WO2012005169A1 - Curable resin composition - Google Patents

Curable resin composition Download PDF

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Publication number
WO2012005169A1
WO2012005169A1 PCT/JP2011/065075 JP2011065075W WO2012005169A1 WO 2012005169 A1 WO2012005169 A1 WO 2012005169A1 JP 2011065075 W JP2011065075 W JP 2011065075W WO 2012005169 A1 WO2012005169 A1 WO 2012005169A1
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WO
WIPO (PCT)
Prior art keywords
component
meth
acrylate
resin composition
curable resin
Prior art date
Application number
PCT/JP2011/065075
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French (fr)
Japanese (ja)
Inventor
佑基 比舎
公彦 依田
渡辺　淳
Original Assignee
電気化学工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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 JP2012523839A priority Critical patent/JPWO2012005169A1/en
Priority to CN201180033945.8A priority patent/CN102985446B/en
Priority to KR1020137001959A priority patent/KR20130091318A/en
Publication of WO2012005169A1 publication Critical patent/WO2012005169A1/en

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Classifications

    • 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
    • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • 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
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • 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
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2202/00—Materials and properties
    • G02F2202/28—Adhesive materials or arrangements

Definitions

  • the present invention relates to a curable resin composition.
  • the present invention relates to an adhesive composition comprising a curable resin composition.
  • the capacitive touch panel has a structure in which a transparent electrode is formed on a transparent substrate and a transparent plate is bonded thereon.
  • the bonding of the decorative plate and the touch panel, the bonding of the icon sheet and the touch panel, and the bonding of the transparent substrate and the transparent plate have used an adhesive.
  • the technique using such an adhesive has a problem of insufficient adhesion.
  • Patent Document 1 proposes a curable adhesive composition for touch panel adhesion containing (A) a (meth) acrylate oligomer having a polyisoprene, polybutadiene or polyurethane as a skeleton and (B) a softening component.
  • Patent Document 2 a (meth) acrylic monomer mainly composed of isobornyl (meth) acrylate is used for the purpose of excellent workability, long-term reliability, quick curing, and further adhesion and moisture resistance.
  • UV curable type comprising 100 parts by weight, 25-100 parts by weight of a prepolymer having polybutadiene in the main chain and having one or more (meth) acryl groups at both ends or side chains of the main chain, and a photopolymerization initiator
  • An adhesive composition is proposed.
  • Patent Document 3 discloses polyurethane acrylate, polyisoprene acrylate or the like as a resin composition for forming a cured resin layer interposed between an image display portion of an image display device and a translucent protective portion.
  • One or more polymers such as esterified products, terpene hydrogenated resins, butadiene polymers, one or more acrylate monomers such as isobornyl acrylate, dicyclopentenyloxyethyl methacrylate, 2-hydroxybutyl methacrylate, and 1
  • a resin composition containing a photopolymerization initiator such as -hydroxy-cyclohexyl-phenyl-ketone is disclosed.
  • Patent Document 1 discloses phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, nonylphenol EO adduct (meth) acrylate, methoxytri Cyclic (meth) acrylates such as (meth) acrylate monomers selected from ethylene glycol (meth) acrylate and tetrahydrofurfuryl (meth) acrylate are used.
  • Patent Documents 2 and 3 since it is a highly elastic resin based on a rigid skeleton monomer such as isobornyl (meth) acrylate and dicyclopentenyl (meth) acrylate, it is difficult to expand and contract the adherend in a high-temperature reliability test. It could not endure and could cause peeling.
  • the present invention has been made in view of the above circumstances. For example, when a decorative plate and an icon sheet used for a display body such as a touch panel are bonded together, when a transparent substrate and a transparent plate are bonded together, printing processing is performed. When pasting parts, it is difficult to provide sufficient initial adhesion and wet heat resistance, or when the display body and optical functional material are pasted together, the adhesive surface may peel off or display Provided is a curable resin composition that solves the problem of the prior art that the body glass is broken.
  • the present invention contains the following components (A) to (D), and the total amount of the components (A) and (B) accounts for 80 to 99% by mass of the curable resin composition.
  • the amount of component (D) used is a curable resin composition that is 0 to 10 parts by mass in a total of 100 parts by mass of component (A), component (B) and component (D).
  • (meth) acrylate (meth) acrylate,
  • the curable resin composition of the present invention is a compound of component (B), the general formula (1).
  • General formula (1) Z—O—R 1 Wherein, Z is shown a (meth) acryloyl group, R 1 represents a number 9-20 alkyl group having a carbon. ]
  • the component (A) in a total of 100 parts by mass of the component (A) and the component (B), the component (A) is 30 to 98 parts by mass, and the component (B) is 2 to 70 parts by mass.
  • the component (B) is isostearyl (meth) acrylate, lauryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-ethylhexyl. From (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 2-hydroxypropyl (meth) acrylate One or more members of the group.
  • the component (B) is lauryl (meth) acrylate and / or isostearyl (meth) acrylate.
  • a silane coupling agent is further contained as the component (E).
  • the diene-based or hydrogenated diene-based skeleton of the component (A) is polybutadiene, polyisoprene, a hydrogenated polybutadiene, and a hydrogen of polyisoprene.
  • the molecular weight of the oligomer (A) having a diene-based or hydrogenated diene-based skeleton is 500 to 70000.
  • the component (A) is 50 to 90 parts by mass
  • the component (B) is a total of 100 parts by mass of the component (A) and the component (B).
  • the amount of the component (C) used is 0.01 to 10 parts by mass with respect to 100 parts by mass in total of the components (A), (B) and (D).
  • the amount of the component (E) used is 0.01 to 10 parts by mass with respect to 100 parts by mass in total of the components (A), (B) and (D).
  • the present invention is an adhesive composition comprising the curable resin composition described above.
  • the present invention provides a cured product of an adhesive composition comprising the curable resin composition described above.
  • the present invention is a composite in which the adherend is coated or bonded to each other by the cured body described above.
  • the adherend described above is a composite that is at least one selected from the group consisting of triacetylcellulose, a fluorine-based polymer, polyester, polycarbonate, polyolefin, glass, and metal. .
  • the present invention is a touch panel laminate in which an adherend is bonded using the adhesive composition described above.
  • the present invention is a display including the touch panel laminate described above.
  • the curable resin composition of the present invention exhibits high initial adhesion and wet heat resistance.
  • the component (A) in the present invention is an oligomer having a diene-based or hydrogenated diene-based skeleton.
  • the main chain skeleton of the oligomer in the present invention is a diene-based or hydrogenated diene-based skeleton.
  • the diene-based or hydrogenated diene-based skeleton is preferably at least one skeleton selected from the group consisting of polybutadiene, polyisoprene, a hydrogenated polybutadiene, and a hydrogenated polyisoprene.
  • at least one selected from the group consisting of polybutadiene and polyisoprene is preferable, and polybutadiene is more preferable in terms of high adhesion durability.
  • the oligomer preferably has one or more (meth) acryloyl groups at the terminal 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.
  • the molecular weight of the oligomer is preferably 500 to 70000, more preferably 1000 to 60000, and most preferably 1000 to 55000. If molecular weight is 500 or more, since the hardness of the hardening body obtained by irradiating light to the curable resin composition of this invention is high, it will become easy to form an adhesive bond layer. If the molecular weight is 70,000 or less, the viscosity of the resulting curable resin composition is small, so that the workability in mixing during the production process and the workability in practical applications are improved.
  • the molecular weight of the oligomer refers to the number average molecular weight calculated as the average molecular weight per molecule.
  • the number average molecular weight of polystyrene conversion measured by GPC gel permeation chromatography
  • oligomer of the component (A) “UC-203” manufactured by Kuraray (esterified oligomer of maleic anhydride adduct of isoprene polymer and 2-hydroxyethyl methacrylate), “LIR-50” (isoprene manufactured by Kuraray) Oligomer), Kuraray “LBR-50” “LBR-307” (butadiene oligomer), Nippon Soda "TEAI-1000” (terminal acrylic modified hydrogenated 1,2-polybutadiene oligomer), Nippon Soda "TE -2000 "(terminal methacryl-modified 1,2-polybutadiene oligomer) and the like.
  • esterified oligomers of maleic anhydride adduct of isoprene polymer and 2-hydroxyethyl (meth) acrylate isoprene oligomers
  • terminal (meth) acryl-modified 1,2-polybutadiene oligomers Preferably, one or more members of the group consisting of an esterified oligomer of maleic anhydride adduct of isoprene polymer and 2-hydroxyethyl (meth) acrylate and / or a terminal (meth) acryl-modified 1,2-polybutadiene oligomer are used.
  • esterified oligomer of maleic anhydride adduct of isoprene polymer and 2-hydroxyethyl (meth) acrylate More preferred is an esterified oligomer of maleic anhydride adduct of isoprene polymer and 2-hydroxyethyl (meth) acrylate.
  • the oligomer of a component may be used independently and may mix and use 2 or more types.
  • the component (B) in the present invention is an acyclic (meth) acrylate having a homopolymer glass transition temperature of ⁇ 100 ° C. to 60 ° C.
  • Acyclic refers to (meth) acrylate having no alicyclic group or aromatic ring group, and is typically linear or branched (meth) acrylate. Examples of acyclic (meth) acrylates having a homopolymer glass transition temperature of ⁇ 100 ° C. to 60 ° C.
  • isostearyl (meth) acrylate (homopolymer glass transition temperature of acrylate: ⁇ 58 ° C.), lauryl (meth) acrylate ( Homopolymer glass transition temperature of acrylate: -30 ° C, homopolymer glass transition temperature of methacrylate: -65 ° C, 2-ethylhexyl (meth) acrylate (hompolymer glass transition temperature of acrylate: -85 ° C, homopolymer glass of methacrylate Transition temperature: ⁇ 10 ° C.), n-butyl (meth) acrylate (methacrylate homopolymer glass transition temperature: 20 ° C.), i-butyl (meth) acrylate (methacrylate homopolymer glass transition temperature: 20 ° C.), t- Butyl (meth) acrylate Homopolymer glass transition temperature of methacrylate: 20 ° C, methoxyethyl (meth) acrylate (
  • (meth) acrylates can be used alone or in combination of two or more.
  • isostearyl (meth) acrylate, lauryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate , Ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, and 2-hydroxypropyl (meth) acrylate are preferably selected from the group consisting of isostearyl (meth) acrylate, lauryl ( One or more members selected from the group consisting of (meth) acrylate and 2-hydroxyethyl (meth) acrylate are more preferable, and lauryl (meth) acrylate and / or isostearyl (meth) acrylate are most preferable.
  • the glass transition refers to, for example, a change in which a substance such as glass that is liquid at a high temperature suddenly increases its viscosity in a certain temperature range due to a temperature drop, almost loses fluidity and becomes an amorphous solid.
  • Examples of the method for measuring the glass transition temperature include thermogravimetry, differential scanning calorimetry, differential heat measurement, and dynamic viscoelasticity measurement. In this invention, it measured by the dynamic viscoelasticity measurement.
  • the glass transition temperature of the (meth) acrylate homopolymer is described in J. Org. Brandrup, E.M. H. Immersut, Polymer Handbook, 2nd Ed. , J .; Wiley, New York 1975, photocuring technology data book (Technonet Books), etc.
  • the compound of the general formula (1) further improves the flexibility of the cured product and further improves the adhesion to polyethylene terephthalate and the like.
  • R 1 is preferably an alkyl group having 10 to 19 carbon atoms, more preferably an alkyl group having 11 to 18 carbon atoms, and most preferably a lauryl group and / or an isostearyl group.
  • These (meth) acrylates can be used alone or in combination of two or more.
  • a component is a photoinitiator (henceforth a photoinitiator).
  • the photopolymerization agent is not particularly limited as long as it initiates polymerization of (meth) acrylate such as component (A), component (B), and component (D).
  • (C) As a photoinitiator although an ultraviolet polymerization initiator, a visible light polymerization initiator, etc. are mentioned, both are used without a restriction
  • the ultraviolet polymerization initiator include benzoin, benzophenone, and acetophenone.
  • visible light polymerization initiators include acylphosphine oxide, thioxanthone, metallocene, quinone, and ⁇ -aminoalkylphenone.
  • Photoinitiators include benzophenone, 4-phenylbenzophenone, benzoylbenzoic acid, 2,2-diethoxyacetophenone, bisdiethylaminobenzophenone, benzyl, benzoin, benzoylisopropyl ether, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone Thioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropane-1 -One, 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-fur Nylpropan-1-one, camphorquinone, 2,4,6-
  • the curable resin composition of the present invention contains (meth) acrylates other than the (A) component and the (B) component as the (D) component, particularly for the purpose of further improving the adhesion to each adherend. can do.
  • (meth) acrylates other than component (A) and component (B) include monofunctional (meth) acrylates, polyfunctional (meth) acrylates such as bifunctional, trifunctional, tetrafunctional, pentafunctional, and hexafunctional. Can be mentioned. Among these, monofunctional (meth) acrylate is preferable.
  • the component (D) lowers the heat and moisture resistance, it is preferable that the component (D) is small, and when importance is attached to the heat and humidity resistance, it is preferable not to contain it at all. The specific addition amount will be described later.
  • monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, tetrahydrofurfuryl (meth) ) Acrylate, caprolactone modified tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenyl ( (Meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxypoly Tylene glycol (meth) acrylate, nonyl (meth) acrylate, methyl (meth) acrylate,
  • dicyclopentenyloxyethyl (meth) acrylate dicyclopentenyloxypropyl (meth) acrylate
  • examples include (meth) acrylates having a dicyclopentenyl group such as dicyclopentenyl (meth) acrylate.
  • isobornyl (meth) acrylate is more preferable in terms of improving adhesion to cycloolefin.
  • a silane coupling agent can be contained as the component (E) for the purpose of improving the adhesion to glass.
  • 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, ⁇ -ureidopropyltriethoxysilane, and the like.
  • ⁇ -glycidoxypropyltrimethoxysilane and / or ⁇ - (meth) acryloxypropyltrimethoxysilane are preferable from the viewpoint of adhesion to glass or the like, and ⁇ -glycidoxypropyltrimethoxysilane is preferable. Is more preferable.
  • the present invention contains the components (A) to (C) as essential components. Therefore, curing with light is possible with the components (A) to (C).
  • the curable resin composition in the present invention contains 30 to 98 parts by weight of component (A) and 2 to 70 parts by weight of component (B) in a total of 100 parts by weight of component (A) and component (B). More preferably, it contains 40 to 95 parts by weight of component (A), 5 to 60 parts by weight of component (B), 50 to 90 parts by weight of component (A), and 10 parts of component (B). Most preferably, it contains ⁇ 50 parts by weight.
  • the total mass of the component (A) and the component (B) accounts for 80 to 99% by mass of the curable resin composition in the present invention, and typically accounts for 90 to 98% by mass. .
  • Component (C) is used in an amount of 0.01 to 10 parts by mass with respect to a total of 100 parts by mass of component (A), component (B) and component (D) used as necessary.
  • the adhesive property of the curable resin composition to the adherend is particularly high, and the curability is favorable, and the content of 0.1 to 5 parts by mass is more preferable.
  • Component (D) is preferably used in an amount of 0 to 10 parts by mass, and 0 to 7 parts by mass, in a total of 100 parts by mass of component (A), component (B) and component (D) used as necessary. More preferred is 0 to 4 parts by mass. (D) It is not necessary to contain a component. When the component (D) is included, the lower limit is preferably 1 part by mass, and more preferably 2 parts by mass.
  • Component (E) is preferably used in an amount of 0.01 to 10 parts by weight, based on a total of 100 parts by weight of component (A), component (B) and component (D) used as necessary. 5 parts by mass is more preferable.
  • a commercially available antioxidant containing a polymerization inhibitor can be used.
  • elastomers various paraffins, plasticizers, fillers, colorants, rust inhibitors and the like can be used as desired.
  • the curable resin composition of the present invention can be used as an adhesive composition.
  • a composite can be produced by bonding or coating an adherend with a cured body of the adhesive composition.
  • the various materials of the adherend are preferably at least one selected from the group consisting of polyolefins such as cycloolefin polymers, triacetyl cellulose, fluorine-based polymers, polyesters, polycarbonates, glasses and metals, and groups consisting of polycarbonates, polyolefins and glasses. 1 or more types selected from are more preferable.
  • the adherend adhered with the curable resin composition of the present invention can be reworked (reused) after being completely cured.
  • the rework method is not particularly limited, but the adherends are disassembled by applying a load of 0.01 to 100 N between the one or two kinds of adherends bonded together, and the adherend after disassembly The body can be reused.
  • A-1 Methacrylate-modified 1,2-polybutadiene oligomer (“TE-2000” manufactured by Nippon Soda Co., Ltd.) (number average molecular weight 2000 in terms of polystyrene by GPC)
  • A-2) Isoprene oligomer (“LIR-50” manufactured by Kuraray Co., Ltd.) (Number average molecular weight in terms of polystyrene by GPC 54000)
  • (B-1) Lauryl methacrylate (“Light Ester L” manufactured by Kyoeisha Chemical Co., Ltd .: homopolymer glass transition temperature: ⁇ 65 ° C.)
  • B-2) 2-hydroxyethyl methacrylate (“Kyoeisha Chemical Co., Ltd.“ Light Ester HO ”: homopolymer glass transition temperature: 55 ° C.)
  • B-3) Isostearyl acrylate (“ISTA” manufactured by Osaka Organic Chemical Industry Co., Ltd .: homopolymer glass transition temperature: ⁇ 58 ° C.)
  • the following compounds were selected as the photoinitiator for component (C).
  • (D) component as the component (A) and (B) other than the component (meth) acrylate, select the following compounds.
  • (D-1) Dicyclopentenyl acrylate (homopolymer glass transition temperature: 120 ° C.)
  • (D-2) Isobornyl methacrylate (homopolymer glass transition temperature: 120 ° C.)
  • the following compounds were selected as the silane coupling agent of component (E).
  • PET Polyethylene terephthalate
  • peel adhesion strength between polyethylene terephthalate test pieces A test piece (width 50 mm ⁇ length 10 mm ⁇ thickness 0.times.) Of a biaxially stretched PET film (Lumirror T60, manufactured by Toray Industries, Inc.). 05 mm) were bonded using a curable resin composition as an adhesive composition with an adhesive layer thickness of 30 ⁇ m and an adhesive area of 40 mm long ⁇ 10 mm wide.
  • the peel adhesion strength (unit: N / cm) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.
  • the tensile shear bond strength (unit: MPa) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.
  • the bond strength was measured.
  • the light irradiation conditions followed the method described in [Photocurability].
  • the peel adhesion strength (unit: N / cm) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.
  • the appearance of the bonded part was visually observed to determine whether it was yellowed.
  • the peel adhesion strength (unit: N / cm) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.
  • Triacetyl cellulose adhesion evaluation peeleling adhesive strength between triacetyl cellulose test pieces
  • Triacetyl cellulose (TAC) film average thickness 40 ⁇ m, manufactured by Fuji Film Co., Ltd.
  • test piece width 50 mm ⁇ length 10 mm ⁇
  • a thickness of 0.04 mm was bonded to each other with the adhesive layer having a thickness of 10 ⁇ m and a bonding area of 40 mm in length and 10 mm in width by using the curable resin composition as an adhesive composition.
  • the bond strength was measured.
  • the light irradiation conditions followed the method described in [Photocurability].
  • the peel adhesion strength (unit: N / cm) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 50 mm / min.
  • PVDF film average thickness 40 ⁇ m, “DX film” manufactured by Denki Kagaku Kogyo Co., Ltd.
  • test piece width 50 mm ⁇ length 10 mm ⁇ thickness 0.04 mm
  • curable resin composition as an adhesive composition with an adhesive layer thickness of 10 ⁇ m and an adhesive area of 40 mm long ⁇ 10 mm wide.
  • the bond strength was measured.
  • the light irradiation conditions followed the method described in [Photocurability].
  • the peel adhesive strength (unit: N / cm) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 50 mm / min.
  • an adhesive composition “G-55” manufactured by Denki Kagaku Kogyo Co., Ltd. was used on the Tempax test piece side, and a galvanized steel sheet (width 100 mm ⁇ length 25 mm ⁇ A thickness of 2.0 mm, manufactured by Engineering Test Service Co., Ltd.) was adhered.
  • the galvanized steel sheet was chucked, and the initial tensile shear bond strength was measured.
  • the tensile shear bond strength (unit: MPa) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.
  • the curable resin composition of the present invention exhibits high adhesiveness.
  • the curable resin composition of the present invention exhibits high adhesiveness. In particular, it exhibits high adhesion to polycarbonate, polyolefin, and glass. Since the curable resin composition of the present invention exhibits high adhesiveness, when a display body such as a thin glass LCD is bonded to an optical functional material such as an acrylic plate or a polycarbonate plate, the adhesive surface may be peeled off, or the LCD Will not break or the LCD will not display unevenly.
  • the curable resin composition of the present invention has a high resistance to moist heat and can follow the deformation of the adherend in a heated atmosphere, so that the adherend is not peeled off.
  • Experimental Example 14 does not contain a silane coupling agent, but has higher adhesion than the comparative example.
  • Experimental Example 15 does not contain a component (C)
  • a curable resin composition does not harden
  • cure and adhesiveness is small.
  • Experimental Example 16 and Experimental Example 17 contain a large amount of an alicyclic (meth) acrylate having a rigid skeleton such as isobornyl methacrylate and dicyclopentenyl acrylate, and do not contain the component (B).
  • the resin composition does not have flexibility and has low adhesiveness.
  • the curable resin composition of the present invention can be used for an adhesive composition for a touch panel laminate.
  • the touch panel laminate is generally composed of a cover material / touch panel sensor / liquid crystal panel layer.
  • the curable resin composition according to the present invention can be used as an adhesive for bonding a touch panel sensor and a cover material.
  • a cover material such as a decorative plate or an icon sheet for designating a touch position is bonded to the surface of the touch panel. It can be used as an adhesive. It can also be used as an adhesive that bonds the touch panel sensor and the liquid crystal panel together.
  • a transparent electrode is formed on a transparent substrate, and a transparent plate is bonded thereon.
  • the curable resin composition of the present invention is also suitable as an adhesive when a transparent electrode is formed on a transparent substrate and a transparent plate is bonded thereon.
  • the touch panel laminate of the present invention can be used as a display.

