “heat-resistant Pyrex (registered trademark) glass”, width 25 mm × length 25 mm × thickness 2.0 mm) as an adherend, the adhesion site is a circle having a diameter of 8 mm, Two sheets of heat-resistant glass were bonded together with the prepared composition, and cured using a dryer at 150 ° C. for 10 minutes to prepare a tensile strength test piece. The produced test piece was measured for tensile shear bond strength in an environment of 23 ° C. and humidity of 50% using a universal testing machine.
〔貯蔵安定性試験〕
　該組成物の初期粘度（Ｖ0）を測定した後、容器に入れて蓋をした状態（密閉系）にし、５℃の環境下で３ヵ月後の該組成物の粘度（Ｖ3）を測定した。そして、式：Ｖ3／Ｖ0にしたがって粘度変化率を求めた。粘度変化率が２以下のものを保存貯蔵安定性良好と判断した。 [Storage stability test]
After measuring the initial viscosity (V 0 ) of the composition, put it in a container and cover it (sealed system), and measure the viscosity (V 3 ) of the composition after 3 months in an environment of 5 ° C. did. The viscosity change rate was determined according to the formula: V 3 / V 0 . Those having a viscosity change rate of 2 or less were judged to have good storage and storage stability.
〔粘度の測定〕
　該組成物の粘度はＥ型粘度計を用い、温度２５℃の条件下で測定した。 (Measurement of viscosity)
The viscosity of the composition was measured using an E-type viscometer at a temperature of 25 ° C.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　以上のように、本実施例の硬化性組成物は、エネルギー線を照射することにより硬化することに加え、熱により硬化することも可能である。本実施例の硬化性組成物は、密着性が高い。熱ラジカル重合開始剤の１時間半減期温度を１２７℃以下にすることにより、密着性が更に向上する。熱ラジカル重合開始剤の貯蔵最高温度を２６～４０℃にすることにより、貯蔵安定性に優れる。実験例１４は、貯蔵最高温度が２６～４０℃の範囲外であるが、密着性に優れる。実験例１５は、（Ｃ）成分の１時間半減期温度が１２７℃を超えるが、密着性に優れる。 As described above, the curable composition of the present example can be cured by heat in addition to being cured by irradiation with energy rays. The curable composition of this example has high adhesion. By setting the one-hour half-life temperature of the thermal radical polymerization initiator to 127 ° C. or less, the adhesion is further improved. By setting the maximum storage temperature of the thermal radical polymerization initiator to 26 to 40 ° C., the storage stability is excellent. In Experimental Example 14, the maximum storage temperature is outside the range of 26 to 40 ° C., but the adhesion is excellent. In Experimental Example 15, the 1-hour half-life temperature of the component (C) exceeds 127 ° C., but the adhesion is excellent.
　本発明の硬化性組成物は、エネルギー線を照射することにより硬化することに加え、遮光エリアを熱により硬化することが可能である。本発明の硬化性組成物は、１時間半減期温度、貯蔵最高温度を設定することにより、１剤型であっても貯蔵安定性に優れ、作業性も良好で、密着性が高い接着剤を提供できる。 The curable composition of the present invention can be cured by irradiating energy rays, and in addition, the light shielding area can be cured by heat. The curable composition of the present invention is an adhesive that has excellent storage stability, good workability, and high adhesiveness even if it is a one-component type by setting the half-life temperature for 1 hour and the maximum storage temperature. Can be provided.
　本発明の硬化性組成物は、１剤型組成物として使用可能な貯蔵安定性を有すると共に、光の透過性が異なる材料間を固定する接着剤として、密着性に優れるので、産業上産業上非常に有用である。 The curable composition of the present invention has storage stability that can be used as a one-part composition, and has excellent adhesion as an adhesive that fixes materials having different light transmission properties. Very useful.

