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WO2011046120A1 - Resin composition and adhesive agent - Google Patents

Resin composition and adhesive agent Download PDF

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Publication number
WO2011046120A1
WO2011046120A1 PCT/JP2010/067895 JP2010067895W WO2011046120A1 WO 2011046120 A1 WO2011046120 A1 WO 2011046120A1 JP 2010067895 W JP2010067895 W JP 2010067895W WO 2011046120 A1 WO2011046120 A1 WO 2011046120A1
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WO
WIPO (PCT)
Prior art keywords
component
adhesive
meth
resin composition
acrylate
Prior art date
Application number
PCT/JP2010/067895
Other languages
French (fr)
Japanese (ja)
Inventor
佑基 比舎
公彦 依田
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 CN201080046336.1A priority Critical patent/CN102686622B/en
Priority to JP2011536141A priority patent/JP5684714B2/en
Priority to KR1020127012210A priority patent/KR101696332B1/en
Publication of WO2011046120A1 publication Critical patent/WO2011046120A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1807—C7-(meth)acrylate, e.g. heptyl (meth)acrylate or benzyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride

Definitions

  • the present invention relates to an adhesive.
  • Cycloolefin polymers are used in applications such as electronic materials, optical lenses and medical materials. Cycloolefin polymers are known as difficult adherends because of their low polarity and lack of many functional groups on the surface. Examples of the adhesive for adhering such a cycloolefin-based resin include a solvent-type adhesive and a hot melt adhesive.
  • Patent Document 1 As a method for adhering an olefin resin, there is a method of adhering with an instantaneous adhesive after performing a treatment with a primer as disclosed in Patent Document 1. Moreover, as disclosed in Patent Document 2, an energy ray-curable resin composition containing (meth) acrylate is disclosed.
  • a solvent type adhesive uses a solvent. Solvent-type adhesives are harmful to the human body, and it takes time for the solvent to evaporate, so that sufficient adhesive strength itself cannot be obtained.
  • the hot melt adhesive requires labor and equipment for melting the adhesive. Also, this adhesive cannot provide sufficient adhesive strength. In the case of using a hot melt adhesive, if the cycloolefin polymer is heated in advance, the adhesive strength is improved, but a new problem that the resin is deformed occurs.
  • Patent Document 1 According to the adhesion method disclosed in Patent Document 1, there is a problem that it takes time and effort for primer treatment, and a sufficient adhesion strength cannot be obtained.
  • Patent Document 2 discloses an energy ray curable resin composition containing (meth) acrylate. However, there is no description about (meth) acrylate having a dicyclopentenyl group.
  • An object of this invention is to provide the adhesive agent for cycloolefin polymers which can express sufficient adhesive strength in a short time with respect to a cycloolefin polymer, for example, and is a solvent-free type and environmentally friendly.
  • the present inventor has intensively studied to solve the above-described problems and has arrived at the present invention.
  • a resin composition comprising the following components (A) to (E).
  • (A) component is a (meth) acrylate having a dicyclopentenyl group
  • (B) component is a (meth) acrylate having a hydroxyl group
  • (C) component is having a (meth) acryloyl group and is a diene skeleton
  • the (meth) acrylate (D) component having a hydrogenated diene-based skeleton is a silane coupling agent (E) component is a photopolymerization initiator.
  • the resin composition according to the present invention further comprises (meth) acrylic acid as the component (F).
  • the resin composition according to the present invention further contains polyvinyl alcohol as the component (G).
  • the component (A) is dicyclopentenyl (meth) acrylate.
  • the component (C) has a number average molecular weight of 500 to 50,000.
  • the resin composition according to the present invention has a thickness of 0.03 mm, and when cured by irradiation for 15 seconds under conditions of a wavelength of 365 nm and an integrated light quantity of 2000 mJ / cm 2 , the storage elasticity of the cured product.
  • the rate is in the range of 0.1 to 100,000 MPa (23 ° C.).
  • the present invention is an adhesive comprising the resin composition according to the present invention.
  • the adhesive according to the present invention is a cycloolefin polymer adhesive.
  • the adhesive according to the present invention is an adhesive for a cycloolefin polymer having a dicyclopentadiene ring structure.
  • the present invention is an adhesive body in which adherends are bonded to each other using the adhesive according to the present invention.
  • the adherend according to the present invention is at least one member selected from the group consisting of cycloolefin polymer, polycarbonate, cellulose triacetate, polyvinyl alcohol and glass.
  • the adhesive according to the present invention is applied to the surface of the adherend so as to have a thickness of 0.0001 to 5 mm, and the adherends are bonded to each other to obtain a wavelength of 200 to 500 nm.
  • This is a method for producing an adhesive body comprising curing the adhesive under conditions of an integrated light quantity of 200 to 6000 J / cm 2 and an irradiation time of 1 to 60 seconds.
  • the resin composition of the present invention is characterized by high adhesive strength and excellent moisture resistance.
  • the component (A) in the present invention is a (meth) acrylate having a dicyclopentenyl group. More specifically, the component (A) is a (meth) acrylate containing one or more dicyclopentenyl groups at the terminal or side chain of the molecule.
  • Examples of (A) component (meth) acrylate include dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyloxypropyl (meth) acrylate, and dicyclopentenyl (meth) acrylate. Of these, dicyclopentenyl (meth) acrylate is preferred.
  • the component (B) is a (meth) acrylate containing a hydroxyl group. More specifically, the component (B) is a (meth) acrylate containing one or more hydroxyl groups at the end or side chain of the molecule.
  • hydroxyl group-containing (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate.
  • 2-hydroxy-3-phenoxypropyl (meth) acrylate is more preferable from the viewpoint of resin film adhesion.
  • the component (C) is a (meth) acrylate having a (meth) acryloyl group and having a diene skeleton or a hydrogenated diene skeleton. More specifically, the component (C) has one or more (meth) acryloyl groups at the terminal or side chain of the molecule, and has a diene skeleton or a hydrogenated diene skeleton.
  • (Meth) acrylates preferably (meth) acrylates having one or more (meth) acryloyl groups at the end of the molecule and having a diene skeleton or a hydrogenated diene skeleton. is there. This includes the following components from the viewpoint of imparting flexibility to the resin.
  • the main chain skeleton of (meth) acrylate is a diene skeleton or a hydrogenated diene skeleton.
  • the diene skeleton or the hydrogenated diene skeleton include one or more skeletons selected from the group consisting of polybutadiene, polyisoprene, a hydrogenated polybutadiene, and a hydrogenated polyisoprene.
  • at least one selected from the group consisting of polyisoprene and a hydrogenated product of polyisoprene is preferable, and polyisoprene is more preferable.
  • the (meth) acrylate of the component (C) 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 number average molecular weight of the component (C) (meth) acrylate is preferably 500 to 50,000, and more preferably 8000 to 45,000. If the number average molecular weight is 500 or more, the cured product obtained by irradiating the adhesive of the present invention with energy rays has a high hardness, so that it is easy to form an adhesive layer. If the number average molecular weight is 50000 or less, the viscosity of the resulting adhesive is small, so that the workability in mixing during the production process and the workability when using the adhesive in practical applications are good.
  • the component (C) (meth) acrylate includes “UC-203” manufactured by Kuraray Co., Ltd. (an esterified oligomer of maleic anhydride adduct of isoprene polymer and 2-hydroxyethyl methacrylate), “TEAI-” manufactured by Nippon Soda Co., Ltd. 1000 ”(hydrogenated 1,2-polybutadiene terminated urethane methacrylate),“ TE-2000 ”(1,2-polybutadiene terminated urethane methacrylate) manufactured by Nippon Soda Co., Ltd. and derivatives thereof,“ CN-301 ”“ CN-303 ”manufactured by Sartomer "CN-307" (polybutadiene acrylate oligomer).
  • Silane coupling agents include ⁇ -chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinylpropyltrimethoxysilane, vinyl-tris ( ⁇ -methoxyethoxy) silane, ⁇ - (meta ) Acryloxypropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, N - ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropylmethyldime
  • one of the group consisting of ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - (meth) acryloxypropyltrimethoxysilane and vinylpropyltrimethoxysilane is preferable.
  • a component is a photoinitiator.
  • the photopolymerization initiator include an ultraviolet polymerization initiator and a visible light polymerization initiator, both of which are used without limitation.
  • examples of the ultraviolet polymerization initiator include benzoin, benzophenone, and acetophenone.
  • examples of visible light polymerization initiators include acylphosphine oxide, thioxanthone, metallocene, quinone, and ⁇ -aminoalkylphenone.
  • Photopolymerization initiators include benzophenone, 4-phenylbenzophenone, benzoylbenzoic acid, 2,2-diethoxyacetophenone, bisdiethylaminobenzophenone, benzyl, benzoin, benzoyl isopropyl 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-methylpropan-1-one 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenyl Rupropan-1-one, camphorquinone, 2,4,6-tri
  • the resin composition of the present invention contains the components (A) to (E) as essential components.