Abstract

Provided is a curable resin composition that exhibits high initial adhesiveness and adhesion durability. The curable resin composition comprises (A) oligomer with a diene or hydrogenated diene backbone, (B) acyclic (meth)acrylate with a glass transition temperature for the homopolymer of -100°C to 60°C, (C) photopolymerization initiator, and (D) (meth)acrylate other than Component (A) and Component (B). The total amount used of the Component (A) and Component (B) is 80-99 mass% of the curable resin composition and the amount of Component (D) used is 0 to 10 parts by mass in 100 parts by mass of the total of Component (A), Component (B) and Component (D).

Description

硬化性樹脂組成物Curable resin composition
本発明は、硬化性樹脂組成物に関する。とりわけ、本発明は硬化性樹脂組成物からなる接着剤組成物に関する。 The present invention relates to a curable resin composition. In particular, the present invention relates to an adhesive composition comprising a curable resin composition.
ＬＣＤ（液晶ディスプレイ）等の表示体の上に搭載するタッチパネルには、抵抗膜式、静電容量式、電磁誘導式、光学式等がある。これらのタッチパネルの表面に、見た目のデザイン性を良くするための化粧板や、タッチする位置を指定するアイコンシートを貼り合わせる場合がある。静電容量式タッチパネルは、透明基板の上に透明電極を形成し、その上に透明板を貼り合わせた構造を有している。 There are a resistive film type, a capacitance type, an electromagnetic induction type, an optical type and the like as a touch panel mounted on a display body such as an LCD (liquid crystal display). There is a case where a decorative board for improving the appearance design and an icon sheet for designating a touch position are attached to the surface of these touch panels. The capacitive touch panel has a structure in which a transparent electrode is formed on a transparent substrate and a transparent plate is bonded thereon.
従来、上記の化粧板とタッチパネルの貼り合わせ、上記のアイコンシートとタッチパネルの貼り合わせ、上記の透明基板と透明板の貼り合わせは、接着剤を用いていた。このような接着剤を使用する技術では、接着が不十分であるという課題があった。 Conventionally, the bonding of the decorative plate and the touch panel, the bonding of the icon sheet and the touch panel, and the bonding of the transparent substrate and the transparent plate have used an adhesive. The technique using such an adhesive has a problem of insufficient adhesion.
そこで、特許文献１では（Ａ）ポリイソプレン、ポリブタジエン又はポリウレタンを骨格にもつ（メタ）アクリレートオリゴマー及び（Ｂ）柔軟化成分を含むタッチパネル接着用硬化型接着組成物が提案されている。 Thus, Patent Document 1 proposes a curable adhesive composition for touch panel adhesion containing (A) a (meth) acrylate oligomer having a polyisoprene, polybutadiene or polyurethane as a skeleton and (B) a softening component.
特許文献２では、作業性に優れ、長期信頼性を有すると共に、硬化が早く、更に接着力及び耐湿性をさせることを目的として、イソボロニル（メタ）アクリレートを主体とする（メタ）アクリル単量体１００重量部と、ポリブタジエンを主鎖にもち、該主鎖の両端または側鎖に一種以上の（メタ）アクリル基を有するプレポリマー２５～１００重量部と、光重合開始剤とを含む紫外線硬化型接着剤組成物を提案している。 In Patent Document 2, a (meth) acrylic monomer mainly composed of isobornyl (meth) acrylate is used for the purpose of excellent workability, long-term reliability, quick curing, and further adhesion and moisture resistance. UV curable type comprising 100 parts by weight, 25-100 parts by weight of a prepolymer having polybutadiene in the main chain and having one or more (meth) acryl groups at both ends or side chains of the main chain, and a photopolymerization initiator An adhesive composition is proposed.
特許文献３には、画像表示装置の画像表示部と、透光性の保護部との間に介在させる樹脂硬化物層を形成するための樹脂組成物として、ポリウレタンアクリレート、ポリイソプレン系アクリレート又はそのエステル化物、テルペン系水素添加樹脂、ブタジエン重合体等の１種以上のポリマーと、イソボルニルアクリレート、ジシクロペンテニルオキシエチルメタクリレート、２－ヒドロキシブチルメタクリレート等の１種以上のアクリレート系モノマーと、１－ヒドロキシ－シクロヘキシル－フェニル－ケトン等の光重合開始剤とを含有する樹脂組成物が開示されている。 Patent Document 3 discloses polyurethane acrylate, polyisoprene acrylate or the like as a resin composition for forming a cured resin layer interposed between an image display portion of an image display device and a translucent protective portion. One or more polymers such as esterified products, terpene hydrogenated resins, butadiene polymers, one or more acrylate monomers such as isobornyl acrylate, dicyclopentenyloxyethyl methacrylate, 2-hydroxybutyl methacrylate, and 1 A resin composition containing a photopolymerization initiator such as -hydroxy-cyclohexyl-phenyl-ketone is disclosed.
国際公開第２０１０／０２７０４１号International Publication No. 2010/027041 特開昭６４－８５２０９号公報JP-A 64-85209 特開２００９－１８６９５７号公報JP 2009-186957 A
特許文献１は、フェノキシエチル（メタ）アクリレート、フェノキシポリエチレングリコール（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、シクロヘキシル（メタ）アクリレート、ノニルフェノールＥＯ付加物（メタ）アクリレート、メトキシトリエチレングリコール（メタ）アクリレート及びテトラヒドロフルフリル（メタ）アクリレートから選択した（メタ）アクリレートモノマーのような環式（メタ）アクリレートを使用している。
特許文献２及び３ではイソボルニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレートのような剛直な骨格モノマーをベースとした高弾性樹脂であるが故に、高温信頼性試験において被着体の膨張収縮に耐えることができず、剥がれを生じてしまう可能性があった。 Patent Document 1 discloses phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, nonylphenol EO adduct (meth) acrylate, methoxytri Cyclic (meth) acrylates such as (meth) acrylate monomers selected from ethylene glycol (meth) acrylate and tetrahydrofurfuryl (meth) acrylate are used.
In Patent Documents 2 and 3, since it is a highly elastic resin based on a rigid skeleton monomer such as isobornyl (meth) acrylate and dicyclopentenyl (meth) acrylate, it is difficult to expand and contract the adherend in a high-temperature reliability test. It could not endure and could cause peeling.
化粧板とタッチパネルの貼り合わせ、アイコンシートとタッチパネルの貼り合わせ、透明基板と透明板の貼り合わせ等の用途では、使用環境を想定した加温雰囲気での被着体の変形に追随できる程度の柔軟性を有することが望ましいとされている。 For applications such as bonding of decorative plates and touch panels, bonding of icon sheets and touch panels, bonding of transparent substrates and transparent plates, etc., flexibility that can follow the deformation of the adherend in a heated atmosphere assuming the usage environment It is considered desirable to have sex.
本発明は上記事情に鑑みてなされたものであり、例えば、タッチパネル等の表示体に使用される化粧板やアイコンシートを貼り合わせる場合、透明基板と透明板とを貼り合わせる場合、印刷加工された部分を貼り合わせる場合に、十分な初期接着性及び耐湿熱性を付与することが困難であるという従来技術の課題、或いは表示体と光学機能材料とを貼り合わせる場合に、接着面が剥がれたり、表示体のガラスが割れたりするという従来技術の課題を解決する硬化性樹脂組成物を提供する。 The present invention has been made in view of the above circumstances. For example, when a decorative plate and an icon sheet used for a display body such as a touch panel are bonded together, when a transparent substrate and a transparent plate are bonded together, printing processing is performed. When pasting parts, it is difficult to provide sufficient initial adhesion and wet heat resistance, or when the display body and optical functional material are pasted together, the adhesive surface may peel off or display Provided is a curable resin composition that solves the problem of the prior art that the body glass is broken.
即ち、本発明は一側面において、下記（Ａ）～（Ｄ）成分を含有し、（Ａ）成分及び（Ｂ）成分の合計使用量が硬化性樹脂組成物の８０～９９質量％を占め、（Ｄ）成分の使用量は、（Ａ）成分、（Ｂ）成分及び（Ｄ）成分の合計１００質量部中、０～１０質量部である硬化性樹脂組成物である。
（Ａ）ジエン系又は水素添加されたジエン系の骨格を有するオリゴマー、
（Ｂ）ホモポリマーガラス転移温度が－１００～６０℃を示す非環式(メタ)アクリレート、
（Ｃ）光重合開始剤
（Ｄ）（Ａ）成分及び（Ｂ）成分以外の(メタ)アクリレート That is, in one aspect, the present invention contains the following components (A) to (D), and the total amount of the components (A) and (B) accounts for 80 to 99% by mass of the curable resin composition. The amount of component (D) used is a curable resin composition that is 0 to 10 parts by mass in a total of 100 parts by mass of component (A), component (B) and component (D).
(A) an oligomer having a diene-based or hydrogenated diene-based skeleton,
(B) acyclic homopolymer glass transition temperature indicating the -100 ~ 60 ° C. (meth) acrylate,
(C) Photopolymerization initiator (D) (Meth) acrylate other than components (A) and (B)
本発明に係る硬化性樹脂組成物の一実施形態においては、（Ｂ）成分が、一般式（１）の化合物である。
一般式（１） Ｚ－Ｏ－Ｒ1
〔式中、Ｚは（メタ）アクリロイル基を示し、Ｒ1 は炭素数９～２０個のアルキル基を表す。〕 In one embodiment of the curable resin composition of the present invention is a compound of component (B), the general formula (1).
General formula (1) Z—O—R 1
Wherein, Z is shown a (meth) acryloyl group, R 1 represents a number 9-20 alkyl group having a carbon. ]
本発明に係る硬化性樹脂組成物の別の一実施形態においては、（Ａ）成分及び（Ｂ）成分の合計１００質量部中、(Ａ)成分が３０～９８質量部、（Ｂ）成分が２～７０質量部である。 In another embodiment of the curable resin composition according to the present invention, in a total of 100 parts by mass of the component (A) and the component (B), the component (A) is 30 to 98 parts by mass, and the component (B) is 2 to 70 parts by mass.
本発明に係る硬化性樹脂組成物の更に別の一実施形態においては、（Ｂ）成分が、イソステアリル（メタ）アクリレート、ラウリル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、１，３－ブチレングリコールジ（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレートからなる群のうちの１種以上である。 In yet another embodiment of the curable resin composition according to the present invention, the component (B) is isostearyl (meth) acrylate, lauryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-ethylhexyl. From (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 2-hydroxypropyl (meth) acrylate One or more members of the group.
本発明に係る硬化性樹脂組成物の更に別の一実施形態においては、（Ｂ）成分が、ラウリル（メタ）アクリレート及び／又はイソステアリル（メタ）アクリレートである。 In still another embodiment of the curable resin composition according to the present invention, the component (B) is lauryl (meth) acrylate and / or isostearyl (meth) acrylate.
本発明に係る硬化性樹脂組成物の一実施形態においては、更に、（Ｅ）成分として、シランカップリング剤を含有する。 In one embodiment of the curable resin composition according to the present invention, a silane coupling agent is further contained as the component (E).
本発明に係る硬化性樹脂組成物の一実施形態においては、（Ａ）成分のジエン系又は水素添加されたジエン系の骨格が、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１種以上の骨格である。 In one embodiment of the curable resin composition according to the present invention, the diene-based or hydrogenated diene-based skeleton of the component (A) is polybutadiene, polyisoprene, a hydrogenated polybutadiene, and a hydrogen of polyisoprene. One or more skeletons selected from the group consisting of additives.
本発明に係る硬化性樹脂組成物の更に別の一実施形態においては、（Ａ）成分のジエン系又は水素添加されたジエン系の骨格を有するオリゴマーの分子量が５００～７００００である。 In still another embodiment of the curable resin composition according to the present invention, the molecular weight of the oligomer (A) having a diene-based or hydrogenated diene-based skeleton is 500 to 70000.
