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WO2011161827A1 - Adhesive composition and laminate body - Google Patents

Adhesive composition and laminate body Download PDF

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Publication number
WO2011161827A1
WO2011161827A1 PCT/JP2010/060888 JP2010060888W WO2011161827A1 WO 2011161827 A1 WO2011161827 A1 WO 2011161827A1 JP 2010060888 W JP2010060888 W JP 2010060888W WO 2011161827 A1 WO2011161827 A1 WO 2011161827A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
meth
adhesive composition
acrylate
mgkoh
Prior art date
Application number
PCT/JP2010/060888
Other languages
French (fr)
Japanese (ja)
Inventor
田坂　道久
弘康 管野
Original Assignee
リケンテクノス株式会社
ビーエーエスエフ ソシエタス・ヨーロピア
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 リケンテクノス株式会社, ビーエーエスエフ ソシエタス・ヨーロピア filed Critical リケンテクノス株式会社
Priority to PCT/JP2010/060888 priority Critical patent/WO2011161827A1/en
Publication of WO2011161827A1 publication Critical patent/WO2011161827A1/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
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10018—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising only one glass sheet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10733—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing epoxy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/712—Weather resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2419/00—Buildings or parts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles

Definitions

  • the present invention relates to an adhesive composition and a laminate, and particularly to an adhesive composition for adhering a polyester resin such as polyethylene terephthalate and glass, a laminate using the same, and a window glass.
  • Adhesive composition consisting of vinyl ester resin (urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate), reactive diluent, curing agent, packaging materials, display materials such as labels, electronic parts Widely used in various fields such as precision equipment and construction materials.
  • the thermosetting type has been used for the purpose of speeding up the manufacturing process and improving productivity, but recently, an active energy ray curable liquid curable adhesive that is cured by ultraviolet rays and electron beams has been widely used. It's being used. As the application field expands and the demand for the purpose of use increases, the demand for high-performance liquid-curing adhesives of the active energy ray curable type has become stronger.
  • Patent Document 1 discloses an adhesive composed of a specific epoxy compound, urethane (meth) acrylate, a reactive diluent, a specific long-chain alkyl (meth) acrylate, and a photopolymerizable initiator. The balance between the adhesion between the polyester resin and the glass, and the transparency, surface smoothness, flexibility, and impact resistance was not sufficient.
  • Patent Document 2 discloses a technique in which a pressure-sensitive adhesive layer is provided on one side of a plastic film such as polyethylene terephthalate, and this is adhered to glass. In such a technique, various characteristics required for the window glass are disclosed. Therefore, improvement was demanded.
  • the conventional pressure-sensitive adhesive layer is usually a two-component room-temperature-curing pressure-sensitive adhesive in which an epoxy resin is diluted with a solvent, and takes a long time (for example, 1 hour or more) until volatile organic compound (VOC) and odor are generated and dried. There were problems such as.
  • an object of the present invention is to use an adhesive composition that provides excellent adhesion between a polyester-based resin and glass, and is excellent in balance of transparency, surface smoothness, flexibility, and impact resistance.
  • the object is to provide a laminate.
  • Another object of the present invention is to provide a window glass that imparts excellent adhesion between a polyester resin and glass, and is excellent in transparency, surface smoothness, flexibility, impact resistance, water resistance, and weather resistance. It is to provide.
  • composition containing the following components (a), (b), (c) and (d) in a specific quantitative relationship can solve the above problems.
  • the headline and the present invention were completed.
  • the present invention is as follows. 1. (A) Vinyl ester resin or unsaturated polyester resin 10 to 40% by mass (B) Vinyl monomer and / or (meth) acrylate monomer 30 to 70% by mass (C) modifying agent 5-40% by mass, (However, the total of the components (a) to (c) is 100% by mass) And (d) initiator An adhesive composition for adhering a polyester resin and glass, containing 0.1 to 15 parts by mass with respect to 100 parts by mass in total of the components (a) to (c). 2. 2. The adhesive composition according to 1 above, wherein the component (a) is an epoxy (meth) acrylate. 3. 3. 3.
  • the component (c) is a polyol (c-1) having a hydroxyl value of 40 to 330 mgKOH / g; and a polyol (c-2) having a hydroxyl value of 40 to 330 mgKOH / g and an acid value of 2 to 20 mgKOH / g Modified rubber (c-3); at least one selected from the group consisting of compound (c-4) having an epoxy equivalent of 150 to 700 g / mol;
  • the adhesive composition as described. 5.
  • the component (c-1) is a castor oil-based polyol (c-1-1) having a hydroxyl value of 40 to 330 mgKOH / g; a polybutadiene-based polyol (c-1-2) having a hydroxyl value of 40 to 330 mgKOH / g; 5.
  • the adhesive composition as described in 4 above which is at least one selected from the group consisting of a polyisoprene-based polyol having a value of 40 to 330 mg KOH / g or a hydrogenated product thereof (c-1-3). 6). 6.
  • the component (c-2) is a castor oil-based polyol (c-2-1) having a hydroxyl value of 40 to 330 mgKOH / g and an acid value of 2 to 20 mgKOH / g.
  • the adhesive composition of the present invention contains the components (a), (b), (c) and (d) in a specific quantitative relationship, it is excellent between the polyester resin and the glass. It has excellent balance of transparency, surface smoothness, flexibility and impact resistance. In addition, problems such as generation of volatile organic compounds (VOC) and odors and long time for drying can be solved.
  • the laminate of the present invention comprises a polyester resin layer through an adhesive composition containing the components (a), (b), (c) and (d) in a specific quantitative relationship, Since it is characterized by being laminated with a glass layer, it has excellent adhesion between both layers. Moreover, it is excellent in the balance of transparency, surface smoothness, flexibility and impact resistance. Moreover, since the window glass of the present invention is characterized by comprising the laminate, it has excellent adhesion between both layers, and is excellent in transparency, surface smoothness, flexibility, impact resistance, water resistance, and weather resistance.
  • Component (a) of the adhesive composition of the present invention is a vinyl ester resin or an unsaturated polyester resin.
  • the vinyl ester resin is selected from urethane (meth) acrylate resin, epoxy (meth) acrylate resin, and polyester (meth) acrylate resin, and epoxy (meth) acrylate resin is excellent in adhesiveness. preferable.
  • the (meth) acrylate referred to in the present invention refers to acrylate or methacrylate.
  • Such urethane (meth) acrylate resin is preferably obtained by reaction of polyol, polyisocyanate and (meth) acrylate having one or more hydroxyl groups in one molecule, and two or more (meth) acrylates in one molecule. ) It has an acryloyl group.
  • the polyol used in the urethane (meth) acrylate resin preferably has a number average molecular weight of 200 to 3000, particularly preferably 400 to 2000.
  • Typical examples of the polyol include polyether polyols, polyester polyols, polycarbonate polyols, polybutadiene polyols, and the like. These polyols are used alone or in combination of two or more.
  • the polyether polyol may include a polyol obtained by adding the alkylene oxide to bisphenol A and bisphenol F, in addition to a polyalkylene oxide such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
  • the polyester polyol is a condensation polymer of dibasic acids and polyhydric alcohols or a ring-opening polymer of a cyclic ester compound such as polycaprolactone.
  • Dibasic acids used here are, for example, phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, Hexahydroterephthalic acid, hexahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2 , 3-naphthalenedicarboxylic acid, 2,3-naphthal
  • Polyhydric alcohols include, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, 1,3 -Butanediol, neopentyl glycol, hydrogenated bisphenol A, 1,4-butanediol, 1,6-hexanediol, adducts of bisphenol A and propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, Glycerin, trimethylolpropane, 1,3-propanediol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, 1,4-cycl Hexane dimethanol, paraxylene glycol, bicyclohexyl-4,4'-diol, 2,6-decalin
  • Examples of the polyisocyanate used in the urethane (meth) acrylate resin include 2,4-TDI and its isomer or a mixture of isomers, MDI, HDI, IPDI, XDI, hydrogenated XDI, dicyclohexylmethane diisocyanate, tolidine diisocyanate, and naphthalene.
  • MDI, HDI, IPDI, XDI, hydrogenated XDI, dicyclohexylmethane diisocyanate, tolidine diisocyanate, and naphthalene examples of the polyisocyanate used in the urethane (meth) acrylate resin.
  • Examples of the (meth) acrylate (hydroxyl group-containing (meth) acrylate) having one or more hydroxyl groups per molecule used in the urethane (meth) acrylate resin include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( Mono (meth) acrylates such as (meth) acrylate, 3-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, tris (hydroxyethyl) isocyanuric acid di (meth) acrylate, And polyvalent (meth) acrylates such as pentaerythritol tri (meth) acrylate.
  • the epoxy (meth) acrylate resin used as the vinyl ester resin preferably has two or more (meth) acryloyl groups in one molecule, and is an esterification catalyst for epoxy resin and unsaturated monobasic acid. It is obtained by reacting in the presence of.
  • Examples of the epoxy resin mentioned here include a bisphenol type or novolac type epoxy resin alone, or a resin in which a bisphenol type and a novolac type epoxy resin are mixed, and the average epoxy equivalent is preferably 150 to It is in the range of 450.
  • the bisphenol type epoxy resin a glycidyl ether type epoxy resin substantially having two or more epoxy groups in one molecule obtained by the reaction of epichlorohydrin and bisphenol A or bisphenol F is used.
  • An epoxy resin a methyl glycidyl ether-type epoxy resin obtained by reaction of methyl epichlorohydrin and bisphenol A or bisphenol F, an epoxy resin obtained from an alkylene oxide adduct of bisphenol A and epichlorohydrin or methyl epichlorohydrin, or the like.
  • Typical examples of the novolak type epoxy resin include an epoxy resin obtained by a reaction of phenol novolak or cresol novolak with epichlorohydrin or methyl epichlorohydrin.
  • Typical examples of unsaturated monobasic acids used for epoxy (meth) acrylate resins include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, monomethyl maleate, monopropyl maleate, and monoester maleate. (2-ethylhexyl) or sorbic acid. These unsaturated monobasic acids may be used alone or in combination of two or more.
  • the reaction between the epoxy resin and the unsaturated monobasic acid is preferably carried out using an esterification catalyst at a temperature of 60 to 140 ° C., particularly preferably 80 to 120 ° C.
  • esterification catalyst known catalysts such as tertiary amines such as triethylamine, N, N-dimethylbenzylamine, N, N-dimethylaniline or diazabicyclooctane, triphenylphosphine or diethylamine hydrochloride Can be used as is.
  • the polyester (meth) acrylate resin used as the vinyl ester resin is a saturated or unsaturated polyester having two or more (meth) acryloyl groups in one molecule, and (meth) acrylic at the end of the saturated or unsaturated polyester. A compound is reacted.
  • the number average molecular weight of such a resin is preferably 500 to 5,000.
  • the saturated polyester used in the present invention is a condensation reaction between a saturated dibasic acid and a polyhydric alcohol
  • the unsaturated polyester is a dibasic acid containing an ⁇ , ⁇ -unsaturated dibasic acid and a polyhydric alcohol. It is obtained by the condensation reaction.
  • the resin which made the terminal of unsaturated polyester react with the (meth) acryl compound shall be contained in vinyl ester resin in this invention, and shall be distinguished from the unsaturated polyester resin demonstrated below.
  • saturated dibasic acid examples include the compounds shown in the above-mentioned polyester polyol, and examples of the ⁇ , ⁇ -unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, and itaconic acid. And itaconic anhydride.
  • the compound shown to the term of the said polyester polyol can be mentioned also about polyhydric alcohol.
  • the (meth) acrylic compound of the polyester (meth) acrylate resin used as the vinyl ester resin includes unsaturated glycidyl compounds, various unsaturated monobasic acids such as acrylic acid or methacrylic acid, and glycidyl esters thereof. is there.
  • glycidyl (meth) acrylate is used.
  • the unsaturated polyester resin is obtained by polycondensing an acid component and an alcohol component by a known method, and the kind thereof is not particularly limited as long as it is known as a thermosetting resin.
  • the acid component for example, unsaturated dibasic acids such as maleic anhydride, maleic acid, fumaric acid and itaconic acid are used. If necessary, use a saturated dibasic acid such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, and sebacic acid, and acids other than dibasic acids such as benzoic acid and trimellitic acid. be able to.