Claims (14)

  1. 　（Ａ）分子の末端又は側鎖に１個以上の（メタ）アクリロイル基を有し、ポリブタジエン、ポリイソプレン、及び、これらの水素添加物からなる群から選ばれる１種以上である（メタ）アクリル変性オリゴマー、（Ａ）成分、および必要に応じて含有する（Ｆ）多官能（メタ）アクリレート、必要に応じて含有する（Ｇ）飽和脂環式炭化水素基を有する単官能（メタ）アクリレートならびに必要に応じて含有する（Ｈ）水酸基含有（メタ）アクリレートの合計１００質量部に対して、（Ｂ）カルボキシル基含有（メタ）アクリレート１～１０質量部、（Ｃ）熱ラジカル重合開始剤０．０１～３．５質量部、（Ｄ）光ラジカル重合開始剤０．０１～１５質量部、および（Ｅ）酸化防止剤０．０１～５質量部を含有する硬化性組成物。 (A) One or more (meth) acrylic compounds having one or more (meth) acryloyl groups at the terminal or side chain of the molecule and selected from the group consisting of polybutadiene, polyisoprene, and hydrogenated products thereof Modified oligomer, component (A), and optionally contained (F) polyfunctional (meth) acrylate, optionally contained (G) monofunctional (meth) acrylate having a saturated alicyclic hydrocarbon group, and (B) 1 to 10 parts by mass of (B) carboxyl group-containing (meth) acrylate, (C) thermal radical polymerization initiator, based on a total of 100 parts by mass of (H) hydroxyl group-containing (meth) acrylate contained as required. A curable composition containing 01 to 3.5 parts by mass, (D) a radical photopolymerization initiator 0.01 to 15 parts by mass, and (E) an antioxidant 0.01 to 5 parts by mass.
  2. 　前記（Ｃ）成分が１時間半減期温度１２７℃以下である請求項１に記載の硬化性組成物。 The curable composition according to claim 1, wherein the component (C) has a one-hour half-life temperature of 127 ° C or lower.
  3. 　前記（Ｃ）成分が貯蔵最高温度２６～４０℃である請求項１又は２に記載の硬化性組成物。 The curable composition according to claim 1 or 2, wherein the component (C) has a maximum storage temperature of 26 to 40 ° C.
  4. 　前記（Ｃ）成分が２５℃にて液状である請求項１～３のいずれか１項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 3, wherein the component (C) is liquid at 25 ° C.
  5. 　前記（Ｂ）成分が２－（メタ）アクリロイルオキシエチルジカルボン酸モノエステルを含有する請求項１～４のいずれか１項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 4, wherein the component (B) contains 2- (meth) acryloyloxyethyl dicarboxylic acid monoester.
  6. 　更に（Ｆ）多官能（メタ）アクリレートを含有する請求項１～５のいずれか１項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 5, further comprising (F) a polyfunctional (meth) acrylate.
  7. 　前記（Ｆ）成分が脂環式構造を有する多官能（メタ）アクリレートである請求項６に記載の硬化性組成物。 The curable composition according to claim 6, wherein the component (F) is a polyfunctional (meth) acrylate having an alicyclic structure.
  8. 　更に（Ｇ）飽和脂環式炭化水素基を有する単官能（メタ）アクリレートを含有する請求項１～７のいずれか１項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 7, further comprising (G) a monofunctional (meth) acrylate having a saturated alicyclic hydrocarbon group.
  9. 　前記（Ｇ）成分がイソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、２－メチル－２－アダマンチル（メタ）アクリレートからなる群から選択される少なくとも１種である請求項８に記載の硬化性組成物。 The component (G) is at least one selected from the group consisting of isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and 2-methyl-2-adamantyl (meth) acrylate. Curable composition.
  10. 　更に（Ｈ）水酸基含有（メタ）アクリレートを含有する請求項１～９のいずれか一項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 9, further comprising (H) a hydroxyl group-containing (meth) acrylate.
  11. 　更に（Ｉ）シランカップリング剤を含有する請求項１～１０のいずれか一項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 10, further comprising (I) a silane coupling agent.
  12. 　請求項１～１１のいずれか一項に記載の硬化性組成物からなる接着剤。 An adhesive comprising the curable composition according to any one of claims 1 to 11.
  13. 　請求項１２に記載の接着剤を用いてなる接合体。 A joined body using the adhesive according to claim 12.
  14. 　請求項１～１１のいずれか一項に記載の硬化性組成物を硬化してなる硬化体。 A cured product obtained by curing the curable composition according to any one of claims 1 to 11.
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