本発明に係る硬化性樹脂組成物の更に別の一実施形態においては、（Ａ）成分及び（Ｂ）成分の合計１００質量部中、(Ａ)成分が５０～９０質量部、（Ｂ）成分が１０～５０質量部であり、（Ｃ）成分の使用量は、（Ａ）成分、（Ｂ）成分及び（Ｄ）成分の合計１００質量部に対して、０．０１～１０質量部であり、（Ｅ）成分の使用量は、（Ａ）成分、（Ｂ）成分及び（Ｄ）成分の合計１００質量部に対して、０．０１～１０質量部である。 In still another embodiment of the curable resin composition according to the present invention, the component (A) is 50 to 90 parts by mass, and the component (B) is a total of 100 parts by mass of the component (A) and the component (B). Is 10 to 50 parts by mass, and the amount of the component (C) used is 0.01 to 10 parts by mass with respect to 100 parts by mass in total of the components (A), (B) and (D). The amount of the component (E) used is 0.01 to 10 parts by mass with respect to 100 parts by mass in total of the components (A), (B) and (D).
本発明は別の一側面において、上記に記載の硬化性樹脂組成物からなる接着剤組成物である。 In another aspect, the present invention is an adhesive composition comprising the curable resin composition described above.
本発明は更に別の一側面において、上記に記載の硬化性樹脂組成物からなる接着剤組成物の硬化体である。 In yet another aspect, the present invention provides a cured product of an adhesive composition comprising the curable resin composition described above.
本発明は更に別の一側面において、上記に記載の硬化体により被着体が被覆又は被着体同士が接合された複合体である。 In still another aspect, the present invention is a composite in which the adherend is coated or bonded to each other by the cured body described above.
本発明は更に別の一側面において、上記に記載の被着体がトリアセチルセルロース、フッ素系ポリマー、ポリエステル、ポリカーボネート、ポリオレフィン、ガラス、金属からなる群から選ばれる１種以上である複合体である。 In another aspect of the present invention, the adherend described above is a composite that is at least one selected from the group consisting of triacetylcellulose, a fluorine-based polymer, polyester, polycarbonate, polyolefin, glass, and metal. .
本発明は更に別の一側面において、上記に記載の接着剤組成物により被着体を貼り合わせたタッチパネル積層体である。 In still another aspect, the present invention is a touch panel laminate in which an adherend is bonded using the adhesive composition described above.
本発明は更に別の一側面において、上記に記載のタッチパネル積層体を備えたディスプレイである。 In yet another aspect, the present invention is a display including the touch panel laminate described above.
本発明の硬化性樹脂組成物は、高い初期接着性及び耐湿熱性を示す。 The curable resin composition of the present invention exhibits high initial adhesion and wet heat resistance.
本発明における（Ａ）成分は、ジエン系又は水素添加されたジエン系の骨格を有するオリゴマーである。 The component (A) in the present invention is an oligomer having a diene-based or hydrogenated diene-based skeleton.
本発明における該オリゴマーの主鎖骨格は、ジエン系又は水素添加されたジエン系の骨格である。ジエン系又は水素添加されたジエン系の骨格としては、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１種以上の骨格が好ましい。これらの中では、接着耐久性が大きい点で、ポリブタジエン及びポリイソプレンからなる群から選ばれる１種以上が好ましく、ポリブタジエンがより好ましい。 The main chain skeleton of the oligomer in the present invention is a diene-based or hydrogenated diene-based skeleton. The diene-based or hydrogenated diene-based skeleton is preferably at least one skeleton selected from the group consisting of polybutadiene, polyisoprene, a hydrogenated polybutadiene, and a hydrogenated polyisoprene. Among these, at least one selected from the group consisting of polybutadiene and polyisoprene is preferable, and polybutadiene is more preferable in terms of high adhesion durability.
該オリゴマーは、上記主鎖骨格の末端又は側鎖に１個以上の（メタ）アクリロイル基を有することが好ましい。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 oligomer preferably has one or more (meth) acryloyl groups at the terminal 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.
該オリゴマーの分子量は５００～７００００が好ましく、１０００～６００００がより好ましく、１０００～５５０００が最も好ましい。分子量が５００以上であれば、本発明の硬化性樹脂組成物に光を照射して得られる硬化体の硬度が高いので接着剤層を形成しやすくなる。分子量が７００００以下であれば、得られる硬化性樹脂組成物の粘度が小さいので、製造過程での混合等における作業性や実用用途において作業性が良好になる。 The molecular weight of the oligomer is preferably 500 to 70000, more preferably 1000 to 60000, and most preferably 1000 to 55000. If molecular weight is 500 or more, since the hardness of the hardening body obtained by irradiating light to the curable resin composition of this invention is high, it will become easy to form an adhesive bond layer. If the molecular weight is 70,000 or less, the viscosity of the resulting curable resin composition is small, so that the workability in mixing during the production process and the workability in practical applications are improved.
オリゴマーの分子量は、分子１個あたりの平均の分子量として算出される数平均分子量を指す。本発明の実施例では、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）により測定した、ポリスチレン換算の数平均分子量を使用した。  The molecular weight of the oligomer refers to the number average molecular weight calculated as the average molecular weight per molecule. In the Example of this invention, the number average molecular weight of polystyrene conversion measured by GPC (gel permeation chromatography) was used.
（Ａ）成分のオリゴマーとしては、クラレ社製「ＵＣ－２０３」（イソプレン重合物の無水マレイン酸付加物と２－ヒドロキシエチルメタクリレートとのエステル化物オリゴマー）、クラレ社製「ＬＩＲ－５０」（イソプレンオリゴマー）、クラレ社製「ＬＢＲ－５０」「ＬＢＲ－３０７」（ブタジエンオリゴマー）、日本曹達社製「ＴＥＡＩ－１０００」（末端アクリル変性水素添加１，２－ポリブタジエンオリゴマー）、日本曹達社製「ＴＥ－２０００」（末端メタクリル変性１，２－ポリブタジエンオリゴマー）等が挙げられる。（Ａ）成分のオリゴマーの中では、イソプレン重合物の無水マレイン酸付加物と２－ヒドロキシエチル（メタ）アクリレートとのエステル化物オリゴマー、イソプレンオリゴマー、末端（メタ）アクリル変性１，２－ポリブタジエンオリゴマーからなる群のうちの１種以上が好ましく、イソプレン重合物の無水マレイン酸付加物と２－ヒドロキシエチル（メタ）アクリレートとのエステル化物オリゴマー及び／又は末端（メタ）アクリル変性１，２－ポリブタジエンオリゴマーがより好ましく、イソプレン重合物の無水マレイン酸付加物と２－ヒドロキシエチル（メタ）アクリレートとのエステル化物オリゴマーが最も好ましい。（Ａ）成分のオリゴマーは単独で使用してもよく、２種類以上を混合して使用してもよい。 As the oligomer of the component (A), “UC-203” manufactured by Kuraray (esterified oligomer of maleic anhydride adduct of isoprene polymer and 2-hydroxyethyl methacrylate), “LIR-50” (isoprene manufactured by Kuraray) Oligomer), Kuraray "LBR-50" "LBR-307" (butadiene oligomer), Nippon Soda "TEAI-1000" (terminal acrylic modified hydrogenated 1,2-polybutadiene oligomer), Nippon Soda "TE -2000 "(terminal methacryl-modified 1,2-polybutadiene oligomer) and the like. Among the oligomers of component (A), esterified oligomers of maleic anhydride adduct of isoprene polymer and 2-hydroxyethyl (meth) acrylate, isoprene oligomers, terminal (meth) acryl-modified 1,2-polybutadiene oligomers Preferably, one or more members of the group consisting of an esterified oligomer of maleic anhydride adduct of isoprene polymer and 2-hydroxyethyl (meth) acrylate and / or a terminal (meth) acryl-modified 1,2-polybutadiene oligomer are used. More preferred is an esterified oligomer of maleic anhydride adduct of isoprene polymer and 2-hydroxyethyl (meth) acrylate. (A) The oligomer of a component may be used independently and may mix and use 2 or more types.
本発明における（Ｂ）成分は、ホモポリマーガラス転移温度が－１００℃～６０℃を示す非環式（メタ）アクリレートである。非環式とは、脂環基や芳香環基を有しない（メタ）アクリレートをいい、典型的には直鎖状又は分岐鎖状の（メタ）アクリレートである。ホモポリマーガラス転移温度が－１００℃～６０℃を示す非環式（メタ）アクリレートとしては、イソステアリル（メタ）アクリレート（アクリレートのホモポリマーガラス転移温度：－５８℃）、ラウリル（メタ）アクリレート（アクリレートのホモポリマーガラス転移温度：－３０℃、メタクリレートのホモポリマーガラス転移温度：－６５℃）、２－エチルヘキシル（メタ）アクリレート（アクリレートのホモポリマーガラス転移温度：－８５℃、メタクリレートのホモポリマーガラス転移温度：－１０℃）、ｎ－ブチル（メタ）アクリレート（メタクリレートのホモポリマーガラス転移温度：２０℃）、ｉ－ブチル（メタ）アクリレート（メタクリレートのホモポリマーガラス転移温度：２０℃）、ｔ－ブチル（メタ）アクリレート（メタクリレートのホモポリマーガラス転移温度：２０℃）、メトキシエチル（メタ）アクリレート（アクリレートのホモポリマーガラス転移温度：－５０℃）、エチレングリコールジ（メタ）アクリレート、１，３－ブチレングリコールジ（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート（アクリレートのホモポリマーガラス転移温度：７℃、メタクリレートのホモポリマーガラス転移温度：５５℃）、２－ヒドロキシプロピル（メタ）アクリレート（アクリレートのホモポリマーガラス転移温度：－７℃、メタクリレートのホモポリマーガラス転移温度：２６℃）、２－ヒドロキシブチル（メタ）アクリレート（アクリレートのホモポリマーガラス転移温度：－３８℃）等が挙げられる。これらの（メタ）アクリレートは１種類又は２種類以上を使用できる。これらの中では、イソステアリル（メタ）アクリレート、ラウリル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、１，３－ブチレングリコールジ（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレートからなる群のうちの１種以上が好ましく、イソステアリル（メタ）アクリレート、ラウリル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレートからなる群のうちの１種以上がより好ましく、ラウリル（メタ）アクリレート及び／又はイソステアリル（メタ）アクリレートが最も好ましい。 The component (B) in the present invention is an acyclic (meth) acrylate having a homopolymer glass transition temperature of −100 ° C. to 60 ° C. Acyclic refers to (meth) acrylate having no alicyclic group or aromatic ring group, and is typically linear or branched (meth) acrylate. Examples of acyclic (meth) acrylates having a homopolymer glass transition temperature of −100 ° C. to 60 ° C. include isostearyl (meth) acrylate (homopolymer glass transition temperature of acrylate: −58 ° C.), lauryl (meth) acrylate ( Homopolymer glass transition temperature of acrylate: -30 ° C, homopolymer glass transition temperature of methacrylate: -65 ° C, 2-ethylhexyl (meth) acrylate (hompolymer glass transition temperature of acrylate: -85 ° C, homopolymer glass of methacrylate Transition temperature: −10 ° C.), n-butyl (meth) acrylate (methacrylate homopolymer glass transition temperature: 20 ° C.), i-butyl (meth) acrylate (methacrylate homopolymer glass transition temperature: 20 ° C.), t- Butyl (meth) acrylate Homopolymer glass transition temperature of methacrylate: 20 ° C, methoxyethyl (meth) acrylate (homopolymer glass transition temperature of acrylate: -50 ° C), ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) Acrylate, 2-hydroxyethyl (meth) acrylate (homopolymer glass transition temperature of acrylate: 7 ° C., homopolymer glass transition temperature of methacrylate: 55 ° C.), 2-hydroxypropyl (meth) acrylate (homopolymer glass transition temperature of acrylate) : -7 ° C., methacrylate homopolymer glass transition temperature: 26 ° C., 2-hydroxybutyl (meth) acrylate (acrylate homopolymer glass transition temperature: −38 ° C.), and the like. These (meth) acrylates can be used alone or in combination of two or more. Among these, isostearyl (meth) acrylate, lauryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate , Ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, and 2-hydroxypropyl (meth) acrylate are preferably selected from the group consisting of isostearyl (meth) acrylate, lauryl ( One or more members selected from the group consisting of (meth) acrylate and 2-hydroxyethyl (meth) acrylate are more preferable, and lauryl (meth) acrylate and / or isostearyl (meth) acrylate are most preferable.