  • the alcohol component include polyhydric alcohols shown in the above-mentioned polyester polyol section.
  • Component (b) Vinyl monomer and / or (meth) acrylate monomer
  • Component (b) of the composition of the present invention is a vinyl monomer and / or (meth) acrylate monomer.
  • Specific examples include, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tris (2-hydroxyethyl) ) Isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl
  • Others include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) ) Acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) ) Acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl
  • the component (b) vinyl monomer and / or (meth) acrylate monomer of the composition of the present invention is preferably a cyclic structure from the viewpoint of the adhesion between the polyester resin and the glass (hereinafter sometimes simply referred to as adhesion). And at least one monomer selected from a compound (b-1) having one ethylenically unsaturated group and a diacrylate compound (b-2), wherein (b-1) and (b-2) ) Are more preferably used in combination.
  • Component (b-1) used in the present invention is a compound having a cyclic structure and one ethylenically unsaturated group.
  • the component (b) include alicyclic structure-containing (meth) acrylates such as isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and dicyclopentanyl (meth) acrylate; Examples include benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloylmorpholine, vinylimidazole, vinylpyridine and the like. Furthermore, compounds represented by the following formulas (1) to (3) can be given.
  • R 2 represents a hydrogen atom or a methyl group
  • R 3 represents an alkylene group having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms
  • R 4 represents a hydrogen atom or a methyl group
  • p is preferably Shows the number from 1 to 4.
  • R 5 , R 6 , R 7 and R 8 are independent of each other and are H or CH 3 , and q is an integer of 1 to 5)
  • Examples of the component (b) include monomers having an N-vinyl group in terms of excellent adhesiveness.
  • N-vinylcaprolactam is preferable in terms of excellent adhesiveness.
  • the component (b-2) used in the present invention is a diacrylate monomer.
  • the diacrylate monomer used in the present invention include ethylene glycol diacrylate, dipropylene glycol diacrylate (DPGDA), 1,6-hexanediol diacrylate (HDDA), 1,4-butanediol diacrylate, and tetraethylene glycol diacrylate.
  • DPGDA dipropylene glycol diacrylate
  • HDDA 1,6-hexanediol diacrylate
  • 1,4-butanediol diacrylate 1,4-butanediol diacrylate
  • tetraethylene glycol diacrylate examples include acrylate, tripropylene glycol diacrylate (TPGDA), PO-modified neopentyl glycol diacrylate, and modified bisphenol A diacrylate.
  • TPGDA tripropylene glycol diacrylate
  • PO-modified neopentyl glycol diacrylate and modified bisphenol
  • Denaturant Component (c) used in the present invention is a denaturant.
  • the component (c) modifier has a function of improving adhesiveness in the composition of the present invention.
  • the modifier (c) include a polyol (c-1) having a hydroxyl value of 40 to 330 mgKOH / g; and a polyol (c-) having a hydroxyl value of 40 to 330 mgKOH / g and an acid value of 2 to 20 mgKOH / g. 2); modified rubber (c-3); at least one selected from the group consisting of compound (c-4) having an epoxy equivalent of 150 to 700 g / mol.
  • the hydroxyl value of component (c) contributes to the selective improvement of the adhesion between the polyester resin and the glass.
  • the polyester resin and the glass may be collectively referred to as “adhered body”.
  • the (i) polyol (c-1) having a hydroxyl value of 40 to 330 mgKOH / g includes aromatic, aliphatic, polybutadiene, castor oil, polyisoprene, and the like. As long as it is any type, the selective adhesiveness to the adherend is good.
  • the hydroxyl value is preferably 40 to 330 mgKOH / g from the viewpoint of adhesiveness, and more preferably 150 to 300 mgKOH / g.
  • Castor oil-based polyol (c-1-1) having a hydroxyl value of 40 to 330 mgKOH / g (I) Polybutadiene-based polyol (c-1-2) having a hydroxyl value of 40 to 330 mgKOH / g (I) Polyisoprene polyol having a hydroxyl value of 40 to 330 mgKOH / g or a hydrogenated product thereof (c-1-3)
  • Epoxy polyol resin (c-1-4) having a hydroxyl value of 40 to 330 mgKOH / g Is mentioned.
  • the polyol of component (c) can be used as a mixture of two or more if necessary.
  • the “castor oil” is an oil containing a triester compound of ricinoleic acid and glycerin. Usually, it is a natural fat or oil or a processed natural fat or oil, but it may be a synthetic fat or oil if it contains the above compounds.
  • the ricinoleic acid constituting the triester compound contained in this castor oil is preferably contained in an amount of 90 mol% or more of the fatty acids constituting the whole triester compound.
  • the castor oil may be a processed product such as a hydrogenated product (usually hydrogenated to an intercarbon unsaturated bond in the ricinoleic acid skeleton). Usually, castor oil contains 90 mol% or more (including 100 mol%) of the above-described triester compound (in the case of a hydrogenated product, a hydrogenated product of the triester compound).
  • the “castor oil-based polyol” is an ester compound of ricinoleic acid and / or hydrogenated ricinoleic acid and a polyhydric alcohol. If it has this structure, it may be a polyol obtained by using castor oil as a starting material, or a polyol obtained by using a raw material other than castor oil as a starting material. This polyhydric alcohol is not particularly limited.
  • Castor oil-based polyols include polyols derived from castor oil and polyols obtained by modifying castor oil.
  • the polyol derived from castor oil is a glycerin ester in which part of the ricinoleic acid is replaced with oleic acid, and ricinoleic acid obtained by saponifying castor oil is esterified with trimethylolpropane or other short molecular polyols.
  • fatty acid ester polyols derived from castor oil such as a mixture of these and castor oil.
  • polyols obtained by modifying castor oil include vegetable oil-modified polyols and modified polyols having an aromatic skeleton (such as bisphenol A).
  • a vegetable oil-modified polyol is obtained by replacing a part of glycerin ester ricinoleic acid with a fatty acid obtained from other plants, for example, higher fatty acids such as linoleic acid, linolenic acid, oleic acid obtained from soybean oil, rapeseed oil, olive oil, etc. It is obtained.
  • castor oil-based polyol (c-1-1) having a component (i) hydroxyl value of 40 to 330 mgKOH / g is preferable from the viewpoint of the effect of the present invention.
  • an aromatic castor oil-based polyol (c-1-1-1) having a hydroxyl value of 40 to 330 mgKOH / g is preferable in terms of improving adhesiveness. More preferably, it is 150 to 240 mg KOH / g.
  • the component (c-1-1-1) is a modified polyol derived from castor oil having an aromatic skeleton (for example, bisphenol A).
  • the component (c-1-1-1) is commercially available, and examples thereof include “URIC AC series” (Ito Oil Co., Ltd.).
  • an adduct obtained by adding polyalkylene glycol and bisphenol A to ricinoleic acid is preferable from the viewpoint of improving adhesiveness, and can be represented by, for example, the following formula (4).
  • n represents an average number of 2 to 5.
  • Modified polyols derived from castor oil represented by the formula (4) are, for example, trade names URIC AC-005 (hydroxyl value 194 to 214 mgKOH / mg, viscosity 700 to 1500 mPa ⁇ s / 25 ° C.), AC-006 ( Hydroxyl value 168 to 187 mgKOH / mg, viscosity 3000 to 5000 mPa ⁇ s / 25 ° C., AC-008 (hydroxyl value 180 mgKOH / mg, viscosity 1600 mPa ⁇ s / 25 ° C.), AC-009 (hydroxyl value 225 mgKOH / mg, viscosity 1500 mPa -It can obtain from Ito Oil Co., Ltd. as s / 25 degreeC.
  • polybutadiene-based polyol used in the present invention examples include homopolymers such as 1,2-polybutadiene polyol and 1,4-polybutadiene polyol, poly (pentadiene-butadiene) polyol, poly (butadiene-styrene) polyol, poly ( Examples thereof include copolymers such as butadiene / acrylonitrile) polyols, and hydrogenated polybutadiene-based polyols obtained by adding hydrogen to these polyols.
  • Polybutadiene-based polyols are commercially available.
  • the hydroxyl value of the (c-1-2) polybutadiene-based polyol is preferably 40 to 330 mgKOH / g, more preferably 40 to 110 mgKOH / g.
  • the weight average molecular weight (GPC method) of the polybutadiene-based polyol is preferably 50 to 3000, and more preferably 800 to 1500.
  • Examples of such component (c-1-3) include Polyip (registered trademark) (hydroxyl-terminated liquid polyisoprene) manufactured by Idemitsu. “Poly ip (registered trademark)” (hydroxyl value 46.6 mg KOH / mg, Mn 2500) is a polyisoprene type liquid polymer having a highly reactive hydroxyl group at the molecular end.
  • An example of the hydrogenated product is Epole (registered trademark) (hydroxyl-terminated liquid polyolefin) manufactured by Idemitsu.
  • Epol® hydroxyl value 50.5 mg KOH / mg, Mn 2500
  • the epoxy polyol resin (c-1-4) having a hydroxyl value of 40 to 330 mgKOH / g used in the present invention is obtained by reacting an epoxy resin with an active hydrogen compound.
  • epoxy resin used here examples include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis ( Orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4- Hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobis Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as enol, oxybisphenol, phenol novolak,
  • biphenol methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol (bisphenol AD), isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A
  • a bisphenol type epoxy resin such as a polyglycidyl ether compound such as 1,3-bis (4-hydroxycumylbenzene) and 1,4-bis (4-hydroxycumylbenzene) is preferable because of improving adhesiveness.
  • An epoxy polyol resin (c-1-4) having a hydroxyl value of 40 to 330 mgKOH / g is obtained by reacting an epoxy group of the epoxy resin with an active hydrogen compound such as a carboxylic acid compound, a polyol or an amino compound. It is what
  • carboxylic acid compound examples include acetic acid, propionic acid, 2,2-dimethylolpropionic acid, 12-hydroxystearic acid, lactic acid, butyric acid, octylic acid, ricinoleic acid, lauric acid, benzoic acid, toluic acid, cinnamic acid, phenyl Aliphatic, aromatic or cycloaliphatic monocarboxylic acids such as acetic acid and cyclohexanecarboxylic acid, maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, adipic acid, dimer acid, phthalic acid, isophthalic acid, terephthalic acid, Examples include hexahydro acid and hydroxypolycarboxylic acid.
  • polyol examples include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2-methyl-1,3-propylene glycol, 2,2-dimethyl-1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2,4-trimethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 1,2-octanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol, glycerin, trimethylolpropane, pentaerythritol
  • amino compounds examples include dialkylamine compounds such as dibutylamine and dioctylamine; alkanolamine compounds such as methylethanolamine, butylethanolamine, diethanolamine, diisopropanolamine, and dimethylaminopropylethanolamine; morpholine, piperidine, 4-methylpiperazine And heterocyclic amine compounds such as
  • alkanolamine compounds such as diethanolamine are preferable.
  • the epoxy resin can be chain-extended with a compound having two or more active hydrogen groups such as monoethanolamine and monoisopropanolamine.
  • a normal method of adding the active hydrogen compound to the epoxy resin can be employed.
  • a known catalyst such as a tertiary amine compound or a phosphonium salt.
  • a method in which both are heated to 60 to 200 ° C. and reacted for 3 to 10 hours can be used.
  • a preferable hydroxyl value of the epoxy polyol resin (c-1-4) having a hydroxyl value of 40 to 330 mgKOH / g is 100 to 140 mgKOH / g from the viewpoint of the effect of the present invention.
  • Examples of the epoxy polyol resin (c-1-4) having (i) a hydroxyl value of 40 to 330 mgKOH / g include EPICLON U-125-60BT (hydroxyl value 100 to 140 mgKOH / g) manufactured by DIC Corporation.
  • the polyol (c-2) having a hydroxyl value of 40 to 330 mg KOH / g and (ii) an acid value of 2 to 20 mg KOH / g is aromatic, aliphatic or castor oil-based.
  • the adhesiveness is improved by satisfying the hydroxyl value of (i) and the acid value of (ii).
  • the hydroxyl value of (i) is more preferably 230 to 300 mgKOH / g.
  • the acid value of (ii) is more preferably 4 to 15 mg KOH / g.