  • the resin composition containing the components (A) to (E) is cured when irradiated with light.
  • the cured product has good adhesiveness to the cycloolefin polymer and has a high surface curability during the curing.
  • the resin composition of the present invention exhibits high adhesive strength even for general-purpose plastic resins such as polycarbonate, cellulose triacetate, and polyvinyl alcohol, and glass adherends.
  • the resin composition in the present invention can contain (meth) acrylic acid as the component (F). This is particularly used from the viewpoint of durability such as moisture resistance.
  • the resin composition in the present invention can contain polyvinyl alcohol as the component (G). This includes the following components from the viewpoint of adhesiveness to the polyvinyl alcohol resin.
  • the polyvinyl alcohol is not particularly limited as long as it is a polyvinyl alcohol derivative obtained by saponifying polyvinyl acetate.
  • the average degree of polymerization of polyvinyl alcohol is preferably from 100 to 5,000, more preferably from 1,000 to 4,000.
  • the average degree of saponification of polyvinyl alcohol is preferably 85 to 100 mol%, more preferably 90 to 100 mol%.
  • the use amount of the resin composition of the present invention is as follows, from the viewpoint that the adhesiveness of the adhesive to the cycloolefin polymer is particularly high and also has high adhesive strength to other adherends. It is as follows.
  • Component (D) is used in an amount of 0.01 to 10 masses per 100 parts by mass of the total amount of component (A), component (B), component (C) and component (F) used as necessary. Part is preferable, 0.1 to 5 parts by weight is more preferable, and typically 0.5 to 1.0 part by weight.
  • Component (E) is used in an amount of 0.01 to 30 masses per 100 parts by mass of the total amount of component (A), component (B), component (C) and component (F) used as necessary. Part is preferable, 0.1 to 20 parts by weight is more preferable, and typically 5 to 10 parts by weight.
  • Component (F) is used in an amount of 0.1 to 30 parts by mass in 100 parts by mass of the total amount of component (A), component (B), component (C) and component (F) used as necessary.
  • the amount is preferably 1 to 20 parts by mass, and typically 10 to 15 parts by mass.
  • Component (G) is used in an amount of 0.01 to 50 masses per 100 parts by mass of the total amount of component (A), component (B), component (C) and component (F) used as necessary. Part is preferable, 0.1 to 30 parts by weight is more preferable, and typically 0.5 to 1.0 part by weight.
  • the resin composition of the present invention is within the range that does not impair the object of the present invention, and is a graft copolymer, solvent, extender, reinforcing material, plasticizer, thickener, dye, pigment, flame retardant, antioxidant. , And additives such as surfactants can be used.
  • the cured product of the resin composition of the present invention preferably has a storage elastic modulus of 0.1 to 100000 MPa (23 ° C.), more preferably has a storage elastic modulus of 10 to 10000 MPa, typically 500 to 5000 MPa. It is.
  • the storage elastic modulus of the cured product of the resin composition is 0.1 MPa or more, the cured product is cured and no unreacted component remains.
  • the storage elastic modulus is 100000 MPa or less, the cured product does not become too rigid and the adhesive force does not decrease.
  • the resin composition of the present invention can be used as an adhesive.
  • the adhesive of the present invention exhibits high adhesive strength with respect to one or more selected from the group consisting of, for example, cycloolefin polymer, polycarbonate, cellulose triacetate, polyvinyl alcohol, and glass. In particular, it exhibits high adhesive strength for cycloolefin polymers.
  • the cycloolefin polymer of the present invention is a thermoplastic resin having a structural unit derived from a cyclic olefin (cycloolefin) monomer such as norbornene or a polycyclic norbornene monomer.
  • cycloolefin polymers include cycloolefin ring-opening polymers, hydrogenated ring-opening copolymers using two or more cycloolefins, chain olefins, aromatic compounds having a vinyl group, and cycloolefins.
  • the adhesive according to the present invention is particularly effective for cycloolefin polymers having a dicyclopentadiene ring structure. Moreover, you may introduce
  • cycloolefin polymers examples include “Topas” manufactured by Ticona®, Germany, “Arton” manufactured by JSR, “ZEONOR” and “ZEONEX” manufactured by Zeon Japan, Mitsui Chemicals, Inc. “Appel” made by the manufacturer can be mentioned.
  • the adhesive bonding method of the present invention is as follows, for example.
  • An adhesive is applied to the surface of at least one of the two adherends so as to have a thickness of 0.0001 to 5 mm, typically 0.01 to 0.50 mm.
  • irradiation time 1 to 60 seconds, typically 2 to
  • a method in which the adhesive is cured under a condition of 30 seconds to adhere the adherend is preferable.
  • an antioxidant may be used as the other component.
  • a phenol type or a hydroquinone type can be used, and a phenol type is preferably used.
  • Antioxidants include ⁇ -naphthoquinone, 2-methoxy-1,4-naphthoquinone, methylhydroquinone, hydroquinone, 2,2-methylene-bis (4-methyl-6-tertiarybutylphenol), catechol, hydroquinone monomethyl ether, mono Tertiary butyl hydroquinone, 2,5-ditertiary butyl hydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-ditertiary butyl-p-benzoquinone, picric acid, citric acid, phenothiazine, tertiary Examples thereof include butyl catechol, 2-butyl-4-hydroxyanisole and 2,6-ditertiary butyl-p-
  • the amount of the antioxidant used is 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of component (A), component (B), component (C) and component (F) used as necessary. Is preferable, 0.1 to 8 parts by mass is more preferable, and 2.0 to 8.0 parts by mass is more preferable.
  • component (A) a (meth) acrylate containing a dicyclopentenyl group, dicyclopentenyl acrylate (“FA-511AS” manufactured by Hitachi Chemical Co., Ltd.)
  • component (A) a (meth) acrylate containing a dicyclopentenyl group, dicyclopentenyloxyethyl methacrylate (“FA-512MT” manufactured by Hitachi Chemical Co., Ltd.)
  • component (B) Component, 2-hydroxy-3-phenoxypropyl acrylate (“M-5700” manufactured by Toagosei Co., Ltd.) as a (meth) acrylate containing a hydroxyl group
  • B) Component, 2-hydroxyethyl methacrylate (“light ester HO” manufactured by Kyoeisha Chemical Co., Ltd.) as a (meth) acrylate containing a hydroxyl group
  • C Component, oligomer, “UC-203” (esterified oligomer of maleic anhydride
  • Light Ester BZ Lauryl methacrylate (Kyoeisha Chemical Co., Ltd. “Light Ester L”) Antioxidant, (D-1) 2,2-methylene-bis (4-methyl-6-tertiary butylphenol) (“Sumilyzer MDP-S” manufactured by Sumitomo Chemical Co., Ltd.)
  • Test piece 12a width 25 mm ⁇ length 100 mm ⁇ thickness 2.0 mm
  • a Teflon (registered trademark) tape 10 thickness 80 ⁇ m ⁇ width 25 mm ⁇ length 25 mm having a hole 11 having a size of 0.5 cm 2 in the center was attached to control the adhesive thickness.
  • Test pieces 25 mm ⁇ 25 mm ⁇ 0.03 mm are 80 ⁇ m thick ⁇ 11.5 mm wide ⁇ length
  • An adhesive was adhered using a 25 mm Teflon (registered trademark) tape as a spacer (adhesion area: 3.125 cm 2 ). After curing, the tensile bond strength was measured using the test piece bonded with an adhesive. Curing conditions followed the method described in [Photocurability].
  • a galvanized steel sheet 100 mm ⁇ 25 mm ⁇ 2.0 mm, engineering test service
  • the tensile bond strength was measured using the test piece adhered with an adhesive.
  • the tensile shear bond strength (unit: MPa) was measured at a tensile rate of 10 mm / min in an environment of a temperature of 23 ° C. and a humidity of 50%.
  • Adhesives were prepared by mixing raw materials of the types shown in Table 1 with the compositions shown in Table 1. Various physical properties of the obtained adhesive were measured. The results are shown in Table 1.
  • This invention can express sufficient adhesive strength with respect to a cycloolefin polymer, a polycarbonate, polyvinyl alcohol, and glass.
  • the present invention has moisture resistance.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polymerisation Methods In General (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

Provided is a resin composition exhibiting high adhesive strength. The resin composition contains the following components (A) to (E). Component (A) is a (meth)acrylate having a dicyclopentenyl group; component (B) is a (meth)acrylate having a hydroxyl group; component (C) is a (meth)acrylate having a (meth)acryloyl group, and a diene structure or a diene structure added with hydrogen; component (D) is a silane coupling agent; and component (E) is a photopolymerization initiator. Moreover, the resin composition may contain a (meth)acrylic acid as component (F) and a polyvinyl alcohol as component (G).