ガラス転移とは、例えば、高温では液体であるガラス等の物質が温度降下により、ある温度範囲で急激にその粘度を増し、ほとんど流動性を失って非晶質固体になるという変化を指す。ガラス転移温度の測定方法としては、熱重量測定、示差走査熱量測定、示差熱測定、動的粘弾性測定等が挙げられる。本発明では動的粘弾性測定により測定した。 The glass transition refers to, for example, a change in which a substance such as glass that is liquid at a high temperature suddenly increases its viscosity in a certain temperature range due to a temperature drop, almost loses fluidity and becomes an amorphous solid. Examples of the method for measuring the glass transition temperature include thermogravimetry, differential scanning calorimetry, differential heat measurement, and dynamic viscoelasticity measurement. In this invention, it measured by the dynamic viscoelasticity measurement.
（メタ）アクリレートのホモポリマーのガラス転移温度は、Ｊ．　Ｂｒａｎｄｒｕｐ，　Ｅ．　Ｈ．　Ｉｍｍｅｒｇｕｔ，　Ｐｏｌｙｍｅｒ　Ｈａｎｄｂｏｏｋ，　２ｎｄ　Ｅｄ．，Ｊ．　Ｗｉｌｅｙ，　Ｎｅｗ　Ｙｏｒｋ　１９７５、光硬化技術データブック（テクノネットブックス社）等に記載されている。 The glass transition temperature of the (meth) acrylate homopolymer is described in J. Org. Brandrup, E.M. H. Immersut, Polymer Handbook, 2nd Ed. , J .; Wiley, New York 1975, photocuring technology data book (Technonet Books), etc.
これらの（Ｂ）成分の中では、接着性が大きい点で、一般式（１）の化合物が好ましい。
一般式（１） Ｚ－Ｏ－Ｒ1
〔式中、Ｚは（メタ）アクリロイル基を示し、Ｒ1 は炭素数９～２０個のアルキル基を表す。〕 Among these component (B), in that a large adhesiveness, compounds of general formula (1) are preferred.
General formula (1) Z—O—R 1
Wherein, Z is shown a (meth) acryloyl group, R 1 represents a number 9-20 alkyl group having a carbon. ]
一般式（１）の化合物は、硬化物の柔軟性を一層向上させてポリエチレンテレフタレート等への密着性を一層向上させる。一般式（１）の化合物としては、ノニル基、イソノニル基、デシル基、イソデシル基、ウンデシル基、ラウリル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、エイコデシル基、ステアリル基、イソステアリル基等の、炭素数が９～２０個の直鎖又は分岐のアルキル基を有する（メタ）アクリル酸エステルが挙げられる。Ｒ1は炭素数１０～１９個のアルキル基が好ましく、炭素数１１～１８個のアルキル基がより好ましく、ラウリル基及び／又はイソステアリル基が最も好ましい。これらの（メタ）アクリレートは１種類又は２種類以上を使用できる。 The compound of the general formula (1) further improves the flexibility of the cured product and further improves the adhesion to polyethylene terephthalate and the like. As the compound of the general formula (1), nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, lauryl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicodecyl group (Meth) acrylic acid ester having a linear or branched alkyl group having 9 to 20 carbon atoms, such as a group, a stearyl group, and an isostearyl group. R 1 is preferably an alkyl group having 10 to 19 carbon atoms, more preferably an alkyl group having 11 to 18 carbon atoms, and most preferably a lauryl group and / or an isostearyl group. These (meth) acrylates can be used alone or in combination of two or more.
（Ｃ）成分は、光重合開始剤（以下光開始剤という）である。光重合剤としては、（Ａ）成分、（Ｂ）成分、（Ｄ）成分といった(メタ)アクリレートの重合を開始させるものであれば特に制限はない。 (C) A component is a photoinitiator (henceforth a photoinitiator). The photopolymerization agent is not particularly limited as long as it initiates polymerization of (meth) acrylate such as component (A), component (B), and component (D).
（Ｃ）光開始剤としては、紫外線重合開始剤や可視光重合開始剤等が挙げられるが、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、メタロセン系、キノン系、α－アミノアルキルフェノン系等が挙げられる。 (C) As a photoinitiator, although an ultraviolet polymerization initiator, a visible light polymerization initiator, etc. are mentioned, both are used without a restriction | limiting. Examples of the ultraviolet polymerization initiator include benzoin, benzophenone, and acetophenone. Examples of visible light polymerization initiators include acylphosphine oxide, thioxanthone, metallocene, quinone, and α-aminoalkylphenone.
（Ｃ）光開始剤としては、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、２－メチルチオキサントン、２，４－ジメチルチオキサントン、イソプロピルチオキサントン、２，４－ジエチルチオキサントン、２，４－ジイソプロピルチオキサントン、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）－ブタノン－１、２－ジメチルアミノ－２－（４－メチル－ベンジル）－１－（４－モリフォリン－４－イル－フェニル）－ブタン－１－オン、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。 (C) Photoinitiators include benzophenone, 4-phenylbenzophenone, benzoylbenzoic acid, 2,2-diethoxyacetophenone, bisdiethylaminobenzophenone, benzyl, benzoin, benzoylisopropyl ether, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone Thioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropane-1 -One, 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-fur Nylpropan-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) -butanone-1,2-dimethylamino-2- (4-methyl-benzyl)- Examples include 1- (4-morpholin-4-yl-phenyl) -butan-1-one and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide.
本発明の硬化性樹脂組成物は、特に各被着体に対する接着性を一層向上させることを目的に、（Ｄ）成分として、（Ａ）成分や（Ｂ）成分以外の(メタ)アクリレートを含有することができる。（Ａ）成分や（Ｂ）成分以外の(メタ)アクリレートとしては、単官能（メタ）アクリレートや、２官能、３官能、４官能、５官能、６官能等の多官能（メタ）アクリレート等が挙げられる。これらの中では、単官能（メタ）アクリレートが好ましい。ただし、（Ｄ）成分の添加は耐湿熱性を低下させるため、（Ｄ）成分は少ない方が好ましく、耐湿熱性を重視する場合は全く含有しない方が好ましい。具体的な添加量は後述する。 The curable resin composition of the present invention contains (meth) acrylates other than the (A) component and the (B) component as the (D) component, particularly for the purpose of further improving the adhesion to each adherend. can do. Examples of (meth) acrylates other than component (A) and component (B) include monofunctional (meth) acrylates, polyfunctional (meth) acrylates such as bifunctional, trifunctional, tetrafunctional, pentafunctional, and hexafunctional. Can be mentioned. Among these, monofunctional (meth) acrylate is preferable. However, since the addition of the component (D) lowers the heat and moisture resistance, it is preferable that the component (D) is small, and when importance is attached to the heat and humidity resistance, it is preferable not to contain it at all. The specific addition amount will be described later.
本発明における（Ｄ）成分として用いられる（メタ）アクリレートの中で、単官能（メタ）アクリレートとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、カプロラクトン変性テトラヒドロフルフリル（メタ）アクリレート、シクロヘキシル（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、ジシクロペンテニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、フェノキシテトラエチレングリコール（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、ノニルフェノキシエチル（メタ）アクリレート、ノニルフェノキシテトラエチレングリコール（メタ）アクリレート、メトキシジエチレングリコール（メタ）アクリレート、エトキシジエチレングリコール（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、ブトキシトリエチレングリコール（メタ）アクリレート、２－エチルヘキシルポリエチレングリコール（メタ）アクリレート、ノニルフェニルポリプロピレングリコール（メタ）アクリレート、メトキシジプロピレングリコール（メタ）アクリレート、グリシジル（メタ）アクリレート、グリセロール（メタ）アクリレート、ポリエチレングリコール（メタ）アクリレート、ポリプロピレングリコール（メタ）アクリレート、エピクロロヒドリン（以下ＥＣＨと略記）変性ブチル（メタ）アクリレート、エピクロロヒドリン（以下ＥＣＨと略記）変性フェノキシ（メタ）アクリレート、エチレンオキサイド（以下ＥＯと略記）変性フタル酸（メタ）アクリレート、ＥＯ変性コハク酸（メタ）アクリレート、カプロラクトン変性２－ヒドロキシエチル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノエチル（メタ）アクリレート、モルホリノ（メタ）アクリレート、ＥＯ変性リン酸（メタ）アクリレート等が挙げられる。イミド（メタ）アクリレート（製品名：Ｍ－１４０、東亞合成社製）のようなイミド基を有する（メタ）アクリレート等も挙げられる。 Among (meth) acrylates used as component (D) in the present invention, monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, tetrahydrofurfuryl (meth) ) Acrylate, caprolactone modified tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenyl ( (Meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxypoly Tylene glycol (meth) acrylate, nonylphenoxyethyl (meth) acrylate, nonylphenoxytetraethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, butoxyethyl (meth) acrylate, butoxytriethylene glycol (Meth) acrylate, 2-ethylhexyl polyethylene glycol (meth) acrylate, nonylphenyl polypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, glycidyl (meth) acrylate, glycerol (meth) acrylate, polyethylene glycol (meth) Acrylate, polypropylene glycol (meth) acrylate, Chlorohydrin (hereinafter abbreviated as ECH) modified butyl (meth) acrylate, epichlorohydrin (hereinafter abbreviated as ECH) modified phenoxy (meth) acrylate, ethylene oxide (hereinafter abbreviated as EO) modified phthalic acid (meth) acrylate, EO modified succinate Acid (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, morpholino (meth) acrylate, EO-modified phosphoric acid (Meth) acrylate etc. are mentioned. Examples thereof include (meth) acrylate having an imide group such as imide (meth) acrylate (product name: M-140, manufactured by Toagosei Co., Ltd.).
単官能（メタ）アクリレートとしては、シクロオレフィンポリマーを始めとするポリオレフィン等への接着性を向上させることを目的として、ジシクロペンテニルオキシエチル（メタ）アクリレート、ジシクロペンテニルオキシプロピル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート等を初めとするジシクロペンテニル基を有する(メタ)アクリレート等も挙げられる。 As monofunctional (meth) acrylates, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyloxypropyl (meth) acrylate, for the purpose of improving adhesion to polyolefins including cycloolefin polymers, Examples include (meth) acrylates having a dicyclopentenyl group such as dicyclopentenyl (meth) acrylate.
単官能（メタ）アクリレートの中では、シクロオレフィンへの接着性を向上する点で、イソボルニル（メタ）アクリレートがより好ましい。 Among monofunctional (meth) acrylates, isobornyl (meth) acrylate is more preferable in terms of improving adhesion to cycloolefin.
本発明ではガラスへの密着力を向上させる目的で、（Ｅ）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。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、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。これらの中では、ガラス等への密着性の点で、γ－グリシドキシプロピルトリメトキシシラン及び／又は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く、γ－グリシドキシプロピルトリメトキシシランがより好ましい。 In the present invention, a silane coupling agent can be contained as the component (E) for the purpose of improving the adhesion to glass. 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, γ-ureidopropyltriethoxysilane, and the like. Among these, γ-glycidoxypropyltrimethoxysilane and / or γ- (meth) acryloxypropyltrimethoxysilane are preferable from the viewpoint of adhesion to glass or the like, and γ-glycidoxypropyltrimethoxysilane is preferable. Is more preferable.
本発明は、前記（Ａ）～（Ｃ）成分を必須成分として含有する。故に（Ａ）～（Ｃ）成分にて光による硬化を可能とする。 The present invention contains the components (A) to (C) as essential components. Therefore, curing with light is possible with the components (A) to (C).