  • a castor oil-based polyol (c-2-1) having a hydroxyl value of 40 to 330 mg KOH / g and (ii) an acid value of 2 to 20 mg KOH / g is a polyol derived from castor oil. As disclosed in JP-A-2005-89712, it contains a castor oil-based polyol derived from ricinoleic acid, an acidic phosphate ester compound having a total carbon number of 12 or more, and, if necessary, terpene phenols Polyol compositions can also be used. These can be obtained from Ito Refinery under the trade names URIC H-1262 and H2151U, for example.
  • the Ito Oil URIC H-1262 is a polyol containing a castor oil-based polyol and an acidic phosphate ester compound having a total carbon number of 12 or more (viscosity: 3,500 to 8,500 mPa ⁇ s / 25 ° C., hydroxyl value: 240 to 290 (unit mgKOH / g), acid value: 4 to 15 (unit mgKOH / g)), and excellent in adhesion and hydrolysis resistance.
  • the Ito Oil URIC H-2151U is a polyol containing a castor oil-based polyol, an acidic phosphate compound having a total carbon number of 12 or more, and a terpene phenol (viscosity: 3,500 to 8,500 mPa ⁇ s / 25). ° C, hydroxyl value: 240 to 290 (unit mgKOH / g), acid value: 4 to 15 (unit mgKOH / g)), and excellent in adhesion and hydrolysis resistance.
  • the modified rubber (c-3) will be described.
  • Examples of the modified rubber (c-3) used in the present invention include (c-3-1) liquid carboxylated polyisoprene and (c-3-2) carboxylated polybutadiene.
  • (C-3-1) Carboxylated polyisoprene
  • the carboxylated polyisoprene (c-3-1) used in the present invention is mainly used when adhering the composition of the present invention to an adherend. Improves wettability and improves the adhesion.
  • Examples of the component (c-3-1) include LIR-420 manufactured by Kuraray as maleated polyisoprene.
  • Component (c-3-2) is a liquid liquid which is transparent at room temperature, and has a main chain microstructure of polybutadiene consisting of vinyl 1,2-bond type, trans 1,4-bond type, cis 1,4-bond type. It is a polymer.
  • the vinyl 1,2-bond is preferably 30% by weight or less, and if the vinyl 1,2-bond exceeds 30% by weight, the storage stability of the resulting composition is deteriorated.
  • the cis 1,4-bond is preferably 40% by weight or more. If the cis 1,4-bond is less than 40% by weight, the adhesiveness of the resulting composition is lowered, which is not preferable.
  • the carboxylated polybutadiene (c-3-2) component is obtained by reacting liquid polybutadiene with a carboxyl group-introducing compound, and the ratio of 1,3-butadiene and carboxyl group-introducing compound constituting the liquid polybutadiene is 1,3. -80 to 98% by weight of butadiene and 2 to 20% by weight of the carboxyl group-introducing compound are preferred.
  • the liquid polybutadiene used in the reaction preferably has a number average molecular weight of 500 to 10,000, more preferably 1,000 to 7,000, and a wide molecular weight distribution.
  • the liquid polybutadiene more preferably has an iodine value measured according to DIN 53241, iodine of 30 to 500 g / 100 g of substance.
  • the liquid polybutadiene preferably has a molecular structure of 70 to 90% cis-double bonds, 10 to 30% trans-double bonds and 0 to 3% vinyl double bonds.
  • an ethylenically unsaturated dicarboxy compound for example, an ethylenically unsaturated dicarboxylic acid, its anhydride or monoester
  • the compound include maleic acid, fumaric acid, itaconic acid, 3,6-tetrahydrophthalic acid, itaconic anhydride, 1,2-dimethylmaleic anhydride, maleic acid monomethyl ester and maleic acid monoethyl ester. be able to.
  • maleic anhydride is preferable because of safety, economy and reactivity. (Maleed polybutadiene is preferred.)
  • Production of a polybutadiene / maleic anhydride-addition product comprising polybutadiene and maleic anhydride can be carried out by a known method.
  • the acid value of maleated liquid polybutadiene according to DIN ISO 3682 is preferably 50 to 120 (mgKOH / g), more preferably 70 to 90 (mgKOH / g).
  • the acid value is less than 50 (mgKOH / g)
  • the adhesiveness of the resulting composition is lowered
  • it exceeds 120 (mgKOH / g) the viscosity of the obtained composition is increased and workability is lowered.
  • the maleation rate of the maleated liquid polybutadiene is related to the viscosity, but is preferably 6 to 20%, more preferably 6 to 15%, and still more preferably 7 to 10%.
  • the viscosity (20 ° C.) of maleated liquid polybutadiene measured by DIN 53214 is preferably 3 to 16 Pa ⁇ s, more preferably 5 to 13 Pa ⁇ s, and further preferably 6 to 9 Pa ⁇ s.
  • maleated liquid polybutadiene has a vinyl-double bond of 30% or less, and those having a cis-double bond in the above range have higher flexibility than liquid polybutadiene in which the cis-double bond is less than the above lower limit. And has a high maleation rate (acid value) as described above. Therefore, the obtained composition is rich in adhesiveness and sufficiently polarized, so that it can be made more flexible and the flexibility can be easily adjusted.
  • Liquid polybutadiene having a cis-double bond less than the above lower limit rapidly increases in viscosity as the maleation rate increases, but those having a cis-double bond in the above range have a small increase in viscosity. Since the viscosity is low as in the above range, the reactivity is increased and workability is improved. Moreover, the composition obtained is excellent in terms of low viscosity expression and adhesiveness.
  • Examples of commercially available maleated liquid polybutadiene include Degussa's POLYVEST OC 800S (registered trademark) and 1200S.
  • One form of the compound (c-4) having an epoxy equivalent of 150 to 700 g / mol used in the present invention is a polyepoxy compound (c-4-1) having an epoxy equivalent of 150 to 250 g / mol. .
  • Examples of the polyepoxy compound (c-4-1) having an epoxy equivalent of 150 to 250 g / mol in the composition of the present invention include mononuclear polyhydric phenols such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol.
  • Examples of the polyepoxy compound (c-4-1) having an epoxy equivalent of 150 to 250 g / mol used in the present invention include biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropyl Ridenbisphenol (bisphenol A), isopropylidenebis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1, Polyphenols of bisphenol compounds such as 1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, terpene diphenol Glycidyl Jill ether is more preferable in terms of adhesion.
  • polyglycidyl ethers of bisphenol compounds having an epoxy equivalent of 150 to 250 g / mol examples include Adeka Resin EP-4100E (Asahi Denka Kogyo; bisphenol A diglycidyl ether, epoxy equivalent 190).
  • Another form of the compound (c-4) having an epoxy equivalent of 150 to 700 g / mol used in the present invention is a polyolefin polymer (c-4-2) having an epoxy equivalent of 500 to 700 g / mol. It is.
  • a polyolefin polymer having a hydroxyl group at one end and having an epoxy group introduced is preferred. More preferably, it is liquid.
  • a specific example of the polymer (c-4) having an epoxy equivalent of 150 to 700 g / mol is Kuraray L-207 (same as KRATON LIQUID TM L-207 POLYMER).
  • L-207 is a heavy saturated skeleton (epoxidized ethylene / propylene / ethylene / butylene-OH structure) having an epoxy equivalent of 590 g / mol, a hydroxyl group equivalent of 7000 g / mol and a glass transition temperature of ⁇ 53 ° C. It is a coalescence and is preferable in terms of adhesiveness.
  • the adhesive composition of the present invention comprises (d) an initiator as an essential component.
  • the oligomer component for example, vinyl ester resin or unsaturated polyester resin (a)
  • the oligomer component has a double bond such as a (meth) acryloyl group.
  • a photopolymerization initiator is added, it can be easily cured in a short time by ultraviolet irradiation or electron beam irradiation using an ultraviolet fluorescent lamp or a high-pressure mercury lamp. When it is desired to avoid heating the adherend and the adhesive composition, ultraviolet irradiation is preferred.
  • the adhesive composition of the present invention When the adhesive composition of the present invention is cured by heating, it can be cured by heating at about room temperature to 90 ° C.
  • the thermal polymerization initiator include benzoyl peroxide, lauroyl peroxide, succinic acid peroxide, methyl ethyl ketone peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, and cyclohexanone peroxide. Is mentioned. For example, when the (1 minute) half-life temperature of the peroxides is 100 ° C. to 180 ° C., sufficient curability can be obtained at 80 ° C. ⁇ 10 minutes to 160 ° C. ⁇ 5 minutes.
  • photopolymerization initiator examples include benzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, acetophenone, benzoin, benzoin ethyl ether, benzoin-n-propyl ether, benzoin isopropyl ether, benzoin-n- Butyl ether, benzoin isobutyl ether, benzyl-1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl 1-phenylpropan-1-one, benzyl sulfide, thioxanthone Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-chlorothixant and the like.
  • the component (a) is blended in an amount of 10 to 40% by mass from the viewpoints of adhesiveness, flexibility and impact resistance.
  • a more preferable blending ratio of the component (a) is 15 to 35% by mass in terms of a viscosity that is easy to process.
  • the component (b) is blended in an amount of 30 to 70% by mass from the viewpoints of adhesiveness, flexibility and impact resistance.
  • a more preferable amount of component (b) is 40 to 65% by mass from the viewpoint of easy processing viscosity.
  • the compounding amount of the component (b) exceeds 70% by mass, adhesiveness, flexibility, impact resistance, and weather resistance are lowered.
  • flexibility, and impact resistance will deteriorate, and workability will fall by thickening.
  • the component (c) is blended in an amount of 5 to 40% by mass from the viewpoints of adhesiveness and flexibility. Further, the blending ratio of the component (c) is 10 to 30% by mass, particularly preferably 10 to 25% by mass in terms of adhesion, toughness (impact resistance) and bleed resistance.
  • the toughness (impact resistance) decreases due to the deterioration of the bleed resistance, the adhesive strength also decreases, and the water resistance and weather resistance also deteriorate.
  • flexibility, impact resistance, and a weather resistance will fall.
  • the component (d) is a total of the components (a) to (c) from the viewpoint of practical photocuring time (irradiation intensity of 500 mJ / cm 2 and irradiation for 10 seconds or less). 0.1 to 15 parts by mass is blended with respect to 100 parts by mass.
  • the amount of the component (d) is more preferably 1 to 10 parts by weight, particularly preferably 2 to 5 parts by weight in terms of practical photocuring time (irradiation intensity of 500 mJ / cm 2 for 3 seconds or less). Part.
  • the compounding amount of the component (d) exceeds 15 parts by mass, flexibility, adhesiveness and impact resistance are lowered.
  • it is less than 0.1 mass part since photocuring is inadequate, it is inferior to adhesiveness.
  • the same compounding quantity as the above may be sufficient.
  • a functional filler or the like generally used as a filler can be added and blended as long as the object of the present invention is not impaired.
  • Examples of imparting rigidity include talc and mica, and these are used singly or in combination of two or more.
  • thermal conductivity imparting examples include barium sulfate and magnesium oxide, and these are used alone or in combination of two or more.
  • Examples of imparting thermal expansion include thermal expansion microcapsules.
  • Examples of the leveling property imparting include a silicone leveling agent.
  • the viscosity at 25 ° C. of the adhesive composition of the present invention is not particularly limited, but is preferably 3,000 mPa ⁇ s or less, more preferably 100 to 2,000 mPa ⁇ s. If the viscosity is within this range, stable storage stability that does not separate with time can be obtained, bubbles are not easily generated, and smooth surface properties can be obtained. ⁇ The viscosity can be measured with a B-type viscometer.
  • the adherend of the adhesive composition of the present invention is a polyester resin and glass.
  • the polyester resin include polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), and PET is particularly preferable from the viewpoint of adhesiveness.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PET is particularly preferable from the viewpoint of adhesiveness.
  • the glass is not particularly limited, and examples thereof include hard and light soda lime glass, quartz glass having a high refractive index and transparency, and low but hard and light borosilicate glass.
  • the components (b) and (c) are added as reactive diluents to the component (a) in a container equipped with a stirrer.