Description

樹脂組成物及び接着剤Resin composition and adhesive
本発明は、接着剤に関する。 The present invention relates to an adhesive.
シクロオレフィンポリマーは、電子材料、光学レンズ及び医療材料等の用途に使用されている。シクロオレフィンポリマーは極性が小さく、表面に多くの官能基を持たないことから、難被着体として知られている。このようなシクロオレフィン系樹脂を接着する接着剤としては溶剤型接着剤やホットメルト接着剤が挙げられる。 Cycloolefin polymers are used in applications such as electronic materials, optical lenses and medical materials. Cycloolefin polymers are known as difficult adherends because of their low polarity and lack of many functional groups on the surface. Examples of the adhesive for adhering such a cycloolefin-based resin include a solvent-type adhesive and a hot melt adhesive.
又、オレフィン系樹脂を接着する方法として、特許文献１に開示されているように、プライマーによる処理を行ってから瞬間接着剤により接着するという方法がある。また、特許文献２に開示されるように、（メタ）アクリレートを含有することを特徴とするエネルギー線硬化性樹脂組成物が開示されている。 As a method for adhering an olefin resin, there is a method of adhering with an instantaneous adhesive after performing a treatment with a primer as disclosed in Patent Document 1. Moreover, as disclosed in Patent Document 2, an energy ray-curable resin composition containing (meth) acrylate is disclosed.
特開昭６２－１８４８５号公報JP-A-62-18485 特開２００７－７７３２１号公報JP 2007-77321 A
溶剤型接着剤は、溶剤を使用する。溶剤型接着剤は、人体に有害である上、溶剤の揮発に時間がかかり、接着強度自体も十分なものが得られない。 A solvent type adhesive uses a solvent. Solvent-type adhesives are harmful to the human body, and it takes time for the solvent to evaporate, so that sufficient adhesive strength itself cannot be obtained.
ホットメルト接着剤は、接着剤を溶融させる手間及び装置が必要である。又、この接着剤の場合も十分な接着強度を得ることができない。尚、ホットメルト接着剤を用いる場合、シクロオレフィンポリマーを予め加熱しておけば、接着強度は向上するが、樹脂が変形してしまうという新たな問題が発生する。 The hot melt adhesive requires labor and equipment for melting the adhesive. Also, this adhesive cannot provide sufficient adhesive strength. In the case of using a hot melt adhesive, if the cycloolefin polymer is heated in advance, the adhesive strength is improved, but a new problem that the resin is deformed occurs.
特許文献１に開示されている接着方法によれば、プライマー処理に手間がかかるという問題がある上、接着強度も十分なものが得られない。 According to the adhesion method disclosed in Patent Document 1, there is a problem that it takes time and effort for primer treatment, and a sufficient adhesion strength cannot be obtained.
特許文献２は、（メタ）アクリレートを含有することを特徴とするエネルギー線硬化性樹脂組成物が開示されている。しかし、ジシクロペンテニル基を有する(メタ)アクリレートについては記載がない。 Patent Document 2 discloses an energy ray curable resin composition containing (meth) acrylate. However, there is no description about (meth) acrylate having a dicyclopentenyl group.
本発明はそのような実情に鑑みてなされたものである。本発明は、例えば、シクロオレフィンポリマーに対して短時間で十分な接着強度を発現でき、且つ無溶剤型で環境に優しいシクロオレフィンポリマー用接着剤の提供を目的とする。 The present invention has been made in view of such circumstances. An object of this invention is to provide the adhesive agent for cycloolefin polymers which can express sufficient adhesive strength in a short time with respect to a cycloolefin polymer, for example, and is a solvent-free type and environmentally friendly.
本発明者は、前記の課題を解決するべく鋭意研究を重ね、本発明に至ったものである。 The present inventor has intensively studied to solve the above-described problems and has arrived at the present invention.
即ち、本発明は一側面において、
下記（Ａ）～（Ｅ）成分を含有してなる樹脂組成物である。
（Ａ）成分は、ジシクロペンテニル基を有する(メタ)アクリレート
（Ｂ）成分は、水酸基を有する(メタ)アクリレート
（Ｃ）成分は、（メタ）アクリロイル基を有し、かつ、ジエン系の骨格又は水素添加されたジエン系の骨格を有する（メタ）アクリレート
（Ｄ）成分は、シランカップリング剤
（Ｅ）成分は、光重合開始剤 That is, the present invention in one aspect,
A resin composition comprising the following components (A) to (E).
(A) component is a (meth) acrylate having a dicyclopentenyl group (B) component is a (meth) acrylate having a hydroxyl group (C) component is having a (meth) acryloyl group and is a diene skeleton Alternatively, the (meth) acrylate (D) component having a hydrogenated diene-based skeleton is a silane coupling agent (E) component is a photopolymerization initiator.
本発明に係る樹脂組成物は一実施形態において、更に（Ｆ）成分として、（メタ）アクリル酸を含有してなる。 In one embodiment, the resin composition according to the present invention further comprises (meth) acrylic acid as the component (F).
本発明に係る樹脂組成物は一実施形態において、更に（Ｇ）成分として、ポリビニルアルコールを含有してなる。 In one embodiment, the resin composition according to the present invention further contains polyvinyl alcohol as the component (G).
本発明に係る樹脂組成物は一実施形態において、（Ａ）成分がジシクロペンテニル（メタ）アクリレートである。 In one embodiment of the resin composition according to the present invention, the component (A) is dicyclopentenyl (meth) acrylate.
本発明に係る樹脂組成物は一実施形態において、更に（Ｃ）成分の数平均分子量が５００～５００００である。 In one embodiment of the resin composition according to the present invention, the component (C) has a number average molecular weight of 500 to 50,000.
本発明に係る樹脂組成物は一実施形態において、厚み０．０３ｍｍとして、波長３６５ｎｍ、積算光量２０００ｍＪ／ｃｍ2の条件にて１５秒間照射することによって、硬化させたときに、硬化物の貯蔵弾性率が０．１～１０００００ＭＰａ（２３℃）の範囲内となる。 In one embodiment, the resin composition according to the present invention has a thickness of 0.03 mm, and when cured by irradiation for 15 seconds under conditions of a wavelength of 365 nm and an integrated light quantity of 2000 mJ / cm 2 , the storage elasticity of the cured product. The rate is in the range of 0.1 to 100,000 MPa (23 ° C.).
本発明は別の一側面において、本発明に係る該樹脂組成物からなる接着剤である。 In another aspect, the present invention is an adhesive comprising the resin composition according to the present invention.
本発明に係る接着剤は一実施形態において、シクロオレフィンポリマー用接着剤である。 In one embodiment, the adhesive according to the present invention is a cycloolefin polymer adhesive.
本発明に係る接着剤は一実施形態において、ジシクロペンタジエン環構造を有するシクロオレフィンポリマー用接着剤である。 In one embodiment, the adhesive according to the present invention is an adhesive for a cycloolefin polymer having a dicyclopentadiene ring structure.
本発明は更に別の一側面において、本発明に係る該接着剤を用いて被着体同士が接着された接着体である。 In still another aspect, the present invention is an adhesive body in which adherends are bonded to each other using the adhesive according to the present invention.
本発明に係る接着体は一実施形態において、被着体が、シクロオレフィンポリマー、ポリカーボネート、セルローストリアセテート、ポリビニルアルコール及びガラスからなる群から選ばれる１種以上である。 In one embodiment, the adherend according to the present invention is at least one member selected from the group consisting of cycloolefin polymer, polycarbonate, cellulose triacetate, polyvinyl alcohol and glass.
本発明は更に別の一側面において、被着体表面に、本発明に係る該接着剤を厚み０．０００１～５ｍｍになるように塗布し、被着体同士を貼り合わせ、波長２００～５００ｎｍ、積算光量２００～６０００Ｊ／ｃｍ2、照射時間１～６０秒の条件下で接着剤を硬化することを含む接着体の製造方法である。 In yet another aspect of the present invention, the adhesive according to the present invention is applied to the surface of the adherend so as to have a thickness of 0.0001 to 5 mm, and the adherends are bonded to each other to obtain a wavelength of 200 to 500 nm. This is a method for producing an adhesive body comprising curing the adhesive under conditions of an integrated light quantity of 200 to 6000 J / cm 2 and an irradiation time of 1 to 60 seconds.
本発明の樹脂組成物は、高い接着強度を示し、耐湿性にも優れているという特徴を有する。 The resin composition of the present invention is characterized by high adhesive strength and excellent moisture resistance.
実施例における引張接着強さの測定手順を示す模式図である。It is a schematic diagram which shows the measurement procedure of the tensile bond strength in an Example.