本発明における硬化性樹脂組成物は、（Ａ）成分及び（Ｂ）成分の合計１００質量部中、（Ａ）成分を３０～９８質量部、（Ｂ）成分を２～７０質量部を含有することが好ましく、（Ａ）成分を４０～９５質量部、（Ｂ）成分を５～６０質量部を含有することがより好ましく、（Ａ）成分を５０～９０質量部、（Ｂ）成分を１０～５０質量部を含有することが最も好ましい。 The curable resin composition in the present invention contains 30 to 98 parts by weight of component (A) and 2 to 70 parts by weight of component (B) in a total of 100 parts by weight of component (A) and component (B). More preferably, it contains 40 to 95 parts by weight of component (A), 5 to 60 parts by weight of component (B), 50 to 90 parts by weight of component (A), and 10 parts of component (B). Most preferably, it contains ˜50 parts by weight.
　好ましい実施形態においては、（Ａ）成分及び（Ｂ）成分の合計質量は、本発明における硬化性樹脂組成物のうちの８０～９９質量％を占め、典型的には９０～９８質量％を占める。 In a preferred embodiment, the total mass of the component (A) and the component (B) accounts for 80 to 99% by mass of the curable resin composition in the present invention, and typically accounts for 90 to 98% by mass. .
（Ｃ）成分の使用量は、（Ａ）成分、（Ｂ）成分及び必要に応じて使用する（Ｄ）成分の合計１００質量部に対して、０．０１～１０質量部を含有することが、硬化性樹脂組成物の被着体に対する接着性が特段に高くなり、且つ、硬化性が良好となる点で、好ましく、０．１～５質量部を含有することが、より好ましい。 Component (C) is used in an amount of 0.01 to 10 parts by mass with respect to a total of 100 parts by mass of component (A), component (B) and component (D) used as necessary. The adhesive property of the curable resin composition to the adherend is particularly high, and the curability is favorable, and the content of 0.1 to 5 parts by mass is more preferable.
（Ｄ）成分の使用量は、（Ａ）成分、（Ｂ）成分及び必要に応じて使用する（Ｄ）成分の合計１００質量部中、０～１０質量部が好ましく、０～７質量部がより好ましく、０～４質量部が最も好ましい。（Ｄ）成分を含有しなくても良い。（Ｄ）成分を含む場合の下限値は、１質量部が好ましく、２質量部がより好ましい。 Component (D) is preferably used in an amount of 0 to 10 parts by mass, and 0 to 7 parts by mass, in a total of 100 parts by mass of component (A), component (B) and component (D) used as necessary. More preferred is 0 to 4 parts by mass. (D) It is not necessary to contain a component. When the component (D) is included, the lower limit is preferably 1 part by mass, and more preferably 2 parts by mass.
（Ｅ）成分の使用量は、（Ａ）成分、（Ｂ）成分及び必要に応じて使用する（Ｄ）成分の合計１００質量部に対して、０．０１～１０質量部が好ましく、１～５質量部がより好ましい。 Component (E) is preferably used in an amount of 0.01 to 10 parts by weight, based on a total of 100 parts by weight of component (A), component (B) and component (D) used as necessary. 5 parts by mass is more preferable.
更に、貯蔵安定性を維持する目的で、重合禁止剤を含む市販の酸化防止剤等を使用することができる。 Furthermore, for the purpose of maintaining storage stability, a commercially available antioxidant containing a polymerization inhibitor can be used.
これらの他にも所望により、エラストマー、各種パラフィン類、可塑剤、充填剤、着色剤、防錆剤等を使用できる。 In addition to these, elastomers, various paraffins, plasticizers, fillers, colorants, rust inhibitors and the like can be used as desired.
本発明の硬化性樹脂組成物は、接着剤組成物として使用できる。本発明では、接着剤組成物の硬化体によって、被着体を接合又は被覆して複合体を作製することができる。被着体の各種材料は、シクロオレフィンポリマー等のポリオレフィン、トリアセチルセルロース、フッ素系ポリマー、ポリエステル、ポリカーボネート、ガラス、金属からなる群から選ばれる１種以上が好ましく、ポリカーボネート、ポリオレフィン、ガラスからなる群から選ばれる１種以上がより好ましい。 The curable resin composition of the present invention can be used as an adhesive composition. In the present invention, a composite can be produced by bonding or coating an adherend with a cured body of the adhesive composition. The various materials of the adherend are preferably at least one selected from the group consisting of polyolefins such as cycloolefin polymers, triacetyl cellulose, fluorine-based polymers, polyesters, polycarbonates, glasses and metals, and groups consisting of polycarbonates, polyolefins and glasses. 1 or more types selected from are more preferable.
本発明の硬化性樹脂組成物にて接着した被着体は、完全硬化させた後にリワーク（再利用）することが可能である。リワークの方法としては特に制限は無いが、貼り合わされた１種又は２種の被着体間に０．０１～１００Ｎの荷重を負荷することにより被着体同士を解体し、解体後の被着体を再利用することが可能となる。 The adherend adhered with the curable resin composition of the present invention can be reworked (reused) after being completely cured. The rework method is not particularly limited, but the adherends are disassembled by applying a load of 0.01 to 100 N between the one or two kinds of adherends bonded together, and the adherend after disassembly The body can be reused.
以下に、実験例をあげて、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。実験例に記載の硬化性樹脂組成物中の各成分としては、以下の化合物を選択した。 Hereinafter, the present invention will be described in more detail with reference to experimental examples, but the present invention is not limited thereto. The following compounds were selected as each component in the curable resin composition described in the experimental examples.
（Ａ）成分の、ジエン系又は水素添加されたジエン系の骨格を有するオリゴマーとして、以下の化合物を選択した。
（Ａ－１）両末端メタクリル変性１，２－ポリブタジエンオリゴマー（日本曹達社製「ＴＥ－２０００」）(ＧＰＣによるポリスチレン換算の数平均分子量２０００)
（Ａ－２）イソプレンオリゴマー（クラレ社製「ＬＩＲ－５０」）（ＧＰＣによるポリスチレン換算の数平均分子量５４０００）
（Ａ－３）ブタジエンオリゴマー（クラレ社製「ＬＢＲ－３０７」）（ＧＰＣによるポリスチレン換算の数平均分子量８０００）
（Ａ－４）イソプレン重合物の無水マレイン酸付加物と２－ヒドロキシエチルメタクリレートとのエステル化物オリゴマー（クラレ社製「ＵＣ－２０３」）（ＧＰＣによるポリスチレン換算の数平均分子量３６０００）
（Ｂ）成分の、ホモポリマーガラス転移温度が－１００～６０℃を示す（メタ）アクリレートとして、以下の化合物を選択した。
（Ｂ－１）ラウリルメタクリレート（共栄社化学社製「ライトエステルＬ」：ホモポリマーガラス転移温度：－６５℃）
（Ｂ－２）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」：ホモポリマーガラス転移温度：５５℃）
（Ｂ－３）イソステアリルアクリレート（大阪有機化学工業社製「ＩＳＴＡ」：ホモポリマーガラス転移温度：－５８℃）
（Ｃ）成分の光開始剤として、以下の化合物を選択した。
（Ｃ－１）１－ヒドロキシシクロヘキシルフェニルケトン（チバスペシャリティケミカル社製「Ｉｒｇａｃｕｒｅ１８４」）
（Ｄ）成分の、（Ａ）成分及び（Ｂ）成分以外の（メタ）アクリレートとして、以下の化合物を選択した。
（Ｄ－１）ジシクロペンテニルアクリレート（ホモポリマーガラス転移温度：１２０℃）
（Ｄ－２）イソボルニルメタクリレート（ホモポリマーガラス転移温度：１２０℃）
（Ｅ）成分の、シランカップリング剤として、以下の化合物を選択した。
（Ｅ－１）γ－グリシドキシプロピルトリメトキシシラン The following compounds were selected as oligomers having a diene-based or hydrogenated diene-based skeleton as the component (A).
(A-1) Methacrylate-modified 1,2-polybutadiene oligomer (“TE-2000” manufactured by Nippon Soda Co., Ltd.) (number average molecular weight 2000 in terms of polystyrene by GPC)
(A-2) Isoprene oligomer (“LIR-50” manufactured by Kuraray Co., Ltd.) (Number average molecular weight in terms of polystyrene by GPC 54000)
(A-3) Butadiene oligomer (“LBR-307” manufactured by Kuraray Co., Ltd.) (Number average molecular weight 8000 in terms of polystyrene by GPC)
(A-4) An esterified oligomer of maleic anhydride adduct of isoprene polymer and 2-hydroxyethyl methacrylate (“UC-203” manufactured by Kuraray Co., Ltd.) (number average molecular weight 36,000 in terms of polystyrene by GPC)
As the component (B), the following compounds were selected as (meth) acrylates having a homopolymer glass transition temperature of −100 to 60 ° C.
(B-1) Lauryl methacrylate (“Light Ester L” manufactured by Kyoeisha Chemical Co., Ltd .: homopolymer glass transition temperature: −65 ° C.)
(B-2) 2-hydroxyethyl methacrylate (“Kyoeisha Chemical Co., Ltd.“ Light Ester HO ”: homopolymer glass transition temperature: 55 ° C.)
(B-3) Isostearyl acrylate (“ISTA” manufactured by Osaka Organic Chemical Industry Co., Ltd .: homopolymer glass transition temperature: −58 ° C.)
The following compounds were selected as the photoinitiator for component (C).
(C-1) 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Specialty Chemicals)
(D) component, as the component (A) and (B) other than the component (meth) acrylate, select the following compounds.
(D-1) Dicyclopentenyl acrylate (homopolymer glass transition temperature: 120 ° C.)
(D-2) Isobornyl methacrylate (homopolymer glass transition temperature: 120 ° C.)
The following compounds were selected as the silane coupling agent of component (E).
(E-1) γ-Glycidoxypropyltrimethoxysilane
各種物性は、次のように測定した。 Various physical properties were measured as follows.
〔光硬化性〕温度２３℃で測定した。光硬化性に関しては、テンパックスガラス（幅２５ｍｍ×長さ２５ｍｍ×厚さ２ｍｍ）の表面に硬化性樹脂組成物を厚み０．１ｍｍになるように塗布した。その後、無電極放電ランプを使用したフュージョン社製硬化装置を用い、波長３６５ｎｍのＵＶ光を積算光量２０００ｍＪ／ｃｍ2の条件にて照射し、硬化させた。
硬化率は、ＦＴ－ＩＲを使用し、以下の式により算出した。炭素と炭素の二重結合の吸収スペクトルは、１６００ｃｍ-1付近のピークを用いた。
（硬化率）＝１００－（硬化後の、炭素と炭素の二重結合の吸収スペクトルの強度）／（硬化前の、炭素と炭素の二重結合の吸収スペクトルの強度）×１００（％） [Photocurability] Measured at a temperature of 23 ° C. Regarding photocurability, a curable resin composition was applied to a surface of Tempax glass (width 25 mm × length 25 mm × thickness 2 mm) to a thickness of 0.1 mm. Thereafter, using a curing device manufactured by Fusion Corporation using an electrodeless discharge lamp, UV light having a wavelength of 365 nm was irradiated and cured under the condition of an integrated light quantity of 2000 mJ / cm 2 .
The curing rate was calculated by the following formula using FT-IR. The peak near 1600 cm −1 was used for the absorption spectrum of the carbon-carbon double bond.
(Curing rate) = 100- (Intensity of absorption spectrum of carbon-carbon double bond after curing) / (Intensity of absorption spectrum of carbon-carbon double bond before curing) × 100 (%)
〔ポリエチレンテレフタレート（ＰＥＴ）接着性評価（ポリエチレンテレフタレート試験片間の剥離接着強さ）〕２軸延伸ＰＥＴフィルム（ルミラーＴ６０、東レ社製）の試験片（幅５０ｍｍ×長さ１０ｍｍ×厚さ０．０５ｍｍ）同士を、硬化性樹脂組成物を接着剤組成物として用いて、接着層の厚み３０μｍで接着面積を縦４０ｍｍ×横１０ｍｍとして接着させた。光照射による硬化後、接着剤で接着した該試験片の、密着されていない２箇所のフィルム端部を引っ張ることで、フィルム同士が密着された部分を剥離させて、初期の１８０°剥離接着強さを測定した。光照射条件は〔光硬化性〕に記載の方法に従った。剥離接着強さ（単位：Ｎ／ｃｍ）は、引張試験器を用いて温度２３℃、湿度５０％の環境下で引張速度１０ｍｍ／分で測定した。 [Polyethylene terephthalate (PET) adhesion evaluation (peel adhesion strength between polyethylene terephthalate test pieces)] A test piece (width 50 mm × length 10 mm × thickness 0.times.) Of a biaxially stretched PET film (Lumirror T60, manufactured by Toray Industries, Inc.). 05 mm) were bonded using a curable resin composition as an adhesive composition with an adhesive layer thickness of 30 μm and an adhesive area of 40 mm long × 10 mm wide. After curing by light irradiation, by pulling the two non-adhered film end portions of the test piece bonded with an adhesive, the film-adhered portions are peeled off, and the initial 180 ° peel adhesion strength Was measured. The light irradiation conditions followed the method described in [Photocurability]. The peel adhesion strength (unit: N / cm) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.