  • the component (b) is added to the component (a) and sufficiently stirred at room temperature. If the viscosity is too high, stirring may be performed while heating at 100 ° C. or lower. If it exceeds 100 ° C., the vapor generation of the component (b) becomes remarkable, which is not preferable in the working environment. Thereafter, after adding component (c) and stirring, when the liquid temperature reaches room temperature, component (d) is added, and the mixture is sufficiently stirred so as not to remain undissolved. When adding other components, add them at the end and stir well.
  • the adhesive composition obtained by stirring is quickly processed or stored in a cool and dark place.
  • the laminate of the present invention is characterized in that a polyester resin layer and a glass layer are laminated via the adhesive composition.
  • the adhesive composition of the present invention is prepared as described above, and then the adhesive composition is laminated on the layer of the adherend (B1). A layer (A) is formed, and then an adherend layer (B2) is further laminated on the layer (A) of the adhesive composition.
  • the adherend (B1) is a polyester resin
  • the adherend (B2) is glass
  • the adherend (B2) is a polyester resin layer.
  • the thickness of the layer (A) (cured coating film) of the adhesive composition is not particularly limited, but is about 2 ⁇ m to 50 ⁇ m, preferably 5 ⁇ m to 30 ⁇ m, and more preferably about 8 ⁇ m to 20 ⁇ m.
  • the adhesive composition of the present invention is blended without solvent (volatile), the coating thickness and the film thickness after curing are not significantly different because there is little shrinkage at the time of curing.
  • Coating methods include spin coating, (doctor) knife coating, micro gravure coating, direct gravure coating, offset gravure, reverse gravure, reverse roll coating, (Meyer) bar coating, die coating, Methods such as spray coating and dip coating can be preferably applied.
  • a manual spinner (ASS-301 type manufactured by Able Co., Ltd.) can be cited as an apparatus for spin coating.
  • the laminate of the present invention has good adhesion between the adherend layers (B1) and (B2) and the adhesive composition layer (A), and has transparency, surface smoothness, flexibility, and impact resistance. Excellent balance of sex.
  • the layer of the adherend and the layer of the adhesive composition can be alternately laminated a plurality of times, and this is also within the scope of the laminate referred to in the present invention.
  • the laminate of the present invention is useful as a window glass from the viewpoint that transparency, surface smoothness, flexibility, impact resistance, water resistance, and weather resistance are all good.
  • the window glass is not particularly limited, and examples thereof include window glass for buildings such as ordinary houses and buildings, vehicles such as automobiles and railways, window glass for vehicles such as airplanes and ships, and viewing windows in mechanical equipment.
  • the window glass for buildings is preferable from a viewpoint that said various characteristics are excellent.
  • various known functional fillers such as an infrared absorbing material, an ultraviolet absorbing material, and an antistatic material are optionally added to the polyester resin layer. Materials, electromagnetic shielding materials and the like can be added.
  • infrared absorbing materials include carbon nanotubes, zinc oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, cesium-containing tungsten oxide, ATO (antimony-tin composite oxide or antimony-doped tin oxide), ITO (indium-tin composite oxide). Thing) etc. are mentioned.
  • the blending amount of the infrared absorbing material may be appropriately determined in consideration of a desired infrared absorptivity. For example, the range of 0.1 to 30% by mass in the polyester resin layer may be mentioned.
  • Examples of the ultraviolet absorbing material include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, triazine-based organic compounds, the carbon nanotubes described above, zinc oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, and titanium dioxide.
  • Inorganic compounds such as hybrid inorganic powder obtained by complexing cerium oxide and titanium dioxide fine particles with iron oxide, and hybrid inorganic powder obtained by coating the surface of cerium oxide fine particles with amorphous silica.
  • the blending amount of the ultraviolet absorbing material may be appropriately determined in consideration of the desired ultraviolet absorptivity, and examples thereof include a range of 0.1 to 30% by mass in the polyester resin layer.
  • the antistatic material examples include metal oxides and metal salts.
  • the metal oxide include zinc oxide, aluminum doped zinc oxide, gallium doped zinc oxide, ATO, ITO, tin oxide, and antimony pentoxide described above. , Zirconium oxide, titanium oxide, aluminum oxide and the like.
  • the carbon nanotube mentioned above can also be utilized.
  • the blending amount of the antistatic material may be appropriately determined in consideration of the desired antistatic property, and examples thereof include a range of 0.1 to 30% by mass in the polyester resin layer.
  • the electromagnetic shielding material examples include conductive particles such as (1) carbon particles or powder; (2) nickel, indium, chromium, gold, vanadium, tin, cadmium, silver, platinum, aluminum, copper, titanium, cobalt , Particles or powders of lead or other metals or alloys or conductive oxides thereof; (3) a coating layer of the conductive material (1) or (2) above is formed on the surface of plastic particles such as polystyrene or polyethylene; And the like.
  • the blending amount of the electromagnetic shielding material may be appropriately determined in consideration of desired electromagnetic shielding properties. For example, a range of 60 to 90% by mass in the polyester resin layer may be mentioned. In the window glass of the present invention, the polyester resin layer may be on the outdoor side or the indoor side.
  • the raw materials used in the examples and comparative examples are as follows.
  • Component (b-1) Compound having a cyclic structure and one ethylenically unsaturated group (i) N-vinylcaprolactam boiling point 117 ° C. (10 mm Hg) manufactured by BASF Vapor pressure ⁇ 0.1 mm Hg (20 °C) Flash point 110 ° C Melting point 35 °C Viscosity 3.5 cps (40 ° C)
  • Component (b-2) Diacrylate monomer (i) Dipropylene glycol diacrylate (DPGDA) manufactured by BASF (Ii) BASF, tripropylene glycol diacrylate (TPGDA)
  • Component (c) Modifier (c-1-2) Polybutadiene polyol manufactured by Idemitsu Kosan Co., Ltd., Poly bd R-15HT Viscosity: 1.5 Pa ⁇ s / 30 ° C., hydroxyl value: 102.7 mg KOH / g (C-1-1-1) Aromatic castor oil-based polyol manufactured by Ito Oil Co., Ltd., URIC (trademark) AC-006, a polyol derived from castor oil represented by the above formula (4), viscosity: 0.7 to 1.5 Pa ⁇ s / 25 ° C., hydroxyl value: 194 to 214 mg KOH / g (C-1-3) Polyisoprene-based polyol manufactured by Idemitsu Kosan Co., Ltd.
  • Epol (trademark) hydroxyl terminated liquid polyolefin (viscosity (Pa ⁇ s / 30 ° C) 75, hydroxyl value (mgKOH / g) 50.5, number average Molecular weight 2500) (C-3-1) Maleinized polyisoprene Kuraray LIR-420 (acid value (mgKOH / g) 40) (C-3-2) Maleic acid-modified polybutadiene SARTOMER Ricon130MA8 (viscosity (Pa ⁇ s / 30 ° C) 6.5, acid value (mgKOH / g) 46, number average molecular weight 2700) (C-3-2) Maleic acid-modified polybutadiene POLYVEST TM OC 800 S manufactured by EVONIK (1,4-cis double bond in polybutadiene: 75%, 1,4-trans double bond: 24%, vinyl bond: 1%, maleation ratio: 7.5 %, Number average molecular weight: 3300
  • Viscosity measurement method The viscometer is measured using a single cylindrical rotational viscometer (B type TVC--5) according to JIS K7117-1. 1. A 500ml beaker (standard) is used for the measuring instrument. 2. The standard rotor is selected from two types: M1 to M4 rotors for low and medium viscosity and H1 to H7 rotors for medium and high viscosity. Hydroxyl value measurement method Hydroxyl value is included in 1g of sample. This is the number of mg of potassium hydroxide required to acetylate the OH group. According to JIS K 1557-1, OH groups in the sample are acetylated using acetic anhydride, and acetic acid not used is titrated with potassium hydroxide solution.
  • A Amount of 0.5 mol / l potassium hydroxide ethanol solution used for the blank test (ml)
  • B 0.5mol / l potassium hydroxide ethanol solution used for titration (ml)
  • f Factor
  • -Acid value measuring method It represents with the mg number of potassium hydroxide required to neutralize the acidic component contained in 1g of sample oils.
  • End-point pH measurement Take 10 mL of buffer stock solution B in a 200-mL beaker, add 100 mL of titration solvent, immerse the electrode, and use the pH that changes within 0.1 pH within 30 seconds as the buffer end point.
  • Measurement of acid value 1. Weigh accurately 20 g of sample into a 200 mL beaker. 2. Add 125mL of toluene / 2-propanol / pure water mixed solvent and titrate with 0.1mol / L potassium hydroxide titrant.
  • Component (d) Component Initiator (i) Photopolymerization initiator CIBA, IRGACURE TM 819, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (ii) Thermal polymerization initiator NOF Corporation Perhexa 25B (1 minute half-life: 179 ° C.), 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane
  • the composition was applied by spin coating (coating thickness 15 to 20 ⁇ m), and this was applied under air to 500 mJ.
  • a laminate was prepared by irradiating with UV light having an energy of / cm 2 to be cured.
  • a thermal polymerization initiator if necessary, 0 to 0.05 part by mass of 6% naphthenic cobalt is added to the composition and cured by heat treatment at 100 ° C. for 30 minutes to prepare a laminate. did.
  • Each adherend used is as follows. ⁇ Glass (slide glass for microscope preparation) ⁇ PET: Unitika Unitika polyester resin MA-2103
  • Transparency test (measurement of haze value and total light transmittance) Using a laminate using glass as the adherend, measurement was performed using a measuring instrument (trade name “COH-300A”) manufactured by Nippon Denshoku Industries Co., Ltd.
  • Cross cut tape test The resulting laminate was subjected to the following cross cut tape test. The measurement was performed as follows in accordance with the cross cut tape test method described in Japanese Industrial Standard K5400.
  • Adhesion test On the polyester resin (B1) having dimensions of 150 mm ⁇ 1 mm thickness ⁇ 25 mm width, the composition was applied by spin coating (coating thickness: 15 to 20 ⁇ m) to form a composition layer (A), Further thereon, glass (B2) having the same dimensions as (B1) shown in Tables 1 to 7 is pressure-bonded, and UV irradiation (wavelength: 325 nm, integrated irradiation intensity: 50 mJ) from the layer (B2) (glass) side. / cm 2 ) and UV curing to prepare a laminate, the layer (B2) was pulled in a direction parallel to the bonding surface of the layer (A) of the composition, and the tensile strength at break was measured.
  • glass (B2) having the same dimensions as (B1) shown in Tables 1 to 7 is pressure-bonded, and UV irradiation (wavelength: 325 nm, integrated irradiation intensity: 50 mJ) from the layer (B2) (glass) side. / cm 2
  • the components (a), (b), (c) and (d) are contained in a specific quantitative relationship. Excellent adhesiveness can be imparted between the resin and the glass, and the balance of transparency, surface smoothness, flexibility, impact resistance, water resistance, and weather resistance is excellent.
  • the addition amount of the component (b) exceeded the upper limit prescribed
  • Comparative Example 2 since the amount of component (a) added exceeded the upper limit defined in the present invention, the adhesiveness deteriorated.
  • Comparative Example 3 since the component (c) was not added, adhesion and weather resistance were deteriorated. In Comparative Example 4, since the amount of component (c) added exceeded the upper limit defined in the present invention, the adhesion, water resistance, and weather resistance deteriorated. In Comparative Example 5, since the amount of component (d) added was less than the lower limit specified in the present invention, the composition was not cured. In Comparative Example 6, since the amount of component (d) added exceeded the upper limit specified in the present invention, the adhesion, impact resistance, and flexibility deteriorated.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)

Abstract

The disclosed adhesive composition is capable of imparting excellent adhesion between polyester resin and glass, and contains (a) a vinyl ester resin or an unsaturated polyester resin (10-40 mass%), (b) vinyl monomers and / or (meth) acrylate monomers (30-70 mass%), (c) a denaturant (5-40 mass% (wherein the sum of the mass percentages of the aforementioned components (a) to (c) is 100 mass%) and (d) an initiator (0.1-15 parts mass per 100 parts mass of the aforementioned components (a) to (c) combined).