本発明における（Ａ）成分は、ジシクロペンテニル基を有する(メタ)アクリレートである。より具体的には、（Ａ）成分は分子の末端又は側鎖に１個以上のジシクロペンテニル基を含有する（メタ）アクリレートである。（Ａ）成分の（メタ）アクリレートとしては、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）アクリレート等が挙げられる。これらの中では、ジシクロペンテニル（メタ）アクリレートが好ましい。 The component (A) in the present invention is a (meth) acrylate having a dicyclopentenyl group. More specifically, the component (A) is a (meth) acrylate containing one or more dicyclopentenyl groups at the terminal or side chain of the molecule. Examples of (A) component (meth) acrylate include dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyloxypropyl (meth) acrylate, and dicyclopentenyl (meth) acrylate. Of these, dicyclopentenyl (meth) acrylate is preferred.
（Ｂ）成分は、水酸基を含有する（メタ）アクリレートである。より具体的には、（Ｂ）成分は分子の末端又は側鎖に１個以上の水酸基を含有する（メタ）アクリレートである。水酸基を含有する（メタ）アクリレートとしては、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、２－（メタ）アクリロイルオキシエチル－２－ヒドロキシプロピルフタレート、４－ヒドロキシシクロヘキシル（メタ）アクリレート等が挙げられる。これらの中では、樹脂フィルム接着性の観点から、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレートがより好ましい。 The component (B) is a (meth) acrylate containing a hydroxyl group. More specifically, the component (B) is a (meth) acrylate containing one or more hydroxyl groups at the end or side chain of the molecule. Examples of hydroxyl group-containing (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate. 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 4-hydroxycyclohexyl (meth) acrylate, and the like. Among these, 2-hydroxy-3-phenoxypropyl (meth) acrylate is more preferable from the viewpoint of resin film adhesion.
（Ｃ）成分は、（メタ）アクリロイル基を有してなり、かつ、ジエン系の骨格又は水素添加されたジエン系の骨格を有する（メタ）アクリレートである。より具体的には、（Ｃ）成分は分子の末端又は側鎖に１個以上の（メタ）アクリロイル基を有してなり、かつ、ジエン系の骨格又は水素添加されたジエン系の骨格を有する（メタ）アクリレートであり、好ましくは分子の末端に１個以上の（メタ）アクリロイル基を有してなり、かつ、ジエン系の骨格又は水素添加されたジエン系の骨格を有する（メタ）アクリレートである。これは、樹脂の柔軟性付与の観点から、以下のような成分が挙げられる。 The component (C) is a (meth) acrylate having a (meth) acryloyl group and having a diene skeleton or a hydrogenated diene skeleton. More specifically, the component (C) has one or more (meth) acryloyl groups at the terminal or side chain of the molecule, and has a diene skeleton or a hydrogenated diene skeleton. (Meth) acrylates, preferably (meth) acrylates having one or more (meth) acryloyl groups at the end of the molecule and having a diene skeleton or a hydrogenated diene skeleton. is there. This includes the following components from the viewpoint of imparting flexibility to the resin.
（メタ）アクリレートの主鎖骨格は、ジエン系の骨格又は水素添加されたジエン系の骨格である。ジエン系の骨格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種以上の骨格が挙げられる。これらの中では、ポリイソプレン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種以上が好ましく、ポリイソプレンがより好ましい。 The main chain skeleton of (meth) acrylate is a diene skeleton or a hydrogenated diene skeleton. Examples of the diene skeleton or the hydrogenated diene skeleton include one or more skeletons 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 polyisoprene and a hydrogenated product of polyisoprene is preferable, and polyisoprene is more preferable.
（Ｃ）成分の（メタ）アクリレートは、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。これらの中では、主鎖骨格の両末端に（メタ）アクリロイル基を有するものが好ましい。 The (meth) acrylate of the component (C) 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.
（Ｃ）成分の（メタ）アクリレートの数平均分子量は５００～５００００が好ましく、８０００～４５０００がより好ましい。数平均分子量が５００以上であれば、本発明の接着剤にエネルギー線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。数平均分子量が５００００以下であれば、得られる接着剤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当該接着剤を用いる際の作業性が良好である。 The number average molecular weight of the component (C) (meth) acrylate is preferably 500 to 50,000, and more preferably 8000 to 45,000. If the number average molecular weight is 500 or more, the cured product obtained by irradiating the adhesive of the present invention with energy rays has a high hardness, so that it is easy to form an adhesive layer. If the number average molecular weight is 50000 or less, the viscosity of the resulting adhesive is small, so that the workability in mixing during the production process and the workability when using the adhesive in practical applications are good.
（Ｃ）成分の（メタ）アクリレートとしては、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）、日本曹達社製「ＴＥＡＩ－１０００」（水素添加１，２－ポリブタジエン末端ウレタンメタクリレート）、日本曹達社製「ＴＥ－２０００」（１,２－ポリブタジエン末端ウレタンメタクリレート）及びその誘導体、サートマー社製「ＣＮ－３０１」「ＣＮ－３０３」「ＣＮ－３０７」（ポリブタジエン系アクリレートオリゴマー）等が挙げられる。 The component (C) (meth) acrylate includes “UC-203” manufactured by Kuraray Co., Ltd. (an esterified oligomer of maleic anhydride adduct of isoprene polymer and 2-hydroxyethyl methacrylate), “TEAI-” manufactured by Nippon Soda Co., Ltd. 1000 ”(hydrogenated 1,2-polybutadiene terminated urethane methacrylate),“ TE-2000 ”(1,2-polybutadiene terminated urethane methacrylate) manufactured by Nippon Soda Co., Ltd. and derivatives thereof,“ CN-301 ”“ CN-303 ”manufactured by Sartomer "CN-307" (polybutadiene acrylate oligomer).
（Ｄ）成分は、シランカップリング剤である。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、ビニルプロピルトリメトキシシラン、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、ヒドロキシエチル（メタ）アクリレートリン酸エステル、（メタ）アクリロキシオキシエチルアシッドフォスフェート、（メタ）アクリロキシオキシエチルアシッドフォスフェートモノエチルアミンハーフソルト等が挙げられる。これらの中では、ガラス等への密着性という観点から、γ－グリシドキシプロピルトリメトキシシラン、γ－（メタ）アクリロキシプロピルトリメトキシシラン及びビニルプロピルトリメトキシシランからなる群のうちの１種以上が好ましい。 (D) A component is a silane coupling agent. Silane coupling agents include γ-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinylpropyltrimethoxysilane, vinyl-tris (β-methoxyethoxy) silane, γ- (meta ) Acryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N -Β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, hydroxyethyl (meth) acrylate Ester, (meth) acrylate Roxio carboxyethyl acid phosphate, and (meth) acrylate Roxio carboxyethyl acid phosphate Tomono ethylamine half salt and the like. Among these, from the viewpoint of adhesion to glass and the like, one of the group consisting of γ-glycidoxypropyltrimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane and vinylpropyltrimethoxysilane The above is preferable.
（Ｅ）成分は、光重合開始剤である。光重合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。 (E) A component is a photoinitiator. Examples of the photopolymerization initiator include an ultraviolet polymerization initiator and a visible light polymerization initiator, both of which are used without limitation. Examples of the ultraviolet polymerization initiator include benzoin, benzophenone, and acetophenone. Examples of visible light polymerization initiators include acylphosphine oxide, thioxanthone, metallocene, quinone, and α-aminoalkylphenone.
光重合開始剤としては、ベンゾフェノン、４－フェニルベンゾフェノン、ベンゾイル安息香酸、２，２－ジエトキシアセトフェノン、ビスジエチルアミノベンゾフェノン、ベンジル、ベンゾイン、ベンゾイルイソプロピルエーテル、ベンジルジメチルケタール、１－ヒドロキシシクロヘキシルフェニルケトン、チオキサントン、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）－１－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。これらの中では、ベンジルジメチルケタールが好ましい。 Photopolymerization initiators include benzophenone, 4-phenylbenzophenone, benzoylbenzoic acid, 2,2-diethoxyacetophenone, bisdiethylaminobenzophenone, benzyl, benzoin, benzoyl isopropyl 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-methylpropan-1-one 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenyl Rupropan-1-one, camphorquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-methyl-1- (4- (methylthio) phenyl ) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone-1,2-dimethylamino-2- (4-methyl-benzyl) ) -1- (4-Morifolin-4-yl-phenyl) -butan-1-one, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, and the like. Of these, benzyldimethyl ketal is preferred.
本発明の樹脂組成物は、前記（Ａ）～（Ｅ）成分を必須成分として含有する。前記（Ａ）～（Ｅ）成分を含有する樹脂組成物は、これに光を照射されることにより硬化する。硬化物はシクロオレフィンポリマーに対して接着性が良好であるとともに、前記硬化に際して表面硬化性が高い特徴を示す。本発明の樹脂組成物は、例えば、ポリカーボネート、セルローストリアセテート、ポリビニルアルコール等の汎用プラスチック樹脂、ガラス被着体に対しても高い接着強さを示す。 The resin composition of the present invention contains the components (A) to (E) as essential components. The resin composition containing the components (A) to (E) is cured when irradiated with light. The cured product has good adhesiveness to the cycloolefin polymer and has a high surface curability during the curing. The resin composition of the present invention exhibits high adhesive strength even for general-purpose plastic resins such as polycarbonate, cellulose triacetate, and polyvinyl alcohol, and glass adherends.