〔ガラス接着性評価（耐熱ガラス試験片間の引張接着強さ）〕耐熱ガラス試験片（幅２５ｍｍ×長さ２５ｍｍ×厚さ２．０ｍｍ）同士を、厚み８０μｍ×幅１２．５ｍｍ×長さ２５ｍｍのテフロン（登録商標）テープをスペーサーとして用い、硬化性樹脂組成物を接着剤組成物として用いて接着させた（接着面積３．１２５ｃｍ2）。光照射条件は〔光硬化性〕に記載の方法に従った。上記条件にて接着剤組成物を硬化させた後、更に、試験片の外両面に電気化学工業社製接着剤組成物「Ｇ－５５」を使用し、亜鉛メッキ鋼板（幅１００ｍｍ×長さ２５ｍｍ×厚さ２．０ｍｍ、エンジニアリングテストサービス社製）を接着させた。硬化後、接着剤組成物で接着した該試験片を用いて、亜鉛メッキ鋼板をチャックして、初期の引張剪断接着強さを測定した。引っ張り剪断接着強さ（単位：ＭＰａ）は、引張試験器を用いて温度２３℃、湿度５０％の環境下で引張速度１０ｍｍ／分で測定した。 [Glass Adhesion Evaluation (Tensile Adhesive Strength Between Heat-Resistant Glass Test Pieces)] Heat-resistant glass test pieces (width 25 mm × length 25 mm × thickness 2.0 mm) are 80 μm thick × 12.5 mm wide × 25 mm long. The Teflon (registered trademark) tape was used as a spacer and the curable resin composition was used as an adhesive composition (adhesion area: 3.125 cm 2 ). The light irradiation conditions followed the method described in [Photocurability]. After the adhesive composition was cured under the above conditions, an adhesive composition “G-55” manufactured by Denki Kagaku Kogyo Co., Ltd. was further used on both outer surfaces of the test piece, and a galvanized steel sheet (width 100 mm × length 25 mm). × Thickness 2.0 mm, manufactured by Engineering Test Service Co., Ltd.) was adhered. After the curing, using the test piece bonded with the adhesive composition, the galvanized steel sheet was chucked, and the initial tensile shear bond strength was measured. The tensile shear bond strength (unit: MPa) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.
〔シクロオレフィンポリマー（ＣＯＰ）接着性評価（シクロオレフィンポリマー試験片間の剥離接着強さ）〕ＣＯＰフィルム（ＺＥＯＮＯＲ、日本ゼオン社製）の試験片（幅５０ｍｍ×長さ１０ｍｍ×厚さ０．０５ｍｍ）同士を、硬化性樹脂組成物を接着剤組成物として用いて、接着層の厚み１０μｍで接着面積を縦４０ｍｍ×横１０ｍｍとして接着させた。光照射による硬化後、接着剤組成物で接着した該試験片の、密着されていない２箇所のフィルム端部を引っ張ることで、フィルム同士が密着された部分を剥離させて、初期の１８０°剥離接着強さを測定した。光照射条件は〔光硬化性〕に記載の方法に従った。剥離接着強さ（単位：Ｎ／ｃｍ）は、引張試験器を用いて温度２３℃、湿度５０％の環境下で引張速度１０ｍｍ／分で測定した。 [Evaluation of cycloolefin polymer (COP) adhesion (peel adhesion strength between cycloolefin polymer test pieces)] COP film (ZEONOR, manufactured by Nippon Zeon Co., Ltd.) test piece (width 50 mm × length 10 mm × thickness 0.05 mm) ) Were bonded using a curable resin composition as an adhesive composition, with an adhesive layer thickness of 10 μm and an adhesive area of 40 mm long × 10 mm wide. After curing by light irradiation, by pulling the two end portions of the film that are not in close contact with the test piece bonded with the adhesive composition, the portions where the films are in close contact are peeled off, and the initial 180 ° peeling is performed. The bond strength was measured. The light irradiation conditions followed the method described in [Photocurability]. The peel adhesion strength (unit: N / cm) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.
〔耐湿熱性評価（高温高湿暴露後の耐熱ガラス試験片間の引張接着強さ）〕テンパックスガラス（幅２５ｍｍ×長さ２５ｍｍ×厚さ２ｍｍ）同士を、硬化性樹脂組成物を接着剤組成物として用いて、接着層の厚み１００μｍで接着面積を１．０ｍｍ2として接着させ硬化させた。光照射条件は〔光硬化性〕に記載の方法に従った。硬化後、接着剤組成物で接着した該試験片を、恒温恒湿槽を用いて、温度８５℃、相対湿度８５％の環境下に１０００時間暴露した。暴露後の試験片を用いて、引張剪断接着強さを測定した。接着部位の外観を目視で観察し、黄変しているか否かを調べた。剥離接着強さ（単位：Ｎ／ｃｍ）は、引張試験器を用いて温度２３℃、湿度５０％の環境下で引張速度１０ｍｍ／分で測定した。 [Heat and heat resistance evaluation (tensile bond strength between heat-resistant glass test pieces after exposure to high temperature and high humidity)] Tempax glass (width 25 mm x length 25 mm x thickness 2 mm) and curable resin composition as adhesive composition As a product, the adhesive layer was 100 μm thick, and the adhesive area was set to 1.0 mm 2 to be cured. The light irradiation conditions followed the method described in [Photocurability]. After the curing, the test piece bonded with the adhesive composition was exposed to an environment of a temperature of 85 ° C. and a relative humidity of 85% for 1000 hours using a constant temperature and humidity chamber. The tensile shear bond strength was measured using the test piece after exposure. The appearance of the bonded part was visually observed to determine whether it was yellowed. The peel adhesion strength (unit: N / cm) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.
〔トリアセチルセルロース接着性評価（トリアセチルセルロース試験片間の剥離接着強さ）〕トリアセチルセルロース（ＴＡＣ）フィルム（平均厚さ４０μｍ、富士フィルム社製）の試験片（幅５０ｍｍ×長さ１０ｍｍ×厚さ０．０４ｍｍ）同士を、硬化性樹脂組成物を接着剤組成物として用いて、接着層の厚み１０μｍで接着面積を縦４０ｍｍ×横１０ｍｍとして接着させた。光照射による硬化後、接着剤組成物で接着した該試験片の、密着されていない２箇所のフィルム端部を引っ張ることで、フィルム同士が密着された部分を剥離させて、初期の１８０°剥離接着強さを測定した。光照射条件は〔光硬化性〕に記載の方法に従った。剥離接着強さ（単位：Ｎ／ｃｍ）は、引張試験器を用いて温度２３℃、湿度５０％の環境下で引張速度５０ｍｍ／分で測定した。 [Triacetyl cellulose adhesion evaluation (peeling adhesive strength between triacetyl cellulose test pieces)] Triacetyl cellulose (TAC) film (average thickness 40 μm, manufactured by Fuji Film Co., Ltd.) test piece (width 50 mm × length 10 mm × A thickness of 0.04 mm was bonded to each other with the adhesive layer having a thickness of 10 μm and a bonding area of 40 mm in length and 10 mm in width by using the curable resin composition as an adhesive composition. After curing by light irradiation, by pulling the two end portions of the film that are not in close contact with the test piece bonded with the adhesive composition, the portions where the films are in close contact with each other are peeled off, and the initial 180 ° peeling is performed. The bond strength was measured. The light irradiation conditions followed the method described in [Photocurability]. The peel adhesion strength (unit: N / cm) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 50 mm / min.
〔フッ素系ポリマー接着性評価（フッ素フィルム試験片間の剥離接着強さ）〕ＰＶＤＦフィルム（平均厚さ４０μｍ、電気化学工業社製「ＤＸフィルム」）の試験片（幅５０ｍｍ×長さ１０ｍｍ×厚さ０．０４ｍｍ）同士を、硬化性樹脂組成物を接着剤組成物として用いて、接着層の厚み１０μｍで接着面積を縦４０ｍｍ×横１０ｍｍとして接着させた。光照射による硬化後、接着剤組成物で接着した該試験片の、密着されていない２箇所のフィルム端部を引っ張ることで、フィルム同士が密着された部分を剥離させて、初期の１８０°剥離接着強さを測定した。光照射条件は〔光硬化性〕に記載の方法に従った。剥離接着強さ（単位：Ｎ／ｃｍ）は、引張試験器を用いて温度２３℃、湿度５０％の環境下で引張速度５０ｍｍ／分で測定した。 [Fluorine-based polymer adhesion evaluation (peel adhesion strength between fluorine film test pieces)] PVDF film (average thickness 40 μm, “DX film” manufactured by Denki Kagaku Kogyo Co., Ltd.) test piece (width 50 mm × length 10 mm × thickness) 0.04 mm) were bonded to each other using a curable resin composition as an adhesive composition with an adhesive layer thickness of 10 μm and an adhesive area of 40 mm long × 10 mm wide. After curing by light irradiation, by pulling the two end portions of the film that are not in close contact with the test piece bonded with the adhesive composition, the portions where the films are in close contact are peeled off, and the initial 180 ° peeling is performed. The bond strength was measured. The light irradiation conditions followed the method described in [Photocurability]. The peel adhesive strength (unit: N / cm) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 50 mm / min.
〔ポリカーボネート接着性評価（ポリカーボネート試験片間の引張接着強さ）〕ポリカーボネート(帝人社製「パンライト」)試験片（幅２５ｍｍ×長さ２５ｍｍ×厚さ２．０ｍｍ）同士を、厚み８０μｍ×幅１２．５ｍｍ×長さ２５ｍｍのテフロン（登録商標）テープをスペーサーとして用い、硬化性樹脂組成物を接着剤組成物として用いて接着させた（接着面積３．１２５ｃｍ2）。光照射条件は〔光硬化性〕に記載の方法に従った。引っ張り剪断接着強さ（単位：ＭＰａ）は、引張試験器を用いて温度２３℃、湿度５０％の環境下で引張速度１０ｍｍ／分で測定した。 [Polycarbonate Adhesion Evaluation (Tensile Adhesive Strength Between Polycarbonate Specimens)] Polycarbonate (“Panlite” manufactured by Teijin Ltd.) Specimens (width 25 mm × length 25 mm × thickness 2.0 mm), 80 μm × width A Teflon (registered trademark) tape of 12.5 mm × 25 mm in length was used as a spacer and a curable resin composition was used as an adhesive composition (adhesion area 3.125 cm 2 ). The light irradiation conditions followed the method described in [Photocurability]. The tensile shear bond strength (unit: MPa) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.
〔金属接着性評価（ＳＰＣＣ試験片とガラス試験片間の引張接着強さ）〕ＳＰＣＣ試験片（幅２５ｍｍ×長さ２５ｍｍ×厚さ１．６ｍｍ）とテンパックスガラス（幅２５ｍｍ×長さ２５ｍｍ×厚さ２ｍｍ）を、厚み８０μｍ×幅１２．５ｍｍ×長さ２５ｍｍのテフロン（登録商標）テープをスペーサーとして用い、硬化性樹脂組成物を接着剤組成物として用いて接着させた（接着面積３．１２５ｃｍ2）。光照射条件は〔光硬化性〕に記載の方法に従った。上記条件にて接着剤組成物を硬化させた後、更に、テンパックス試験片側に電気化学工業社製接着剤組成物「Ｇ－５５」を使用し、亜鉛メッキ鋼板（幅１００ｍｍ×長さ２５ｍｍ×厚さ２．０ｍｍ、エンジニアリングテストサービス社製）を接着させた。硬化後、接着剤組成物で接着した該試験片を用いて、亜鉛メッキ鋼板をチャックして、初期の引張剪断接着強さを測定した。引っ張り剪断接着強さ（単位：ＭＰａ）は、引張試験器を用いて温度２３℃、湿度５０％の環境下で引張速度１０ｍｍ／分で測定した。 [Metal adhesion evaluation (tensile bond strength between SPCC test piece and glass test piece)] SPCC test piece (width 25 mm x length 25 mm x thickness 1.6 mm) and Tempax glass (width 25 mm x length 25 mm x 2 mm thick) was adhered using a Teflon (registered trademark) tape having a thickness of 80 μm × width of 12.5 mm × length of 25 mm as a spacer and a curable resin composition as an adhesive composition (adhesion area 3. 125 cm 2 ). The light irradiation conditions followed the method described in [Photocurability]. After the adhesive composition was cured under the above conditions, an adhesive composition “G-55” manufactured by Denki Kagaku Kogyo Co., Ltd. was used on the Tempax test piece side, and a galvanized steel sheet (width 100 mm × length 25 mm × A thickness of 2.0 mm, manufactured by Engineering Test Service Co., Ltd.) was adhered. After the curing, using the test piece bonded with the adhesive composition, the galvanized steel sheet was chucked, and the initial tensile shear bond strength was measured. The tensile shear bond strength (unit: MPa) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.
〔外観観察（黄変度）〕テンパックスガラス（幅２５ｍｍ×長さ２５ｍｍ×厚さ２ｍｍ）同士を、硬化性樹脂組成物を接着剤組成物として用いて、接着層の厚み１００μｍで接着面積を１．０ｍｍ2として接着させ硬化させた。光照射条件は〔光硬化性〕に記載の方法に従った。硬化後、カラー測定装置（ＳＨＩＭＡＤＺＵ社製「ＵＶ－ＶＩＳＩＢＬＥ　ＳＰＥＣＴＲＯＰＯＨＯＴＯＭＥＴＥＲ」）にてΔｂ値を黄変度とした。 [Observation of appearance (degree of yellowing)] Tempax glass (width 25 mm x length 25 mm x thickness 2 mm), using a curable resin composition as an adhesive composition, the adhesive area with an adhesive layer thickness of 100 μm It was made to adhere | attach and harden as 1.0 mm < 2 >. The light irradiation conditions followed the method described in [Photocurability]. After curing, the Δb value was determined as the degree of yellowing with a color measuring device (“UV-VISABLE SPECTROTOPOMETER” manufactured by SHIMADZU).
（実験例）
表1に示す組成の硬化性樹脂組成物を調製し、各種物性を測定した。結果を表1に示す。 (Experimental example)
A curable resin composition having the composition shown in Table 1 was prepared, and various physical properties were measured. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001




















Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002


















Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003


















Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
実施例及び比較例から、以下のことが判る。本発明の硬化性樹脂組成物は、高い接着性を示す。本発明の硬化性樹脂組成物は、高い接着性を示す。特に、ポリカーボネート、ポリオレフィン、ガラスに対して、高い接着性を示す。本発明の硬化性樹脂組成物は、高い接着性を示すので、薄いガラスのＬＣＤ等の表示体と、アクリル板やポリカーボネート板等の光学機能材料とを貼り合わせる場合、接着面が剥がれたり、ＬＣＤが割れたり、ＬＣＤが表示ムラになったりしない。本発明の硬化性樹脂組成物は、耐湿熱性が大きく、加温雰囲気での被着体の変形に追随できるので、被着体が剥がれることもない。実験例１４は、シランカップリング剤を含有しないが、比較例よりも高い接着性を有する。 The following can be seen from the examples and comparative examples. The curable resin composition of the present invention exhibits high adhesiveness. The curable resin composition of the present invention exhibits high adhesiveness. In particular, it exhibits high adhesion to polycarbonate, polyolefin, and glass. Since the curable resin composition of the present invention exhibits high adhesiveness, when a display body such as a thin glass LCD is bonded to an optical functional material such as an acrylic plate or a polycarbonate plate, the adhesive surface may be peeled off, or the LCD Will not break or the LCD will not display unevenly. The curable resin composition of the present invention has a high resistance to moist heat and can follow the deformation of the adherend in a heated atmosphere, so that the adherend is not peeled off. Experimental Example 14 does not contain a silane coupling agent, but has higher adhesion than the comparative example.
比較例の場合、本発明の効果を有しない。実験例１５は、成分（Ｃ）を含有しないので、硬化性樹脂組成物が硬化せず、接着性が小さい。実験例１６と実験例１７は、イソボルニルメタクリレートやジシクロペンテニルアクリレートといった、剛直な骨格を有する脂環式（メタ）アクリレートを多量に含有し、かつ、成分（Ｂ）を含有しないので、硬化性樹脂組成物が柔軟性を有さず、接着性が小さい。 In the case of a comparative example, it does not have the effect of this invention. Since Experimental Example 15 does not contain a component (C), a curable resin composition does not harden | cure and adhesiveness is small. Experimental Example 16 and Experimental Example 17 contain a large amount of an alicyclic (meth) acrylate having a rigid skeleton such as isobornyl methacrylate and dicyclopentenyl acrylate, and do not contain the component (B). The resin composition does not have flexibility and has low adhesiveness.
本発明の硬化性樹脂組成物は、タッチパネル積層体用の接着剤組成物に使用できる。タッチパネル積層体は一般的にカバー材／タッチパネルセンサー／液晶パネルの層で構成されている。本発明に係る硬化性樹脂組成物はタッチパネルセンサーとカバー材を貼り合わせる接着剤として使用でき、例えば、タッチパネルの表面に、化粧板や、タッチする位置を指定するアイコンシートなどのカバー材を貼り合わせる際の接着剤として使用できる。また、タッチパネルセンサーと液晶パネルを貼り合わせる接着剤としても使用できる。また、静電容量式タッチパネルの場合は、透明基板の上に透明電極を形成し、その上に透明板を貼り合わせた構造を有している。本発明の硬化性樹脂組成物は、透明基板の上に透明電極を形成し、その上に透明板を貼り合わせる際の接着剤としても好適である。本発明のタッチパネル積層体は、ディスプレイとして使用できる。 The curable resin composition of the present invention can be used for an adhesive composition for a touch panel laminate. The touch panel laminate is generally composed of a cover material / touch panel sensor / liquid crystal panel layer. The curable resin composition according to the present invention can be used as an adhesive for bonding a touch panel sensor and a cover material. For example, a cover material such as a decorative plate or an icon sheet for designating a touch position is bonded to the surface of the touch panel. It can be used as an adhesive. It can also be used as an adhesive that bonds the touch panel sensor and the liquid crystal panel together. In the case of a capacitive touch panel, a transparent electrode is formed on a transparent substrate, and a transparent plate is bonded thereon. The curable resin composition of the present invention is also suitable as an adhesive when a transparent electrode is formed on a transparent substrate and a transparent plate is bonded thereon. The touch panel laminate of the present invention can be used as a display.