Description

接着剤組成物および積層体Adhesive composition and laminate
　本発明は、接着剤組成物および積層体に関し、とくに、ポリエチレンテレフタレートのようなポリエステル系樹脂とガラスとを接着させるための接着剤組成物、これを用いた積層体および窓ガラスに関する。 The present invention relates to an adhesive composition and a laminate, and particularly to an adhesive composition for adhering a polyester resin such as polyethylene terephthalate and glass, a laminate using the same, and a window glass.
　ビニルエステル系樹脂（ウレタン（メタ）アクリレート、エポキシ（メタ）アクリレート、ポリエステル（メタ）アクリレート）、反応性希釈剤、硬化剤からなる接着剤組成物は、包装材料、ラベル等の表示材料、電子部品、精密機器、建設材料等様々な分野において広く利用されている。近年では製造工程の高速化、生産性向上の目的で、熱硬化タイプが使用されてきたが、最近では、それにかわり紫外線、電子線で硬化する活性エネルギー線硬化タイプの液状硬化性接着剤も広く利用されている。このように利用分野の拡大とその利用目的に対する要求の高性能化が進むにつれ、活性エネルギー線硬化タイプの液状硬化性接着剤についても、高性能化要求が強くなっている。 Adhesive composition consisting of vinyl ester resin (urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate), reactive diluent, curing agent, packaging materials, display materials such as labels, electronic parts Widely used in various fields such as precision equipment and construction materials. In recent years, the thermosetting type has been used for the purpose of speeding up the manufacturing process and improving productivity, but recently, an active energy ray curable liquid curable adhesive that is cured by ultraviolet rays and electron beams has been widely used. It's being used. As the application field expands and the demand for the purpose of use increases, the demand for high-performance liquid-curing adhesives of the active energy ray curable type has become stronger.
　なお、下記特許文献１には、特定のエポキシ化合物、ウレタン（メタ）アクリレート、反応性希釈剤、特定の長鎖アルキル（メタ）アクリレート、光重合性開始剤からなる接着剤が開示されているが、ポリエステル系樹脂とガラスとの接着性、さらに、透明性、表面平滑性、柔軟性、耐衝撃性のバランスが充分なものではなかった。 Patent Document 1 below discloses an adhesive composed of a specific epoxy compound, urethane (meth) acrylate, a reactive diluent, a specific long-chain alkyl (meth) acrylate, and a photopolymerizable initiator. The balance between the adhesion between the polyester resin and the glass, and the transparency, surface smoothness, flexibility, and impact resistance was not sufficient.
　一方、建物用の窓ガラス、車両や船舶等の乗物用の窓ガラスには、一般的に優れた透明性、表面平滑性、柔軟性、耐衝撃性、耐水性、耐候性が求められる。下記特許文献２には、ポリエチレンテレフタレートのようなプラスチックフィルムの片面に粘着剤層を設け、これをガラスに貼着する技術が開示されているが、係る技術では、上記窓ガラスに求められる各種特性を満足することができず、改善が求められていた。
　また従来の粘着剤層は、通常、エポキシ樹脂を溶剤希釈した２液常温硬化型の粘着剤であり、揮発性有機化合物（ＶＯＣ）および臭気の発生、乾燥まで長時間(例えば１時間以上)かかる、等の問題点があった。 On the other hand, window glass for buildings and window glass for vehicles such as vehicles and ships generally require excellent transparency, surface smoothness, flexibility, impact resistance, water resistance, and weather resistance. The following Patent Document 2 discloses a technique in which a pressure-sensitive adhesive layer is provided on one side of a plastic film such as polyethylene terephthalate, and this is adhered to glass. In such a technique, various characteristics required for the window glass are disclosed. Therefore, improvement was demanded.
The conventional pressure-sensitive adhesive layer is usually a two-component room-temperature-curing pressure-sensitive adhesive in which an epoxy resin is diluted with a solvent, and takes a long time (for example, 1 hour or more) until volatile organic compound (VOC) and odor are generated and dried. There were problems such as.
特開平２－２９６８７９号公報JP-A-2-296879 特開２０００－９６００９号公報JP 2000-96009 A
　したがって本発明の目的は、ポリエステル系樹脂とガラスとの間に優れた接着性を付与し、透明性、表面平滑性、柔軟性、耐衝撃性のバランスに優れる接着剤組成物、これを用いた積層体を提供することにある。また本発明の別の目的は、ポリエステル系樹脂とガラスとの間に優れた接着性を付与し、透明性、表面平滑性、柔軟性、耐衝撃性、耐水性、耐候性に優れる窓ガラスを提供することにある。 Therefore, an object of the present invention is to use an adhesive composition that provides excellent adhesion between a polyester-based resin and glass, and is excellent in balance of transparency, surface smoothness, flexibility, and impact resistance. The object is to provide a laminate. Another object of the present invention is to provide a window glass that imparts excellent adhesion between a polyester resin and glass, and is excellent in transparency, surface smoothness, flexibility, impact resistance, water resistance, and weather resistance. It is to provide.
　本発明者は鋭意研究を行った結果、下記成分（ａ）、（ｂ）、（ｃ）および（ｄ）を特定の量的関係でもって含有する組成物が、前記課題を解決し得ることを見出し、本発明を完成した。 As a result of intensive studies, the present inventor has found that a composition containing the following components (a), (b), (c) and (d) in a specific quantitative relationship can solve the above problems. The headline and the present invention were completed.
　すなわち本発明は、以下の通りである。
　１．（ａ）ビニルエステル樹脂または不飽和ポリエステル樹脂　１０～４０質量％
（ｂ）ビニルモノマーおよび／または（メタ）アクリレートモノマー　３０～７０質量％
（ｃ）変性剤　５～４０質量％、
（ただし、前記成分（ａ）～（ｃ）の合計は１００質量％である）
および
（ｄ）開始剤　前記成分（ａ）～（ｃ）の合計１００質量部に対し０．１～１５質量部
を含有する、ポリエステル系樹脂とガラスを接着させるための接着剤組成物。
　２．前記成分（ａ）が、エポキシ（メタ）アクリレートであることを特徴とする前記１に記載の接着剤組成物。
　３．前記成分（ｂ）が、Ｎ－ビニル基を有するモノマーであることを特徴とする前記１または２に記載の接着剤組成物。
　４．前記成分（ｃ）が、水酸基価４０～３３０ｍｇＫＯＨ／ｇのポリオール（ｃ－１）；および水酸基価４０～３３０ｍｇＫＯＨ／ｇであり、かつ酸価が２～２０ｍｇＫＯＨ／ｇであるポリオール（ｃ－２）；変性ゴム（ｃ－３）；エポキシ当量が１５０～７００ｇ／モルである化合物（ｃ－４）からなる群から選択された少なくとも１種であることを特徴とする前記１～３のいずれかに記載の接着剤組成物。
　５．前記成分（ｃ－１）が、水酸基価４０～３３０ｍｇＫＯＨ／ｇのヒマシ油系ポリオール（ｃ－１－１）；水酸基価４０～３３０ｍｇＫＯＨ／ｇのポリブタジエン系ポリオール（ｃ－１－２）；および水酸基価４０～３３０ｍｇＫＯＨ／ｇのポリイソプレン系ポリオールまたはその水素添加物（ｃ－１－３）からなる群から選択された少なくとも１種であることを特徴とする前記４に記載の接着剤組成物。
　６．前記成分（ｃ－１）が、水酸基価４０～３３０ｍｇＫＯＨ／ｇの芳香族系ヒマシ油系ポリオール（ｃ－１－１－１）であることを特徴とする前記５に記載の接着剤組成物。
　７．前記成分（ｃ－２）が、水酸基価４０～３３０ｍｇＫＯＨ／ｇであり、かつ酸価が２～２０ｍｇＫＯＨ／ｇであるヒマシ油系ポリオール（ｃ－２－１）であることを特徴とする前記４に記載の接着剤組成物。
　８．前記成分（ｃ－３）が酸変性ポリブタジエンまたは酸変性ポリイソプレンであることを特徴とする前記４に記載の接着剤組成物。
　９．前記成分（ｃ－４）がエポキシ当量が１５０～２５０ｇ／モルであるポリエポキシ化合物（ｃ－４－１）であることを特徴とする前記４に記載の接着剤組成物。
　１０．前記成分（ｃ－４）がエポキシ当量が５００～７００ｇ／モルである飽和骨格を持つ重合体（ｃ－４－２）であることを特徴とする前記４に記載の接着剤組成物。
　１１．前記ポリエステル系樹脂が、ポリエチレンテレフタレートであることを特徴とする前記１～１０のいずれかに記載の接着剤組成物。
　１２．前記１～１１のいずれかに記載の接着剤組成物を介して、ポリエステル系樹脂の層と、ガラスの層とが積層されてなることを特徴とする積層体。
　１３．前記１２に記載の積層体からなることを特徴とする窓ガラス。 That is, the present invention is as follows.
1. (A) Vinyl ester resin or unsaturated polyester resin 10 to 40% by mass
(B) Vinyl monomer and / or (meth) acrylate monomer 30 to 70% by mass
(C) modifying agent 5-40% by mass,
(However, the total of the components (a) to (c) is 100% by mass)
And (d) initiator An adhesive composition for adhering a polyester resin and glass, containing 0.1 to 15 parts by mass with respect to 100 parts by mass in total of the components (a) to (c).
2. 2. The adhesive composition according to 1 above, wherein the component (a) is an epoxy (meth) acrylate.
3. 3. The adhesive composition as described in 1 or 2 above, wherein the component (b) is a monomer having an N-vinyl group.
4). The component (c) is a polyol (c-1) having a hydroxyl value of 40 to 330 mgKOH / g; and a polyol (c-2) having a hydroxyl value of 40 to 330 mgKOH / g and an acid value of 2 to 20 mgKOH / g Modified rubber (c-3); at least one selected from the group consisting of compound (c-4) having an epoxy equivalent of 150 to 700 g / mol; The adhesive composition as described.
5. The component (c-1) is a castor oil-based polyol (c-1-1) having a hydroxyl value of 40 to 330 mgKOH / g; a polybutadiene-based polyol (c-1-2) having a hydroxyl value of 40 to 330 mgKOH / g; 5. The adhesive composition as described in 4 above, which is at least one selected from the group consisting of a polyisoprene-based polyol having a value of 40 to 330 mg KOH / g or a hydrogenated product thereof (c-1-3).
6). 6. The adhesive composition as described in 5 above, wherein the component (c-1) is an aromatic castor oil-based polyol (c-1-1-1) having a hydroxyl value of 40 to 330 mg KOH / g.
7). The component (c-2) is a castor oil-based polyol (c-2-1) having a hydroxyl value of 40 to 330 mgKOH / g and an acid value of 2 to 20 mgKOH / g. The adhesive composition described in 1.
8). 5. The adhesive composition as described in 4 above, wherein the component (c-3) is acid-modified polybutadiene or acid-modified polyisoprene.
9. 5. The adhesive composition as described in 4 above, wherein the component (c-4) is a polyepoxy compound (c-4-1) having an epoxy equivalent of 150 to 250 g / mol.
10. 5. The adhesive composition as described in 4 above, wherein the component (c-4) is a polymer (c-4-2) having a saturated skeleton having an epoxy equivalent of 500 to 700 g / mol.
11. 11. The adhesive composition as described in any one of 1 to 10 above, wherein the polyester resin is polyethylene terephthalate.
12 12. A laminate comprising a polyester resin layer and a glass layer laminated via the adhesive composition according to any one of 1 to 11 above.
13. A window glass comprising the laminate as described in 12 above.
　本発明の接着剤組成物は、前記成分（ａ）、（ｂ）、（ｃ）および（ｄ）を特定の量的関係でもって含有しているので、ポリエステル系樹脂とガラスとの間に優れた接着性を付与することができ、透明性、表面平滑性、柔軟性、耐衝撃性のバランスに優れる。また、揮発性有機化合物（ＶＯＣ）および臭気の発生の問題点や乾燥に長時間かかる等の問題点が解決できる。
　また本発明の積層体は、前記成分（ａ）、（ｂ）、（ｃ）および（ｄ）を特定の量的関係でもって含有する接着剤組成物を介して、ポリエステル系樹脂の層と、ガラスの層とが積層されてなることを特徴としているので、両層間の接着性に優れる。また、透明性、表面平滑性、柔軟性、耐衝撃性のバランスに優れる。
　また本発明の窓ガラスは、前記積層体からなることを特徴としているので、両層間の接着性に優れ、透明性、表面平滑性、柔軟性、耐衝撃性、耐水性、耐候性に優れる。 Since the adhesive composition of the present invention contains the components (a), (b), (c) and (d) in a specific quantitative relationship, it is excellent between the polyester resin and the glass. It has excellent balance of transparency, surface smoothness, flexibility and impact resistance. In addition, problems such as generation of volatile organic compounds (VOC) and odors and long time for drying can be solved.