本発明における樹脂組成物には、（Ｆ）成分として、（メタ）アクリル酸を含有することができる。これは特に耐湿性などの耐久性の観点より使用する。 The resin composition in the present invention can contain (meth) acrylic acid as the component (F). This is particularly used from the viewpoint of durability such as moisture resistance.
本発明における樹脂組成物には、（Ｇ）成分として、ポリビニルアルコールを含有することができる。これは、ポリビニルアルコール樹脂への密着性の観点から、以下のような成分が挙げられる。 The resin composition in the present invention can contain polyvinyl alcohol as the component (G). This includes the following components from the viewpoint of adhesiveness to the polyvinyl alcohol resin.
前記ポリビニルアルコールは、ポリ酢酸ビニルをけん化して得られるポリビニルアルコール誘導体であれば、特に限定されるものではない。ポリビニルアルコールの平均重合度は１００～５０００が好ましく、１０００～４０００がより好ましい。ポリビニルアルコールの平均けん化度は８５～１００モル％が好ましく、９０～１００モル％がより好ましい。 The polyvinyl alcohol is not particularly limited as long as it is a polyvinyl alcohol derivative obtained by saponifying polyvinyl acetate. The average degree of polymerization of polyvinyl alcohol is preferably from 100 to 5,000, more preferably from 1,000 to 4,000. The average degree of saponification of polyvinyl alcohol is preferably 85 to 100 mol%, more preferably 90 to 100 mol%.
本発明の樹脂組成物の使用量は、接着剤のシクロオレフィンポリマーに対する接着性が特段に高くなり、且つ、他の被着体に対しても高い接着強さを有するようになる観点から、以下の通りである。 The use amount of the resin composition of the present invention is as follows, from the viewpoint that the adhesiveness of the adhesive to the cycloolefin polymer is particularly high and also has high adhesive strength to other adherends. It is as follows.
（Ａ）成分、（Ｂ）成分及び（Ｃ）成分の使用量は、（Ａ）成分、（Ｂ）成分及び（Ｃ）成分の合計１００質量部中、（Ａ）成分：（Ｂ）成分：（Ｃ）成分＝４０～９０：１～２０：５～４５（質量比）が好ましく、（Ａ）成分：（Ｂ）成分：（Ｃ）成分＝５５～８５：３～１０：１０～４０（質量比）がより好ましい。 Component (A), component (B) and component (C) are used in a total of 100 parts by weight of component (A), component (B) and component (C), component (A): component (B): Component (C) is preferably 40 to 90: 1 to 20: 5 to 45 (mass ratio), and component (A): component (B): component (C) = 55 to 85: 3 to 10:10 to 40 ( (Mass ratio) is more preferable.
（Ｄ）成分の使用量は、（Ａ）成分、（Ｂ）成分、（Ｃ）成分及び必要に応じて使用する（Ｆ）成分の合計量１００質量部に対して、０．０１～１０質量部が好ましく、０．１～５質量部がより好ましく、典型的には０．５～１．０質量部である。 Component (D) is used in an amount of 0.01 to 10 masses per 100 parts by mass of the total amount of component (A), component (B), component (C) and component (F) used as necessary. Part is preferable, 0.1 to 5 parts by weight is more preferable, and typically 0.5 to 1.0 part by weight.
（Ｅ）成分の使用量は、（Ａ）成分、（Ｂ）成分、（Ｃ）成分及び必要に応じて使用する（Ｆ）成分の合計量１００質量部に対して、０．０１～３０質量部が好ましく、０．１～２０質量部がより好ましく、典型的には５～１０質量部である。 Component (E) is used in an amount of 0.01 to 30 masses per 100 parts by mass of the total amount of component (A), component (B), component (C) and component (F) used as necessary. Part is preferable, 0.1 to 20 parts by weight is more preferable, and typically 5 to 10 parts by weight.
（Ｆ）成分の使用量は、（Ａ）成分、（Ｂ）成分、（Ｃ）成分及び必要に応じて使用する（Ｆ）成分の合計量１００質量部中、０．１～３０質量部が好ましく、１～２０質量部がより好ましく、典型的には１０～１５質量部である。 Component (F) is used in an amount of 0.1 to 30 parts by mass in 100 parts by mass of the total amount of component (A), component (B), component (C) and component (F) used as necessary. The amount is preferably 1 to 20 parts by mass, and typically 10 to 15 parts by mass.
（Ｇ）成分の使用量は、（Ａ）成分、（Ｂ）成分、（Ｃ）成分及び必要に応じて使用する（Ｆ）成分の合計量１００質量部に対して、０．０１～５０質量部が好ましく、０．１～３０質量部がより好ましく、典型的には０．５～１．０質量部である。 Component (G) is used in an amount of 0.01 to 50 masses per 100 parts by mass of the total amount of component (A), component (B), component (C) and component (F) used as necessary. Part is preferable, 0.1 to 30 parts by weight is more preferable, and typically 0.5 to 1.0 part by weight.
尚、本発明の樹脂組成物は、本発明の目的を損なわない範囲で、グラフト共重合体、溶剤、増量材、補強材、可塑剤、増粘剤、染料、顔料、難燃剤、酸化防止剤、及び界面活性剤等の添加剤を使用することができる。 The resin composition of the present invention is within the range that does not impair the object of the present invention, and is a graft copolymer, solvent, extender, reinforcing material, plasticizer, thickener, dye, pigment, flame retardant, antioxidant. , And additives such as surfactants can be used.
本発明の樹脂組成物の硬化物は０．１～１０００００ＭＰａ（２３℃）の貯蔵弾性率を有することが好ましく、１０～１００００ＭＰａの貯蔵弾性率を有することがより好ましく、典型的には５００～５０００ＭＰａである。樹脂組成物の硬化物の貯蔵弾性率が０．１ＭＰａ以上である場合、硬化物が硬化し、未反応成分が残らない。貯蔵弾性率が１０００００ＭＰａ以下である場合、硬化物が剛直になりすぎず、接着力が低下しない。 The cured product of the resin composition of the present invention preferably has a storage elastic modulus of 0.1 to 100000 MPa (23 ° C.), more preferably has a storage elastic modulus of 10 to 10000 MPa, typically 500 to 5000 MPa. It is. When the storage elastic modulus of the cured product of the resin composition is 0.1 MPa or more, the cured product is cured and no unreacted component remains. When the storage elastic modulus is 100000 MPa or less, the cured product does not become too rigid and the adhesive force does not decrease.
本発明の樹脂組成物は、接着剤として使用できる。本発明の接着剤は、例えば、シクロオレフィンポリマー、ポリカーボネート、セルローストリアセテート、ポリビニルアルコール及びガラスからなる群から選ばれる１種以上に対して高い接着強度を示す。特に、シクロオレフィンポリマーに対して高い接着強度を示す。 The resin composition of the present invention can be used as an adhesive. The adhesive of the present invention exhibits high adhesive strength with respect to one or more selected from the group consisting of, for example, cycloolefin polymer, polycarbonate, cellulose triacetate, polyvinyl alcohol, and glass. In particular, it exhibits high adhesive strength for cycloolefin polymers.
本発明のシクロオレフィンポリマーとは、例えば、ノルボルネンや多環ノルボルネン系モノマー等の環状オレフィン（シクロオレフィン）モノマー由来の構成単位を有する熱可塑性樹脂である。シクロオレフィンポリマーとしては、例えば、シクロオレフィンの開環重合体、２種以上のシクロオレフィンを用いた開環共重合体の水素添加物、鎖状オレフィンやビニル基を有する芳香族化合物とシクロオレフィンとの付加共重合体等が挙げられ、本発明に係る接着剤はとりわけジシクロペンタジエン環構造を有するシクロオレフィンポリマーに有効である。又、シクロオレフィンポリマーに、極性基を導入してもよい。 The cycloolefin polymer of the present invention is a thermoplastic resin having a structural unit derived from a cyclic olefin (cycloolefin) monomer such as norbornene or a polycyclic norbornene monomer. Examples of cycloolefin polymers include cycloolefin ring-opening polymers, hydrogenated ring-opening copolymers using two or more cycloolefins, chain olefins, aromatic compounds having a vinyl group, and cycloolefins. The adhesive according to the present invention is particularly effective for cycloolefin polymers having a dicyclopentadiene ring structure. Moreover, you may introduce | transduce a polar group into a cycloolefin polymer.