Claims (15)

  1. 下記（Ａ）～（Ｄ）成分を含有し、（Ａ）成分及び（Ｂ）成分の合計使用量が硬化性樹脂組成物の８０～９９質量％を占め、（Ｄ）成分の使用量は、（Ａ）成分、（Ｂ）成分及び（Ｄ）成分の合計１００質量部中、０～１０質量部である硬化性樹脂組成物。
    （Ａ）ジエン系又は水素添加されたジエン系の骨格を有するオリゴマー、
    （Ｂ）ホモポリマーガラス転移温度が－１００～６０℃を示す非環式(メタ)アクリレート、
    （Ｃ）光重合開始剤
    （Ｄ）（Ａ）成分及び（Ｂ）成分以外の(メタ)アクリレート     The following components (A) to (D) are contained, and the total amount of the components (A) and (B) occupies 80 to 99% by mass of the curable resin composition. A curable resin composition that is 0 to 10 parts by mass in a total of 100 parts by mass of the component (A), the component (B), and the component (D).
    (A) an oligomer having a diene-based or hydrogenated diene-based skeleton,
    (B) an acyclic (meth) acrylate having a homopolymer glass transition temperature of −100 to 60 ° C.,
    (C) Photopolymerization initiator (D) (Meth) acrylate other than components (A) and (B)
  2. （Ｂ）成分が、一般式（１）の化合物である請求項１に記載の硬化性樹脂組成物。
    一般式（１） Ｚ－Ｏ－Ｒ1
    〔式中、Ｚは（メタ）アクリロイル基を示し、Ｒ1 は炭素数９～２０個のアルキル基を表す。〕     (B) component, the curable resin composition according to claim 1 which is a compound of the general formula (1).
    General formula (1) Z—O—R 1
    Wherein, Z is shown a (meth) acryloyl group, R 1 represents a number 9-20 alkyl group having a carbon. ]
  3. （Ａ）成分及び（Ｂ）成分の合計１００質量部中、(Ａ)成分が３０～９８質量部、（Ｂ）成分が２～７０質量部である請求項１又は２に記載の硬化性樹脂組成物。 The curable resin according to claim 1 or 2, wherein the component (A) is 30 to 98 parts by mass and the component (B) is 2 to 70 parts by mass in a total of 100 parts by mass of the component (A) and the component (B). Composition.
  4. （Ｂ）成分が、イソステアリル（メタ）アクリレート、ラウリル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、１，３－ブチレングリコールジ（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレートからなる群のうちの１種以上である請求項１又は３に記載の硬化性樹脂組成物。 Component (B) is isostearyl (meth) acrylate, lauryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) The curing according to claim 1 or 3, which is at least one member selected from the group consisting of acrylate, ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. Resin composition.
  5. （Ｂ）成分が、ラウリル（メタ）アクリレート及び／又はイソステアリル（メタ）アクリレートである請求項１～４のうちのいずれか１項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 4, wherein the component (B) is lauryl (meth) acrylate and / or isostearyl (meth) acrylate.
  6. 更に、（Ｅ）成分として、シランカップリング剤を含有する請求項１～５のうちのいずれか１項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 5, further comprising a silane coupling agent as component (E).
  7. （Ａ）成分のジエン系又は水素添加されたジエン系の骨格が、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１種以上の骨格である請求項１～６のうちのいずれか１項に記載の硬化性樹脂組成物。 The diene-based or hydrogenated diene-based skeleton of the component (A) is at least one skeleton selected from the group consisting of polybutadiene, polyisoprene, a hydrogenated polybutadiene, and a hydrogenated polyisoprene. Item 7. The curable resin composition according to any one of Items 1 to 6.
  8. （Ａ）成分のジエン系又は水素添加されたジエン系の骨格を有するオリゴマーの分子量が５００～７００００である請求項１～７のうちのいずれか１項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 7, wherein the molecular weight of the oligomer having a diene-based or hydrogenated diene-based skeleton as the component (A) is 500 to 70000.
  9. 　（Ａ）成分及び（Ｂ）成分の合計１００質量部中、(Ａ)成分が５０～９０質量部、（Ｂ）成分が１０～５０質量部であり、（Ｃ）成分の使用量は、（Ａ）成分、（Ｂ）成分及び（Ｄ）成分の合計１００質量部に対して、０．０１～１０質量部であり、（Ｅ）成分の使用量は、（Ａ）成分、（Ｂ）成分及び（Ｄ）成分の合計１００質量部に対して、０．０１～１０質量部である請求項１～８のうちのいずれか１項に記載の硬化性樹脂組成物。 In 100 parts by mass of the total of component (A) and component (B), component (A) is 50 to 90 parts by mass, component (B) is 10 to 50 parts by mass, and the amount of component (C) used is ( A) component, (B) component, and (D) component are 0.01 to 10 parts by mass with respect to 100 parts by mass in total, and the amount of (E) component used is (A) component, (B) component The curable resin composition according to any one of claims 1 to 8, which is 0.01 to 10 parts by mass with respect to 100 parts by mass in total of the components (D).
  10. 請求項１～９のうちのいずれか１項に記載の硬化性樹脂組成物からなる接着剤組成物。 An adhesive composition comprising the curable resin composition according to any one of claims 1 to 9.
  11. 請求項１０記載の硬化性樹脂組成物からなる接着剤組成物の硬化体。 A cured product of an adhesive composition comprising the curable resin composition according to claim 10.
  12. 請求項１１記載の硬化体により被着体が被覆又は被着体同士が接合された複合体。 The composite_body | complex with which the to-be-adhered body was coat | covered or the to-be-adhered bodies were joined by the hardening body of Claim 11.
  13. 請求項１２記載の被着体がトリアセチルセルロース、フッ素系ポリマー、ポリエステル、ポリカーボネート、ポリオレフィン、ガラス、金属からなる群から選ばれる１種以上である複合体。 The composite_body | complex which the to-be-adhered body of Claim 12 is 1 or more types chosen from the group which consists of a triacetyl cellulose, a fluorine-type polymer, polyester, a polycarbonate, polyolefin, glass, and a metal.
  14. 請求項１０に記載の接着剤組成物により被着体を貼り合わせたタッチパネル積層体。 The touch-panel laminated body which bonded together the to-be-adhered body with the adhesive composition of Claim 10.
  15. 請求項１４に記載のタッチパネル積層体を備えたディスプレイ。 A display comprising the touch panel laminate according to claim 14.
PCT/JP2011/065075 2010-07-08 2011-06-30 Curable resin composition WO2012005169A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014142054A1 (en) * 2013-03-13 2014-09-18 富士フイルム株式会社 Adhesive film, and stacked body for touch panel
WO2014142052A1 (en) * 2013-03-13 2014-09-18 富士フイルム株式会社 Adhesive sheet, stacked body for touch panel, and capacitance-type touch panel
JP2014525960A (en) * 2011-07-25 2014-10-02 ヘンケル・チャイナ・カンパニー・リミテッド Photocurable adhesive composition and use thereof
WO2015025803A1 (en) * 2013-08-21 2015-02-26 富士フイルム株式会社 Adhesive sheet for touch panels, laminate for touch panels and capacitive touch panel
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JP2015105279A (en) * 2013-11-28 2015-06-08 株式会社クラレ Curable resin composition
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* Cited by examiner, † Cited by third party
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JP7282192B2 (en) * 2019-09-27 2023-05-26 ソマール株式会社 UV curable resin composition and UV curable sheet
US20220396645A1 (en) * 2019-12-13 2022-12-15 Nitto Shinko Corporation Curable composition

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58117207A (en) * 1981-12-31 1983-07-12 Matsushita Electric Works Ltd Ultraviolet ray-curable resin composition
JP2003266613A (en) * 2002-03-15 2003-09-24 Toyo Ink Mfg Co Ltd Substrate for gas barrier laminate and gas barrier laminate using the same
JP2006306951A (en) * 2005-04-27 2006-11-09 Mitsubishi Rayon Co Ltd Method for producing acrylic resin plate, polymerizable composition for touch panel, transparent base plate using the polymerizable composition, transparent electrode plate and touch panel
JP2008069239A (en) * 2006-09-13 2008-03-27 Denki Kagaku Kogyo Kk Acrylic adhesive for art glass
JP2010000434A (en) * 2008-06-19 2010-01-07 Jsr Corp Method for manufacturing touch panel

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2865534B2 (en) * 1993-09-22 1999-03-08 積水化学工業株式会社 Adhesive and adhesive tapes
JP2003342335A (en) * 2002-05-28 2003-12-03 Mitsui Takeda Chemicals Inc Aqueous emulsion composition and adhesive composition
JP4645797B2 (en) * 2004-04-23 2011-03-09 株式会社スリーボンド Photo-curable resin composition for difficult-to-adhere materials
JP4916681B2 (en) * 2005-07-04 2012-04-18 電気化学工業株式会社 Photocurable adhesive for temporary fixing method and temporary fixing method of member using the same
JP5052792B2 (en) * 2006-01-13 2012-10-17 電気化学工業株式会社 Resin composition and method for temporarily fixing and protecting surface of workpiece using the same
JP5570752B2 (en) * 2008-05-12 2014-08-13 電気化学工業株式会社 Adhesive
TWI485214B (en) * 2008-09-05 2015-05-21 Kyoritsu Chemical Co Ltd And a photohardenable resin composition for bonding an optical functional material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58117207A (en) * 1981-12-31 1983-07-12 Matsushita Electric Works Ltd Ultraviolet ray-curable resin composition
JP2003266613A (en) * 2002-03-15 2003-09-24 Toyo Ink Mfg Co Ltd Substrate for gas barrier laminate and gas barrier laminate using the same
JP2006306951A (en) * 2005-04-27 2006-11-09 Mitsubishi Rayon Co Ltd Method for producing acrylic resin plate, polymerizable composition for touch panel, transparent base plate using the polymerizable composition, transparent electrode plate and touch panel
JP2008069239A (en) * 2006-09-13 2008-03-27 Denki Kagaku Kogyo Kk Acrylic adhesive for art glass
JP2010000434A (en) * 2008-06-19 2010-01-07 Jsr Corp Method for manufacturing touch panel

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* Cited by examiner, † Cited by third party
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US10081741B2 (en) 2012-11-30 2018-09-25 Lintec Corporation Adhesive agent composition, adhesive sheet, and electronic device
WO2014142052A1 (en) * 2013-03-13 2014-09-18 富士フイルム株式会社 Adhesive sheet, stacked body for touch panel, and capacitance-type touch panel
JP2014198811A (en) * 2013-03-13 2014-10-23 富士フイルム株式会社 Adhesive sheet, laminate for touch panel, and electrostatic capacitance touch panel
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JPWO2014142054A1 (en) * 2013-03-13 2017-02-16 富士フイルム株式会社 Adhesive film, laminate for touch panel
WO2015025803A1 (en) * 2013-08-21 2015-02-26 富士フイルム株式会社 Adhesive sheet for touch panels, laminate for touch panels and capacitive touch panel
CN105492555A (en) * 2013-08-21 2016-04-13 富士胶片株式会社 Adhesive sheet for touch panels, laminate for touch panels and capacitive touch panel
JP2015172921A (en) * 2013-08-21 2015-10-01 富士フイルム株式会社 Touch panel adhesive sheet, touch panel laminate, static capacitance type touch panel
CN105492555B (en) * 2013-08-21 2017-08-01 富士胶片株式会社 Contact panel adhesive sheet, contact panel laminate, capacitive touch panel
KR101847750B1 (en) 2013-08-21 2018-04-10 후지필름 가부시키가이샤 Adhesive sheet for touch panels, laminate for touch panels and capacitive touch panel
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