The laminate of the present invention comprises a polyester resin layer through an adhesive composition containing the components (a), (b), (c) and (d) in a specific quantitative relationship, Since it is characterized by being laminated with a glass layer, it has excellent adhesion between both layers. Moreover, it is excellent in the balance of transparency, surface smoothness, flexibility and impact resistance.
Moreover, since the window glass of the present invention is characterized by comprising the laminate, it has excellent adhesion between both layers, and is excellent in transparency, surface smoothness, flexibility, impact resistance, water resistance, and weather resistance.
　以下、本発明をさらに詳細に説明する。
（ａ）ビニルエステル樹脂または不飽和ポリエステル樹脂
　本発明の接着剤組成物（以下、単に組成物ということがある）の成分（ａ）は、ビニルエステル樹脂または不飽和ポリエステル樹脂である。
　ビニルエステル樹脂として、具体的にはウレタン（メタ）アクリレート樹脂、エポキシ（メタ）アクリレート樹脂、ポリエステル（メタ）アクリレート樹脂から選択されるものであり、接着性に優れることからエポキシ（メタ）アクリレート樹脂が好ましい。なお本発明でいう（メタ）アクリレートとは、アクリレートまたはメタクリレートを指す。 Hereinafter, the present invention will be described in more detail.
(A) Vinyl ester resin or unsaturated polyester resin Component (a) of the adhesive composition of the present invention (hereinafter sometimes simply referred to as composition) is a vinyl ester resin or an unsaturated polyester resin.
Specifically, the vinyl ester resin is selected from urethane (meth) acrylate resin, epoxy (meth) acrylate resin, and polyester (meth) acrylate resin, and epoxy (meth) acrylate resin is excellent in adhesiveness. preferable. In addition, the (meth) acrylate referred to in the present invention refers to acrylate or methacrylate.
　かかるウレタン（メタ）アクリレート樹脂としては、好ましくはポリオール、ポリイソシアネートおよび１分子に１個以上の水酸基を有する（メタ）アクリレートの反応により得られるものであり、１分子中に２個以上の（メタ）アクリロイル基を有するものである。 Such urethane (meth) acrylate resin is preferably obtained by reaction of polyol, polyisocyanate and (meth) acrylate having one or more hydroxyl groups in one molecule, and two or more (meth) acrylates in one molecule. ) It has an acryloyl group.
　前記ウレタン（メタ）アクリレート樹脂に用いられるポリオールとしては、好ましくは数平均分子量が２００～３０００、特に好ましくは４００～２０００のものである。
　このポリオールは、代表的にはポリエーテルポリオール、ポリエステルポリオール、ポリカ－ボネ－トポリオール、ポリブタジエンポリオール等が挙げられ、単独または２種以上を併用して用いられる。 The polyol used in the urethane (meth) acrylate resin preferably has a number average molecular weight of 200 to 3000, particularly preferably 400 to 2000.
Typical examples of the polyol include polyether polyols, polyester polyols, polycarbonate polyols, polybutadiene polyols, and the like. These polyols are used alone or in combination of two or more.
　ここで言うポリエーテルポリオールとは、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等のポリアルキレンオキサイドの他に、ビスフェノールＡおよびビスフェノールＦに前記アルキレンオキサイドを付加させたポリオールも含むことができる。 As used herein, the polyether polyol may include a polyol obtained by adding the alkylene oxide to bisphenol A and bisphenol F, in addition to a polyalkylene oxide such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
　また、ポリエステルポリオールとは、二塩基酸類と多価アルコール類の縮合重合体またはポリカプロラクトンの様に環状エステル化合物の開環重合体である。ここで使用する二塩基酸類とは、例えば、フタル酸、無水フタル酸、ハロゲン化無水フタル酸、イソフタル酸、テレフタル酸、テトラヒドロフタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロフタル酸、ヘキサヒドロ無水フタル酸、ヘキサヒドロテレフタル酸、ヘキサヒドロイソフタル酸、コハク酸、マロン酸、グルタル酸、アジピン酸、セバシン酸、１，１２－ドデカンジカルボン酸、２，６－ナフタレンジカルボン酸、２，７－ナフタレンジカルボン酸、２，３－ナフタレンジカルボン酸、２，３－ナフタレンジカルボン酸無水物、４，４'－ビフェニルジカルボン酸、またこれらのジアルキルエステル等を挙げることができる。また、多価アルコール類とは、例えばエチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、ポリプロピレングリコール、２－メチル－１，３－プロパンジオール、１，３－ブタンジオール、ネオペンチルグリコール、水素化ビスフェノールＡ、１，４－ブタンジオール、１，６－ヘキサンジオール、ビスフェノールＡとプロピレンオキシドまたはエチレンオキシドの付加物、１，２，３，４－テトラヒドロキシブタン、グリセリン、トリメチロールプロパン、１，３－プロパンジオール、１，２－シクロヘキサングリコール、１，３－シクロヘキサングリコール、１，４－シクロヘキサングリコール、１，４－シクロヘキサンジメタノール、パラキシレングリコール、ビシクロヘキシル－４，４'－ジオール、２，６－デカリングリコール、２，７－デカリングリコール等を挙げることができる。 The polyester polyol is a condensation polymer of dibasic acids and polyhydric alcohols or a ring-opening polymer of a cyclic ester compound such as polycaprolactone. Dibasic acids used here are, for example, phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, Hexahydroterephthalic acid, hexahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2 , 3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid anhydride, 4,4′-biphenyldicarboxylic acid, and dialkyl esters thereof. Polyhydric alcohols include, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, 1,3 -Butanediol, neopentyl glycol, hydrogenated bisphenol A, 1,4-butanediol, 1,6-hexanediol, adducts of bisphenol A and propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, Glycerin, trimethylolpropane, 1,3-propanediol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, 1,4-cycl Hexane dimethanol, paraxylene glycol, bicyclohexyl-4,4'-diol, 2,6-decalin glycol, and 2,7-decalin glycol, and the like.
　前記ウレタン（メタ）アクリレート樹脂に用いられるポリイソシアネートとしては、２，４－ＴＤＩおよびその異性体または異性体の混合物、ＭＤＩ、ＨＤＩ、ＩＰＤＩ、ＸＤＩ、水添ＸＤＩ、ジシクロヘキシルメタンジイソシアネート、トリジンジイソシアネート、ナフタリンジイソシアネート、トリフェニルメタントリイソシアネート等を挙げることができ、それらの単独または２種以上で使用することができる。 Examples of the polyisocyanate used in the urethane (meth) acrylate resin include 2,4-TDI and its isomer or a mixture of isomers, MDI, HDI, IPDI, XDI, hydrogenated XDI, dicyclohexylmethane diisocyanate, tolidine diisocyanate, and naphthalene. A diisocyanate, a triphenylmethane triisocyanate, etc. can be mentioned, These can be used individually or in mixture of 2 or more types.
　前記ウレタン（メタ）アクリレート樹脂に用いられる１分子に１個以上の水酸基を有する（メタ）アクリレート（水酸基含有（メタ）アクリレート）としては、例えば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、３－ヒドロキシブチル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート等のモノ（メタ）アクリレート類、トリス（ヒドロキシエチル）イソシアヌル酸ジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート等の多価（メタ）アクリレート類等を挙げることができる。 Examples of the (meth) acrylate (hydroxyl group-containing (meth) acrylate) having one or more hydroxyl groups per molecule used in the urethane (meth) acrylate resin include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( Mono (meth) acrylates such as (meth) acrylate, 3-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, tris (hydroxyethyl) isocyanuric acid di (meth) acrylate, And polyvalent (meth) acrylates such as pentaerythritol tri (meth) acrylate.
　前記ウレタン（メタ）アクリレート樹脂の製造方法の例を挙げれば、（１）先ずポリイソシアネートとポリオールを好ましくはＮＣＯ／ＯＨ＝１．３～２で反応させ、末端イソシアネート化合物を生成させ、次いでそれに水酸基含有（メタ）アクリレートをイソシアネート基に対して水酸基がほぼ等量になるように反応する方法と、（２）ポリイソシアネート化合物と水酸基含有（メタ）アクリレートをＮＣＯ／ＯＨ＝２以上で反応させ、片末端イソシアネートの化合物を生成させ、次いでポリオールを加えて反応する方法等が挙げられる。 Examples of the method for producing the urethane (meth) acrylate resin include: (1) First, a polyisocyanate and a polyol are preferably reacted at NCO / OH = 1.3 to 2 to form a terminal isocyanate compound, and then a hydroxyl group is produced. A method of reacting the containing (meth) acrylate so that the hydroxyl groups are approximately equal to the isocyanate group, and (2) reacting the polyisocyanate compound and the hydroxyl-containing (meth) acrylate at NCO / OH = 2 or more, Examples include a method in which a compound of a terminal isocyanate is produced and then a polyol is added to react.
　また、ビニルエステル樹脂として用いられるエポキシ（メタ）アクリレート樹脂とは、好ましくは１分子中に２個以上の（メタ）アクリロイル基を有するもので、エポキシ樹脂と不飽和一塩基酸とをエステル化触媒の存在下で反応して得られるものである。 The epoxy (meth) acrylate resin used as the vinyl ester resin preferably has two or more (meth) acryloyl groups in one molecule, and is an esterification catalyst for epoxy resin and unsaturated monobasic acid. It is obtained by reacting in the presence of.
　ここでいうエポキシ樹脂の例を挙げれば、ビスフェノールタイプまたはノボラックタイプのエポキシ樹脂単独、または、ビスフェノールタイプとノボラックタイプのエポキシ樹脂とを混合した樹脂などであって、その平均エポキシ当量が好ましくは１５０～４５０の範囲のものである。 Examples of the epoxy resin mentioned here include a bisphenol type or novolac type epoxy resin alone, or a resin in which a bisphenol type and a novolac type epoxy resin are mixed, and the average epoxy equivalent is preferably 150 to It is in the range of 450.
　ここで、前記ビスフェノールタイプのエポキシ樹脂として代表的なものを挙げれば、エピクロルヒドリンとビスフェノールＡ若しくはビスフェノールＦとの反応により得られる実質的に１分子中に２個以上のエポキシ基を有するグリシジルエーテル型のエポキシ樹脂、メチルエピクロルヒドリンとビスフェノールＡ若しくはビスフェノールＦとの反応により得られるメチルグリシジルエーテル型のエポキシ樹脂、あるいはビスフェノールＡのアルキレンオキサイド付加物とエピクロルヒドリン若しくはメチルエピクロルヒドリンとから得られるエポキシ樹脂などである。また、前記ノボラックタイプのエポキシ樹脂として代表的なものには、フェノールノボラックまたはクレゾールノボラックと、エピクロルヒドリンまたはメチルエピクロルヒドリンとの反応により得られるエポキシ樹脂などがある。 Here, as a typical example of the bisphenol type epoxy resin, a glycidyl ether type epoxy resin substantially having two or more epoxy groups in one molecule obtained by the reaction of epichlorohydrin and bisphenol A or bisphenol F is used. An epoxy resin, a methyl glycidyl ether-type epoxy resin obtained by reaction of methyl epichlorohydrin and bisphenol A or bisphenol F, an epoxy resin obtained from an alkylene oxide adduct of bisphenol A and epichlorohydrin or methyl epichlorohydrin, or the like. Typical examples of the novolak type epoxy resin include an epoxy resin obtained by a reaction of phenol novolak or cresol novolak with epichlorohydrin or methyl epichlorohydrin.