市販のシクロオレフィンポリマーとしては、例えば、独 Ｔｉｃｏｎａ 社製の「Ｔｏｐａｓ」、ジェイエスアール社製の「アートン」、日本ゼオン社製の「ゼオノア（ＺＥＯＮＯＲ）」や「ゼオネックス（ＺＥＯＮＥＸ）」、三井化学社製の「アペル」等が挙げられる。 Examples of commercially available cycloolefin polymers include “Topas” manufactured by Ticona®, Germany, “Arton” manufactured by JSR, “ZEONOR” and “ZEONEX” manufactured by Zeon Japan, Mitsui Chemicals, Inc. “Appel” made by the manufacturer can be mentioned.
本発明の接着剤の接着方法は、例えば、以下の通りである。被着体２枚のうち少なくとも１枚の被着体表面に接着剤を厚み０．０００１～５ｍｍ、典型的には０．０１～０．５０ｍｍになるように塗布し、その後、被着体同士を貼り合わせ、波長２００～５００ｎｍ、典型的には３５０～４２０ｎｍ、積算光量２００～６０００ｍＪ／ｃｍ2、典型的には３００～２０００ｍＪ／ｃｍ2、照射時間１～６０秒、典型的には２～３０秒の条件下で接着剤を硬化し、被着体を接着する方法が好ましい。 The adhesive bonding method of the present invention is as follows, for example. An adhesive is applied to the surface of at least one of the two adherends so as to have a thickness of 0.0001 to 5 mm, typically 0.01 to 0.50 mm. Are bonded together, wavelength 200 to 500 nm, typically 350 to 420 nm, integrated light quantity 200 to 6000 mJ / cm 2 , typically 300 to 2000 mJ / cm 2 , irradiation time 1 to 60 seconds, typically 2 to A method in which the adhesive is cured under a condition of 30 seconds to adhere the adherend is preferable.
本発明は、その他の成分として酸化防止剤を使用してもよい。酸化防止剤としてはフェノール系、ハイドロキノン系を使用でき、好ましくはフェノール系が用いられる。酸化防止剤としては、β―ナフトキノン、2－メトキシー１，４－ノフトキノン、メチルハイドロキノン、ハイドロキノン、２，２－メチレン－ビス（４－メチル－６－ターシャリーブチルフェノール）、カテコール、ハイドロキノンモノメチルエーテル、モノターシャリーブチルハイドロキノン、２，５－ジターシャリーブチルハイドロキノン、ｐ－ベンゾキノン、２，５－ジフェニル－ｐ－ベンゾキノン、２，５－ジターシャリーブチル－ｐ－ベンゾキノン、ピクリン酸、クエン酸、フェノチアジン、ターシャリーブチルカテコール、２－ブチル－４－ヒドロキシアニソール及び２，６－ジターシャリーブチル－ｐ－クレゾール等が例示できる。これらの中では、２，２－メチレン－ビス（４－メチル－６－ターシャリーブチルフェノール）が好ましい。 In the present invention, an antioxidant may be used as the other component. As the antioxidant, a phenol type or a hydroquinone type can be used, and a phenol type is preferably used. Antioxidants include β-naphthoquinone, 2-methoxy-1,4-naphthoquinone, methylhydroquinone, hydroquinone, 2,2-methylene-bis (4-methyl-6-tertiarybutylphenol), catechol, hydroquinone monomethyl ether, mono Tertiary butyl hydroquinone, 2,5-ditertiary butyl hydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-ditertiary butyl-p-benzoquinone, picric acid, citric acid, phenothiazine, tertiary Examples thereof include butyl catechol, 2-butyl-4-hydroxyanisole and 2,6-ditertiary butyl-p-cresol. Of these, 2,2-methylene-bis (4-methyl-6-tertiarybutylphenol) is preferred.
酸化防止剤の使用量は、（Ａ）成分、（Ｂ）成分、（Ｃ）成分及び必要に応じて使用する（Ｆ）成分の合計量１００質量部に対して、０．０１～１０質量部が好ましく、０．１～８質量部がより好ましく、２．０～８．０質量部がより好ましい。 The amount of the antioxidant used is 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of component (A), component (B), component (C) and component (F) used as necessary. Is preferable, 0.1 to 8 parts by mass is more preferable, and 2.0 to 8.0 parts by mass is more preferable.
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。尚、実験例に記載の接着剤中の各成分に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. In addition, the following compounds were selected for each component in the adhesive described in the experimental examples.
（Ａ）成分、ジシクロペンテニル基を含有する（メタ）アクリレートとして、ジシクロペンテニルアクリレート(日立化成社製「ＦＡ－５１１ＡＳ」)
（Ａ）成分、ジシクロペンテニル基を含有する（メタ）アクリレートとして、ジシクロペンテニルオキシエチルメタクリレート(日立化成社製社製「ＦＡ－５１２ＭＴ」)
（Ｂ）成分、水酸基を含有する（メタ）アクリレートとして、２－ヒドロキシ－３－フェノキシプロピルアクリレート（東亞合成社製「Ｍ－５７００」）
（Ｂ）成分、水酸基を含有する（メタ）アクリレートとして、２－ヒドロキシエチルメタクリレート(共栄社化学社製社製「ライトエステルＨＯ」)
（Ｃ）成分、オリゴマー、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））（ＧＰＣによるポリスチレン換算の数平均分子量３６０００）
（Ｄ）成分、シランカップリング剤、γ－グリシドキシプロピルトリメトキシシラン（信越化学社製「ＫＢＭ－４０３」）
（Ｄ）成分、シランカップリング剤、ビニルプロピルトリメトキシシラン（信越化学社製「ＫＢＭ－１００３」）
（Ｄ）成分、シランカップリング剤、γ－メタクリロキシプロピルトリメトキシシラン（信越化学社製社製「ＫＢＭ－５０３」）
（Ｅ）成分、光開始剤として、ベンジルジメチルケタール（チバ・スペシャルティー・ケミカルズ社製「ＩＲＧＡＣＵＲＥ６５１」）
（Ｅ）成分、光開始剤として、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(チバ・スペシャルティー・ケミカルズ社製「ＩＲＧＡＣＵＲＥ８１９」)
（Ｆ）成分、メタクリル酸（三菱レイヨン社製「ＡＭ」）
（Ｆ）成分、アクリル酸(日本触媒社製社製「アクリル酸メチルＡＭ」)
（Ｇ）成分、ポリビニルアルコール（電気化学工業社製「デンカポバール　Ｈ－１７」）（平均重合度１２００、平均けん化度９７モル％）
（Ｇ）成分、ポリビニルアルコール（電気化学工業社製「デンカポバール　Ｆ－１２」）（平均重合度１２００、平均けん化度９９モル％）
ベンジルメタクリレート（共栄社化学社製「ライトエステルＢＺ」）
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」）
酸化防止剤、（Ｄ－１)２，２－メチレン－ビス（４－メチル－６－ターシャリーブチルフェノール）（住友化学社製「スミライザーＭＤＰ－Ｓ」）  As component (A), a (meth) acrylate containing a dicyclopentenyl group, dicyclopentenyl acrylate (“FA-511AS” manufactured by Hitachi Chemical Co., Ltd.)
As component (A), a (meth) acrylate containing a dicyclopentenyl group, dicyclopentenyloxyethyl methacrylate ("FA-512MT" manufactured by Hitachi Chemical Co., Ltd.)
(B) Component, 2-hydroxy-3-phenoxypropyl acrylate (“M-5700” manufactured by Toagosei Co., Ltd.) as a (meth) acrylate containing a hydroxyl group
(B) Component, 2-hydroxyethyl methacrylate (“light ester HO” manufactured by Kyoeisha Chemical Co., Ltd.) as a (meth) acrylate containing a hydroxyl group
(C) Component, oligomer, “UC-203” (esterified oligomer of maleic anhydride adduct of isoprene polymer and 2-hydroxyethyl methacrylate) produced by Kuraray Co., Ltd.) (Number average molecular weight 36,000 in terms of polystyrene by GPC)
Component (D), silane coupling agent, γ-glycidoxypropyltrimethoxysilane (“KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.)
Component (D), silane coupling agent, vinylpropyltrimethoxysilane (“KBM-1003” manufactured by Shin-Etsu Chemical Co., Ltd.)
Component (D), silane coupling agent, γ-methacryloxypropyltrimethoxysilane (“KBM-503” manufactured by Shin-Etsu Chemical Co., Ltd.)
As component (E) and photoinitiator, benzyldimethyl ketal (“IRGACURE651” manufactured by Ciba Specialty Chemicals)
As component (E) and photoinitiator, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (“IRGACURE819” manufactured by Ciba Specialty Chemicals)
Component (F), methacrylic acid (“AM” manufactured by Mitsubishi Rayon Co., Ltd.)
Component (F), acrylic acid (“Methyl acrylate AM” manufactured by Nippon Shokubai Co., Ltd.)