　また、エポキシ（メタ）アクリレート樹脂に用いられる不飽和一塩基酸として代表的なものには、例えばアクリル酸、メタアクリル酸、桂皮酸、クロトン酸、マレイン酸モノメチル、マレイン酸モノプロピル、マレイン酸モノ（２－エチルヘキシル）あるいはソルビン酸などが挙げられる。なお、これらの不飽和一塩基酸は、単独でも、２種以上混合しても用いられる。前記エポキシ樹脂と不飽和一塩基酸との反応は、好ましくは６０～１４０℃、特に好ましくは８０～１２０℃の温度においてエステル化触媒を用いて行われる。 Typical examples of unsaturated monobasic acids used for epoxy (meth) acrylate resins include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, monomethyl maleate, monopropyl maleate, and monoester maleate. (2-ethylhexyl) or sorbic acid. These unsaturated monobasic acids may be used alone or in combination of two or more. The reaction between the epoxy resin and the unsaturated monobasic acid is preferably carried out using an esterification catalyst at a temperature of 60 to 140 ° C., particularly preferably 80 to 120 ° C.
　前記のエステル化触媒としては、たとえばトリエチルアミン、Ｎ，Ｎ－ジメチルベンジルアミン、Ｎ，Ｎ－ジメチルアニリン若しくはジアザビシクロオクタンなどの如き三級アミン、トリフェニルホスフィンあるいはジエチルアミン塩酸塩などの如き公知の触媒がそのまま使用できる。 As the esterification catalyst, known catalysts such as tertiary amines such as triethylamine, N, N-dimethylbenzylamine, N, N-dimethylaniline or diazabicyclooctane, triphenylphosphine or diethylamine hydrochloride Can be used as is.
　ビニルエステル樹脂として用いられるポリエステル（メタ）アクリレート樹脂とは、１分子中に２個以上の（メタ）アクリロイル基を有する飽和若しくは不飽和ポリエステルであり、飽和若しくは不飽和ポリエステルの末端に（メタ）アクリル化合物を反応させたものである。かかる樹脂の数平均分子量としては、好ましくは５００～５０００である。 The polyester (meth) acrylate resin used as the vinyl ester resin is a saturated or unsaturated polyester having two or more (meth) acryloyl groups in one molecule, and (meth) acrylic at the end of the saturated or unsaturated polyester. A compound is reacted. The number average molecular weight of such a resin is preferably 500 to 5,000.
　本発明で用いられる飽和ポリエステルとは、飽和二塩基酸類と多価アルコール類との縮合反応、また、不飽和ポリエステルとはα，β－不飽和二塩基酸を含む二塩基酸類と多価アルコール類との縮合反応で得られるものである。なお、不飽和ポリエステルの末端に（メタ）アクリル化合物を反応させた樹脂は、本発明においてはビニルエステル樹脂に含まれるものとし、下記で説明する不飽和ポリエステル樹脂とは区別されるものとする。 The saturated polyester used in the present invention is a condensation reaction between a saturated dibasic acid and a polyhydric alcohol, and the unsaturated polyester is a dibasic acid containing an α, β-unsaturated dibasic acid and a polyhydric alcohol. It is obtained by the condensation reaction. In addition, the resin which made the terminal of unsaturated polyester react with the (meth) acryl compound shall be contained in vinyl ester resin in this invention, and shall be distinguished from the unsaturated polyester resin demonstrated below.
　ここでいう飽和二塩基酸類とは、前記のポリエステルポリオールの項に示した化合物を挙げることができ、α，β－不飽和二塩基酸としては、マレイン酸、無水マレイン酸、フマル酸、イタコン酸、無水イタコン酸等を挙げることができる。また、多価アルコール類についても、前記のポリエステルポリオールの項に示した化合物を挙げることができる。 Examples of the saturated dibasic acid herein include the compounds shown in the above-mentioned polyester polyol, and examples of the α, β-unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, and itaconic acid. And itaconic anhydride. Moreover, the compound shown to the term of the said polyester polyol can be mentioned also about polyhydric alcohol.
　また、ビニルエステル樹脂として用いられるポリエステル（メタ）アクリレート樹脂の（メタ）アクリル化合物としては、不飽和グリシジル化合物、アクリル酸またはメタクリル酸の如き各種の不飽和一塩基酸、およびそのグリシジルエステル類等である。好ましくは、グリシジル（メタ）アクリレートの使用が望ましい。 The (meth) acrylic compound of the polyester (meth) acrylate resin used as the vinyl ester resin includes unsaturated glycidyl compounds, various unsaturated monobasic acids such as acrylic acid or methacrylic acid, and glycidyl esters thereof. is there. Preferably, glycidyl (meth) acrylate is used.
　不飽和ポリエステル樹脂とは、酸成分及びアルコール成分を公知の方法により重縮合させて得られるものであり、熱硬化性樹脂として知られているものであればその種類は特に限定されるものではない。酸成分としては、例えば無水マレイン酸、マレイン酸、フマル酸、イタコン酸等の不飽和二塩基酸が用いられる。また必要に応じてフタル酸、無水フタル酸、イソフタル酸、テレフタル酸、コハク酸、アジピン酸、セバチン酸等の飽和二塩基酸、安息香酸、トリメリット酸等の二塩基酸以外の酸等を用いることができる。アルコール成分としては、前記のポリエステルポリオールの項に示した多価アルコール類を挙げることができる。 The unsaturated polyester resin is obtained by polycondensing an acid component and an alcohol component by a known method, and the kind thereof is not particularly limited as long as it is known as a thermosetting resin. . As the acid component, for example, unsaturated dibasic acids such as maleic anhydride, maleic acid, fumaric acid and itaconic acid are used. If necessary, use a saturated dibasic acid such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, and sebacic acid, and acids other than dibasic acids such as benzoic acid and trimellitic acid. be able to. Examples of the alcohol component include polyhydric alcohols shown in the above-mentioned polyester polyol section.
成分（ｂ）ビニルモノマーおよび／または（メタ）アクリレートモノマー
　本発明の組成物の成分（ｂ）は、ビニルモノマーおよび／または（メタ）アクリレートモノマーである。具体的例としては、例えば、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（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、テトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリメチロールプロパントリオキシエチル（メタ）アクリレート、トリス（２－ヒドロキシエチル）イソシアヌレートトリ（メタ）アクリレート、トリス（２－ヒドロキシエチル）イソシアヌレートジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレートが挙げられる。 Component (b) Vinyl monomer and / or (meth) acrylate monomer Component (b) of the composition of the present invention is a vinyl monomer and / or (meth) acrylate monomer. Specific examples include, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tris (2-hydroxyethyl) ) Isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, and tricyclodecane dimethanol di (meth) acrylate.
　その他には、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、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、イソプロピル（メタ）アクリレート、ブチル（メタ）アクリレート、アミル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、イソアミル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、ラウリル（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、ブトキシエチル（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、ベンジル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、メトキシエチレングリコール（メタ）アクリレート、エトキシエトキシエチル（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、メトキシポリプロピレングリコール（メタ）アクリレート、ジシクロペンタジエン（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、トリシクロデカニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ボルニル（メタ）アクリレート、ジアセトン（メタ）アクリルアミド、イソブトキシメチル（メタ）アクリルアミド、Ｎ－ビニルピロリドン、Ｎ－ビニルカプロラクタム、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、ｔ－オクチル（メタ）アクリルアミド、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、７－アミノ－３，７－ジメチルオクチル（メタ）アクリレート、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド、Ｎ，Ｎ′－ジメチルアミノプロピル（メタ）アクリルアミド、（メタ）アクリロイルモルホリン、ビニルエーテル類である、ヒドロキシブチルビニルエーテル、ラウリルビニルエーテル、セチルビニルエーテル、２－エチルヘキシルビニルエーテルなどを挙げることができる。 Others include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) ) Acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) ) Acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isode (Meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) Acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, methoxypolyethylene glycol (Meth) acrylate, methoxypolypropylene glycol (meth) acrylate, dicyclopentadiene (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, diacetone (meth) acrylamide, iso Butoxymethyl (meth) acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, N, N-diethyl (meth) acrylamide, N, N'-dimethylaminopropyl (meth) acrylamide, (meth) acryloylmo Examples include ruphorin and vinyl ethers such as hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, and 2-ethylhexyl vinyl ether.
　本発明の組成物の成分（ｂ）ビニルモノマーおよび／または（メタ）アクリレートモノマーは、ポリエステル系樹脂とガラスとの接着性（以下、単に接着性ということがある）の点で好ましくは、環状構造および１個のエチレン性不飽和基を有する化合物（ｂ－１）、および、ジアクリレート化合物（ｂ－２）から選ばれる少なくとも1種のモノマーであり、該（ｂ－１）および（ｂ－２）を組み合わせて用いるのがさらに好ましい。 The component (b) vinyl monomer and / or (meth) acrylate monomer of the composition of the present invention is preferably a cyclic structure from the viewpoint of the adhesion between the polyester resin and the glass (hereinafter sometimes simply referred to as adhesion). And at least one monomer selected from a compound (b-1) having one ethylenically unsaturated group and a diacrylate compound (b-2), wherein (b-1) and (b-2) ) Are more preferably used in combination.
（ｂ－１）環状構造および１個のエチレン性不飽和基を有する化合物
　本発明で用いられる成分（ｂ－１）は、環状構造および１個のエチレン性不飽和基を有する化合物である。
　成分（ｂ）としては、例えば、イソボルニル（メタ）アクリレート、ボルニル（メタ）アクリレート、トリシクロデカニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート等の脂環式構造含有（メタ）アクリレート；ベンジル（メタ）アクリレート、４－ブチルシクロヘキシル（メタ）アクリレート、アクリロイルモルホリン、ビニルイミダゾール、ビニルピリジン等が挙げられる。
　さらに、下記式（１）～（３）で表される化合物を挙げることができる。 (B-1) Compound having a cyclic structure and one ethylenically unsaturated group Component (b-1) used in the present invention is a compound having a cyclic structure and one ethylenically unsaturated group.
Examples of the component (b) include alicyclic structure-containing (meth) acrylates such as isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and dicyclopentanyl (meth) acrylate; Examples include benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloylmorpholine, vinylimidazole, vinylpyridine and the like.
Furthermore, compounds represented by the following formulas (1) to (3) can be given.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
（式中、Ｒ2は水素原子またはメチル基を示し、Ｒ3は炭素数２～８、好ましくは２～５のアルキレン基を示し、Ｒ4は水素原子またはメチル基を示し、ｐは好ましくは１～４の数を示す。） (Wherein R 2 represents a hydrogen atom or a methyl group, R 3 represents an alkylene group having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms, R 4 represents a hydrogen atom or a methyl group, and p is preferably Shows the number from 1 to 4.)
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
（式中、Ｒ5、Ｒ6、Ｒ7およびＲ8は互いに独立で、ＨまたはＣＨ3であり、ｑは１～５の整数である） (Wherein R 5 , R 6 , R 7 and R 8 are independent of each other and are H or CH 3 , and q is an integer of 1 to 5)
　また、成分（ｂ）としては接着性に優れる点でＮ－ビニル基を有するモノマーが挙げられ、例えばＮ－ビニルピロリドン、Ｎ－ビニルカプロラクタム、Ｎ－ビニルホルムアミド、Ｎ－ビニルイミダゾール、Ｎ－ビニルカルバゾール等が挙げられる。その中でもＮ－ビニルカプロラクタムが接着性に優れる点で好ましい。 Examples of the component (b) include monomers having an N-vinyl group in terms of excellent adhesiveness. For example, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinylimidazole, N-vinylcarbazole Etc. Among these, N-vinylcaprolactam is preferable in terms of excellent adhesiveness.
　本発明で用いられる（ｂ－２）成分はジアクリレートモノマーである。
　本発明で用いられるジアクリレートモノマーとしては、エチレングリコールジアクリレート、ジプロピレングリコールジアクリレート（ＤＰＧＤＡ）、１,６－ヘキサンジオールジアクリレート（ＨＤＤＡ）、１,４－ブタンジオールジアクリレート、テトラエチレングリコールジアクリレート、トリプロピレングリコールジアクリレート（ＴＰＧＤＡ）、ＰＯ変性ネオペンチルグリコールジアクリレート、変性ビスフェノールＡジアクリレート等を挙げる事ができる。接着性の点において、ジプロピレングリコールジアクリレート、トリプロピレングリコールジアクリレートが好ましい。 The component (b-2) used in the present invention is a diacrylate monomer.