Component (G), polyvinyl alcohol (“DENKA POVAL H-17” manufactured by Denki Kagaku Kogyo Co., Ltd.) (average polymerization degree 1200, average saponification degree 97 mol%)
Component (G), polyvinyl alcohol (“Denkapoval F-12” manufactured by Denki Kagaku Kogyo Co., Ltd.) (average polymerization degree 1200, average saponification degree 99 mol%)
Benzyl methacrylate (Kyoeisha Chemical Co., Ltd. “Light Ester BZ”)
Lauryl methacrylate (Kyoeisha Chemical Co., Ltd. “Light Ester L”)
Antioxidant, (D-1) 2,2-methylene-bis (4-methyl-6-tertiary butylphenol) (“Sumilyzer MDP-S” manufactured by Sumitomo Chemical Co., Ltd.)
各種物性は、次のように測定した。
〔光硬化性〕温度２３℃で測定した。光硬化性に関しては、ＺＥＯＮＥＸ４８０Ｒ(日本ゼオン社製)試験片（２５ｍｍ×２５ｍｍ×２．０ｍｍ）表面に接着剤を厚み０．０３ｍｍになるように塗布した。厚みは０．０３ｍｍガラスビーズによって制御した。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、積算光量２０００ｍＪ／ｃｍ2の条件にて１５秒間照射し、硬化させた。光硬化性として、硬化率を記載した。硬化率は、ＦＴ－ＩＲを使用し、以下の式により算出した。
（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（％） Various physical properties were measured as follows.
[Photocurability] Measured at a temperature of 23 ° C. Regarding photocurability, an adhesive was applied to the surface of a ZEONEX 480R (manufactured by Nippon Zeon) test piece (25 mm × 25 mm × 2.0 mm) to a thickness of 0.03 mm. The thickness was controlled by 0.03 mm glass beads. Thereafter, using a curing device manufactured by Fusion Corporation using an electrodeless discharge lamp, irradiation was carried out for 15 seconds under conditions of a wavelength of 365 nm and an integrated light amount of 2000 mJ / cm 2 , and cured. Curing rate was described as photocurability. The curing rate was calculated by the following formula using FT-IR.
(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 (%)
〔シクロオレフィンポリマー接着性評価（ＺＥＯＮＥＸ　試験片間の引張接着強さ）〕ＺＥＯＮＥＸ４８０Ｒ(日本ゼオン社製)試験片１２ａ（幅２５ｍｍ×長さ１００ｍｍ×厚み２．０ｍｍ）の長さ方向の先端部分に、中央に０．５ｃｍ2の大きさの穴１１が空いたテフロン（登録商標）テープ１０（厚み８０μｍ×幅２５ｍｍ×長さ２５ｍｍ）を接着剤厚さ制御のために貼った。当該穴１１に接着剤１３を厚み８０μｍとなるように供給した後、当該穴１１を覆うようにしてテフロン（登録商標）テープ１０の上に、もう一方のＺＥＯＮＥＸ４８０Ｒ(日本ゼオン社製)試験片１２ｂ（幅２５ｍｍ×長さ１００ｍｍ×厚み２．０ｍｍ）の先端部分を貼り合わせた。このときの様子を図１に示す。硬化後、接着剤で接着した該試験片を用いて図１の矢印の左右に引っ張って引張接着強さを測定した。硬化条件は〔光硬化性〕に記載の方法に従った。 [Evaluation of cycloolefin polymer adhesion (tensile bond strength between ZEONEX test pieces)] ZEONEX 480R (manufactured by Nippon Zeon Co., Ltd.) Test piece 12a (width 25 mm × length 100 mm × thickness 2.0 mm) A Teflon (registered trademark) tape 10 (thickness 80 μm × width 25 mm × length 25 mm) having a hole 11 having a size of 0.5 cm 2 in the center was attached to control the adhesive thickness. After supplying the adhesive 13 to the hole 11 so as to have a thickness of 80 μm, on the Teflon (registered trademark) tape 10 so as to cover the hole 11, another ZEONEX 480R (manufactured by Zeon Corporation) test piece 12b The tip portion (width 25 mm × length 100 mm × thickness 2.0 mm) was bonded. The situation at this time is shown in FIG. After curing, the test piece bonded with an adhesive was pulled to the left and right of the arrow in FIG. 1 to measure the tensile bond strength. Curing conditions followed the method described in [Photocurability].
〔耐湿性〕前記シクロオレフィンポリマー接着性評価用試験片を８５℃×８５％ＲＨに２４時間暴露し、該試験片を用いて引張接着強さを測定した。 [Moisture resistance] The cycloolefin polymer adhesion test piece was exposed to 85 ° C x 85% RH for 24 hours, and the tensile bond strength was measured using the test piece.
〔汎用ポリマー接着性評価（ポリカーボネート(帝人社製)　試験片間の引張接着強さ）〕
パンライト(帝人社製)試験片（２５ｍｍ×２５ｍｍ×２．０ｍｍ）同士を、厚み８０μｍ×幅１１．５ｍｍ×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、接着剤を接着させた（接着面積３．１２５ｃｍ2）。硬化後、接着剤で接着した該試験片を用いて引張接着強さを測定した。硬化条件は〔光硬化性〕に記載の方法に従った。 [General-purpose polymer adhesion evaluation (polycarbonate (manufactured by Teijin Limited) tensile strength between test pieces)]
Panlite (made by Teijin Limited) test pieces (25 mm × 25 mm × 2.0 mm) were bonded to each other using a Teflon (registered trademark) tape having a thickness of 80 μm × width of 11.5 mm × length of 25 mm as a spacer. (Adhesion area 3.125 cm 2 ). After curing, the tensile bond strength was measured using the test piece bonded with an adhesive. Curing conditions followed the method described in [Photocurability].
〔汎用ポリマー接着性評価（ポリビニルアルコール(クラレ社製)　試験片間の引張接着強さ）〕試験片（２５ｍｍ×２５ｍｍ×０．０３ｍｍ）同士を、厚み８０μｍ×幅１１．５ｍｍ×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、接着剤を接着させた（接着面積３．１２５ｃｍ2）。硬化後、接着剤で接着した該試験片を用いて引張接着強さを測定した。硬化条件は〔光硬化性〕に記載の方法に従った。 [General-purpose polymer adhesion evaluation (polyvinyl alcohol (manufactured by Kuraray), tensile adhesive strength between test pieces)] Test pieces (25 mm × 25 mm × 0.03 mm) having a thickness of 80 μm × width 11.5 mm × length 25 mm An adhesive was adhered using a Teflon (registered trademark) tape as a spacer (adhesion area: 3.125 cm 2 ). After curing, the tensile bond strength was measured using the test piece bonded with an adhesive. Curing conditions followed the method described in [Photocurability].
〔汎用ポリマー接着性評価（トリアセチルセルロース（コニカミノルタ社製)試験片間の引張接着強さ）〕試験片（２５ｍｍ×２５ｍｍ×０．０３ｍｍ）同士を、厚み８０μｍ×幅１１．５ｍｍ×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、接着剤を接着させた（接着面積３．１２５ｃｍ2）。硬化後、接着剤で接着した該試験片を用いて引張接着強さを測定した。硬化条件は〔光硬化性〕に記載の方法に従った。 [Evaluation of general-purpose polymer adhesion (tensile bond strength between test pieces of triacetyl cellulose (manufactured by Konica Minolta))] Test pieces (25 mm × 25 mm × 0.03 mm) are 80 μm thick × 11.5 mm wide × length An adhesive was adhered using a 25 mm Teflon (registered trademark) tape as a spacer (adhesion area: 3.125 cm 2 ). After curing, the tensile bond strength was measured using the test piece bonded with an adhesive. Curing conditions followed the method described in [Photocurability].
〔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（２５ｍｍ×２５ｍｍ×２．０ｍｍ）同士を、厚み８０μｍ×幅１１．５ｍｍ×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、接着剤を接着させた（接着面積３．１２５ｃｍ2）。硬化条件は〔光硬化性〕に記載の方法に従った。上記条件にて接着剤を硬化させた後、更に、試験片の裏側に電気化学工業社製接着剤「Ｇ－５５」を使用し、亜鉛メッキ鋼板（１００ｍｍ×２５ｍｍ×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。２３℃×５０％ＲＨ×２４時間養生により硬化後、接着剤で接着した該試験片を用いて引張接着強さを測定した。引っ張り剪断接着強さ（単位：ＭＰａ）は、温度２３℃、湿度５０％の環境下で引張速度１０ｍｍ／分で測定した。 [Evaluation of Glass Adhesion (Tensile Adhesive Strength Between Heat-resistant Glass Test Pieces)] Heat-resistant glass test pieces (25 mm × 25 mm × 2.0 mm) were joined to Teflon (registered trademark) with a thickness of 80 μm × width 11.5 mm × length 25 mm. ) Adhesive was adhered using a tape as a spacer (adhesion area 3.125 cm 2 ). Curing conditions followed the method described in [Photocurability]. After the adhesive is cured under the above conditions, an adhesive “G-55” manufactured by Denki Kagaku Kogyo Co., Ltd. is used on the back side of the test piece, and a galvanized steel sheet (100 mm × 25 mm × 2.0 mm, engineering test service) Were attached. After curing by curing at 23 ° C. × 50% RH × 24 hours, the tensile bond strength was measured using the test piece adhered with an adhesive. The tensile shear bond strength (unit: MPa) was measured at a tensile rate of 10 mm / min in an environment of a temperature of 23 ° C. and a humidity of 50%.
〔貯蔵弾性率評価〕接着剤を硬化させて、長さ２０ｍｍ、幅５ｍｍ、×厚み１ｍｍの硬化物試料を調製した。硬化条件は〔光硬化性〕に記載の方法に従った。この硬化物試料を評価した。セイコー電子工業（株）社製テンションモジュールＤＭＳ２１０を使用し、周波数１Ｈｚ、歪み０．０５％の条件で温度を変更して、引っ張りモードで動的粘弾性スペクトルを測定し、２３℃における貯蔵弾性率Ｅの値を求めた。 [Evaluation of storage elastic modulus] The adhesive was cured to prepare a cured product sample having a length of 20 mm, a width of 5 mm, and a thickness of 1 mm. Curing conditions followed the method described in [Photocurability]. This cured product sample was evaluated. Using a tension module DMS210 manufactured by Seiko Denshi Kogyo Co., Ltd., changing the temperature under conditions of a frequency of 1 Hz and a strain of 0.05%, a dynamic viscoelastic spectrum was measured in a tensile mode, and a storage elastic modulus at 23 ° C. The value of E was determined.
（実験例１～１７）表１に示す種類の原材料を表１に示す組成で混合して接着剤を調製した。得られた接着剤について、各種物性の測定を実施した。それらの結果を表１に示す。 (Experimental Examples 1 to 17) Adhesives were prepared by mixing raw materials of the types shown in Table 1 with the compositions shown in Table 1. Various physical properties of the obtained adhesive 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
本願発明は、シクロオレフィンポリマー、ポリカーボネート、ポリビニルアルコール及びガラスに対して、十分な接着強度を発現できる。本願発明は、耐湿性を有する。 This invention can express sufficient adhesive strength with respect to a cycloolefin polymer, a polycarbonate, polyvinyl alcohol, and glass. The present invention has moisture resistance.
１０　　　　　　　テープ
１１　　　　　　　穴
１２ａ、１２ｂ　　試験片
１３　　　　　　　接着剤 10 Tape 11 Hole 12a, 12b Test piece 13 Adhesive

Claims (13)

  1. 下記（Ａ）～（Ｅ）成分を含有してなる樹脂組成物。
    （Ａ）成分は、ジシクロペンテニル基を有する(メタ)アクリレート
    （Ｂ）成分は、水酸基を有する(メタ)アクリレート
    （Ｃ）成分は、（メタ）アクリロイル基を有し、かつ、ジエン系の骨格又は水素添加されたジエン系の骨格を有する（メタ）アクリレート
    （Ｄ）成分は、シランカップリング剤
    （Ｅ）成分は、光重合開始剤     A resin composition comprising the following components (A) to (E):
    (A) component is a (meth) acrylate having a dicyclopentenyl group (B) component is a (meth) acrylate having a hydroxyl group (C) component is having a (meth) acryloyl group and is a diene skeleton Alternatively, the (meth) acrylate (D) component having a hydrogenated diene-based skeleton is a silane coupling agent (E) component is a photopolymerization initiator.
  2. 更に（Ｆ）成分として、（メタ）アクリル酸を含有してなる請求項１に記載の樹脂組成物。 Furthermore, the resin composition of Claim 1 formed by containing (meth) acrylic acid as (F) component.
  3. 更に（Ｇ）成分として、ポリビニルアルコールを含有してなる請求項１乃至２に記載の樹脂組成物。 Furthermore, the resin composition of Claim 1 thru | or 2 formed by containing polyvinyl alcohol as (G) component.
  4. （Ａ）成分、（Ｂ）成分及び（Ｃ）成分の使用量は、（Ａ）成分、（Ｂ）成分及び（Ｃ）成分の合計１００質量部中、（Ａ）成分：（Ｂ）成分：（Ｃ）成分＝４０～９０：１～２０：５～４５（質量比）であり、
    （Ｄ）成分の使用量は、（Ａ）成分、（Ｂ）成分、及び（Ｃ）成分の合計量１００質量部、又は、（Ｆ）成分が使用されるときは（Ａ）成分、（Ｂ）成分、（Ｃ）成分、及び（Ｆ）成分の合計量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（Ｃ）成分の合計量１００質量部、又は、（Ｆ）成分が使用されるときは（Ａ）成分、（Ｂ）成分、（Ｃ）成分、及び（Ｆ）成分の合計量１００質量部に対して、０．０１～３０質量部である、
    請求項１～３のいずれか１項に記載の樹脂組成物。     Component (A), component (B) and component (C) are used in a total of 100 parts by weight of component (A), component (B) and component (C), component (A): component (B): (C) component = 40-90: 1-20: 5-45 (mass ratio),
    The amount of component (D) used is 100 parts by weight of the total amount of component (A), component (B), and component (C), or component (A) when component (F) is used, ) Component, (C) component, and (F) component is 0.01 to 10 parts by mass with respect to 100 parts by mass in total,
    The amount of component (E) used is 100 parts by weight of the total amount of component (A), component (B), and component (C), or component (A) when component (F) is used, ) Component, (C) component, and (F) component is 0.01 to 30 parts by mass with respect to 100 parts by mass in total.
    The resin composition according to any one of claims 1 to 3.
  5. （Ａ）成分がジシクロペンテニル（メタ）アクリレートである請求項1～４のいずれか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 4, wherein the component (A) is dicyclopentenyl (meth) acrylate.
  6. （Ｃ）成分の数平均分子量が５００～５００００である請求項1～５のいずれか１項に記載の樹脂組成物。 6. The resin composition according to claim 1, wherein the number average molecular weight of the component (C) is 500 to 50,000.
  7. 厚み０．０３ｍｍとして、波長３６５ｎｍ、積算光量２０００ｍＪ／ｃｍ2の条件にて１５秒間照射することによって、硬化させたときに、硬化物の貯蔵弾性率が０．１～１０００００ＭＰａ（２３℃）の範囲内となる請求項１～６のいずれか１項に記載の樹脂組成物。 When cured by irradiation for 15 seconds under conditions of a thickness of 0.03 mm, a wavelength of 365 nm and an integrated light quantity of 2000 mJ / cm 2 , the storage elastic modulus of the cured product is in the range of 0.1 to 100,000 MPa (23 ° C.). The resin composition according to any one of claims 1 to 6, wherein the resin composition is inside.
  8. 請求項１～７のいずれか１項に記載の樹脂組成物からなる接着剤。 An adhesive comprising the resin composition according to any one of claims 1 to 7.
  9. シクロオレフィンポリマー用接着剤である請求項８に記載の接着剤。 The adhesive according to claim 8, which is an adhesive for cycloolefin polymer.
  10. ジシクロペンタジエン環構造を有するシクロオレフィンポリマー用接着剤である請求項８乃至９に記載の接着剤。 The adhesive according to claim 8, which is an adhesive for a cycloolefin polymer having a dicyclopentadiene ring structure.
  11. 請求項８～１０のいずれか１項に記載の接着剤を用いて被着体同士が接着されている接着体。 An adhesive body in which adherends are bonded together using the adhesive according to any one of claims 8 to 10.
  12. 被着体が、シクロオレフィンポリマー、ポリカーボネート、セルローストリアセテート、ポリビニルアルコール及びガラスからなる群から選ばれる１種以上である請求項１０に記載の接着体。 The adherend according to claim 10, wherein the adherend is one or more selected from the group consisting of cycloolefin polymer, polycarbonate, cellulose triacetate, polyvinyl alcohol and glass.
  13. 被着体表面に、請求項８～１０のいずれか１項に記載の接着剤を厚み０．０００１～５ｍｍになるように塗布し、被着体同士を貼り合わせ、波長２００～５００ｎｍ、積算光量２００～６０００Ｊ／ｃｍ2、照射時間１～６０秒の条件下で接着剤を硬化することを含む、接着体の製造方法。 The adhesive according to any one of claims 8 to 10 is applied to the surface of the adherend so as to have a thickness of 0.0001 to 5 mm, and the adherends are bonded to each other, with a wavelength of 200 to 500 nm and an integrated light quantity. A method for producing an adhesive comprising curing an adhesive under conditions of 200 to 6000 J / cm 2 and an irradiation time of 1 to 60 seconds.
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CN102686622A (en) 2012-09-19
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TW201124463A (en) 2011-07-16
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