Examples of the diacrylate monomer used in the present invention include ethylene glycol diacrylate, dipropylene glycol diacrylate (DPGDA), 1,6-hexanediol diacrylate (HDDA), 1,4-butanediol diacrylate, and tetraethylene glycol diacrylate. Examples include acrylate, tripropylene glycol diacrylate (TPGDA), PO-modified neopentyl glycol diacrylate, and modified bisphenol A diacrylate. In terms of adhesiveness, dipropylene glycol diacrylate and tripropylene glycol diacrylate are preferred.
　該（ｂ－１）および（ｂ－２）を組み合わせて用いる場合、その配合割合は、（ｂ－１）＋（ｂ－２）＝１００質量部としたときに、（ｂ－１）は８０～２０質量部、好ましくは７５～２５質量部、（ｂ－２）は２０～８０質量部、好ましくは２５～７５質量部である。
　成分（ｂ）と成分（ｅ）を上記割合で併用する場合は透明性と接着性のバランスが優れる。 When (b-1) and (b-2) are used in combination, when the blending ratio is (b-1) + (b-2) = 100 parts by mass, (b-1) is 80 -20 parts by mass, preferably 75-25 parts by mass, and (b-2) is 20-80 parts by mass, preferably 25-75 parts by mass.
When the component (b) and the component (e) are used in the above proportion, the balance between transparency and adhesiveness is excellent.
（ｃ）変性剤
　本発明で用いられる成分（ｃ）は、変性剤である。
　成分（ｃ）変性剤は、本発明の組成物において接着性向上の機能を有する。
　変性剤（ｃ）としては、例えば水酸基価４０～３３０ｍｇＫＯＨ／ｇのポリオール（ｃ－１）；および水酸基価４０～３３０ｍｇＫＯＨ／ｇであり、かつ酸価が２～２０ｍｇＫＯＨ／ｇであるポリオール（ｃ－２）；変性ゴム（ｃ－３）；エポキシ当量が１５０～７００ｇ／モルである化合物（ｃ－４）からなる群から選択された少なくとも１種が挙げられる。 (C) Denaturant Component (c) used in the present invention is a denaturant.
The component (c) modifier has a function of improving adhesiveness in the composition of the present invention.
Examples of the modifier (c) include a polyol (c-1) having a hydroxyl value of 40 to 330 mgKOH / g; and a polyol (c-) having a hydroxyl value of 40 to 330 mgKOH / g and an acid value of 2 to 20 mgKOH / g. 2); modified rubber (c-3); at least one selected from the group consisting of compound (c-4) having an epoxy equivalent of 150 to 700 g / mol.
（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのポリオール（ｃ－１）について説明する。 (I) The polyol (c-1) having a hydroxyl value of 40 to 330 mgKOH / g will be described.
　成分（ｃ）の水酸基価は、ポリエステル系樹脂とガラスとの選択的な接着性の向上に寄与する。以下、ポリエステル系樹脂およびガラスを総称して「被着体」と称することがある。 The hydroxyl value of component (c) contributes to the selective improvement of the adhesion between the polyester resin and the glass. Hereinafter, the polyester resin and the glass may be collectively referred to as “adhered body”.
　また、（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのポリオール（ｃ－１）としては、芳香族系、脂肪族系、ポリブタジエン系、ヒマシ油系、ポリイソプレン系等が挙げられるが水酸基価が上記範囲であればいずれのタイプであっても被着体に対する選択的な接着性は良好である。
　（ｉ）水酸基価は４０～３３０ｍｇＫＯＨ／ｇであるのが上記接着性の観点から好ましく、１５０～３００ｍｇＫＯＨ／ｇであるのがさらに好ましい。 The (i) polyol (c-1) having a hydroxyl value of 40 to 330 mgKOH / g includes aromatic, aliphatic, polybutadiene, castor oil, polyisoprene, and the like. As long as it is any type, the selective adhesiveness to the adherend is good.
(I) The hydroxyl value is preferably 40 to 330 mgKOH / g from the viewpoint of adhesiveness, and more preferably 150 to 300 mgKOH / g.
　（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのポリオール（ｃ－１）として、被着体に対する選択的な接着性の点でさらに好ましくは、
（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのヒマシ油系ポリオール（ｃ－１－１）
（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのポリブタジエン系ポリオール（ｃ－１－２）
（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのポリイソプレン系ポリオールまたはその水素添加物（ｃ－１－３）
（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのエポキシポリオール樹脂（ｃ－１－４）
が挙げられる。 (I) As a polyol (c-1) having a hydroxyl value of 40 to 330 mgKOH / g, it is more preferable in terms of selective adhesiveness to an adherend.
(I) Castor oil-based polyol (c-1-1) having a hydroxyl value of 40 to 330 mgKOH / g
(I) Polybutadiene-based polyol (c-1-2) having a hydroxyl value of 40 to 330 mgKOH / g
(I) Polyisoprene polyol having a hydroxyl value of 40 to 330 mgKOH / g or a hydrogenated product thereof (c-1-3)
(I) Epoxy polyol resin (c-1-4) having a hydroxyl value of 40 to 330 mgKOH / g
Is mentioned.
　本発明においては、成分（ｃ）のポリオールは必要に応じて２種類以上を混合して用いることができる。 In the present invention, the polyol of component (c) can be used as a mixture of two or more if necessary.
　（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのヒマシ油系ポリオール（ｃ－１－１）について説明する。 (I) A castor oil-based polyol (c-1-1) having a hydroxyl value of 40 to 330 mgKOH / g will be described.
　前記「ヒマシ油」は、リシノレイン酸とグリセリンとのトリエステル化合物を含む油脂である。通常、天然油脂又は天然油脂加工物であるが、上記化合物を含めば合成油脂であってもよい。このヒマシ油に含まれるトリエステル化合物を構成するリシノレイン酸は、トリエステル化合物全体を構成する脂肪酸のうちの９０モル％以上含有されることが好ましい。また、このヒマシ油は、水素添加物（通常、リシノレイン酸骨格中の炭素間不飽和結合に対する水添）等の加工品であってもよい。通常、ヒマシ油には、上記トリエステル化合物（水添物である場合には、上記トリエステル化合物の水添物）が、油脂全体の９０モル％以上（１００モル％を含む）含有される。 The “castor oil” is an oil containing a triester compound of ricinoleic acid and glycerin. Usually, it is a natural fat or oil or a processed natural fat or oil, but it may be a synthetic fat or oil if it contains the above compounds. The ricinoleic acid constituting the triester compound contained in this castor oil is preferably contained in an amount of 90 mol% or more of the fatty acids constituting the whole triester compound. Further, the castor oil may be a processed product such as a hydrogenated product (usually hydrogenated to an intercarbon unsaturated bond in the ricinoleic acid skeleton). Usually, castor oil contains 90 mol% or more (including 100 mol%) of the above-described triester compound (in the case of a hydrogenated product, a hydrogenated product of the triester compound).
　前記「ヒマシ油系ポリオール」は、リシノレイン酸及び／又は水添リシノレイン酸と多価アルコールとのエステル化合物である。この構成を有すればヒマシ油を出発原料して得られたポリオールであっても、ヒマシ油以外の原料を出発原料として得られたポリオールであってもよい。この多価アルコールは特に限定されない。 The “castor oil-based polyol” is an ester compound of ricinoleic acid and / or hydrogenated ricinoleic acid and a polyhydric alcohol. If it has this structure, it may be a polyol obtained by using castor oil as a starting material, or a polyol obtained by using a raw material other than castor oil as a starting material. This polyhydric alcohol is not particularly limited.
　ヒマシ油系ポリオールとしては、ヒマシ油より誘導されるポリオール、ヒマシ油を変性して得られるポリオールが挙げられる。 Castor oil-based polyols include polyols derived from castor oil and polyols obtained by modifying castor oil.
　ヒマシ油より誘導されるポリオールとは、このグリセリンエステルのリシノレイン酸の一部をオレイン酸に置換したもの、ヒマシ油を鹸化して得られるリシノレイン酸をトリメチロールプロパンその他の短分子ポリオールとエステル化したもの、これらとヒマシ油との混合物等、ヒマシ油由来の脂肪酸エステル系ポリオールである。 The polyol derived from castor oil is a glycerin ester in which part of the ricinoleic acid is replaced with oleic acid, and ricinoleic acid obtained by saponifying castor oil is esterified with trimethylolpropane or other short molecular polyols. These are fatty acid ester polyols derived from castor oil, such as a mixture of these and castor oil.
　ヒマシ油を変性して得られるポリオールとしては、例えば植物油変性ポリオール、芳香族骨格（例えばビスフェノールＡ等）を有する変性ポリオール等が挙げられる。植物油変性ポリオールは、グリセリンエステルのリシノレイン酸の一部を、他の植物より得られる脂肪酸、例えば大豆油、なたね油、オリーブ油等より得られるリノール酸、リノレン酸、オレイン酸等の高級脂肪酸に置換して得られるものである。 Examples of polyols obtained by modifying castor oil include vegetable oil-modified polyols and modified polyols having an aromatic skeleton (such as bisphenol A). A vegetable oil-modified polyol is obtained by replacing a part of glycerin ester ricinoleic acid with a fatty acid obtained from other plants, for example, higher fatty acids such as linoleic acid, linolenic acid, oleic acid obtained from soybean oil, rapeseed oil, olive oil, etc. It is obtained.
　ヒマシ油系ポリオールの中でも、本発明の効果の点から、前記成分（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのヒマシ油系ポリオール（ｃ－１－１）が好ましい。
　さらに、接着性を向上させる点で（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇの芳香族系ヒマシ油系ポリオール（ｃ－１－１－１）が好ましい。より好ましくは、１５０～２４０ｍｇＫＯＨ／ｇである。 Among the castor oil-based polyols, castor oil-based polyol (c-1-1) having a component (i) hydroxyl value of 40 to 330 mgKOH / g is preferable from the viewpoint of the effect of the present invention.
Further, (i) an aromatic castor oil-based polyol (c-1-1-1) having a hydroxyl value of 40 to 330 mgKOH / g is preferable in terms of improving adhesiveness. More preferably, it is 150 to 240 mg KOH / g.
　前記成分（ｃ－１－１－１）は、芳香族骨格（例えばビスフェノールＡ等）を有する、ヒマシ油から誘導された変性ポリオールである。当該成分（ｃ－１－１－１）は、市販されており、例えば「ＵＲＩＣ  ＡＣシリーズ」（伊藤製油（株））等が挙げられる。中でも、リシノレイン酸にポリアルキレングリコールとビスフェノールＡを付加させた付加物が、接着性を高める点から好ましく、例えば、次の式（４）で表すことができる。 The component (c-1-1-1) is a modified polyol derived from castor oil having an aromatic skeleton (for example, bisphenol A). The component (c-1-1-1) is commercially available, and examples thereof include “URIC AC series” (Ito Oil Co., Ltd.). Among these, an adduct obtained by adding polyalkylene glycol and bisphenol A to ricinoleic acid is preferable from the viewpoint of improving adhesiveness, and can be represented by, for example, the following formula (4).
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　式（４）中、ｍは平均２～５の数を表し、ｎは平均２～５の数を表す。 In the formula (4), m represents an average number of 2 to 5, and n represents an average number of 2 to 5.
　前記式（４）で表されるヒマシ油から誘導された変性ポリオールは、例えば商品名ＵＲＩＣ　ＡＣ―００５（水酸基価１９４～２１４ｍｇＫＯＨ／ｍｇ、粘度７００～１５００ｍＰａ・ｓ／２５℃）、ＡＣ－００６（水酸基価１６８～１８７ｍｇＫＯＨ／ｍｇ、粘度３０００～５０００ｍＰａ・ｓ／２５℃）、ＡＣ－００８（水酸基価１８０ｍｇＫＯＨ／ｍｇ、粘度１６００ｍＰａ・ｓ／２５℃）、ＡＣ－００９（水酸基価２２５ｍｇＫＯＨ／ｍｇ、粘度１５００ｍＰａ・ｓ／２５℃）として伊藤製油（株）から入手できる。 Modified polyols derived from castor oil represented by the formula (4) are, for example, trade names URIC AC-005 (hydroxyl value 194 to 214 mgKOH / mg, viscosity 700 to 1500 mPa · s / 25 ° C.), AC-006 ( Hydroxyl value 168 to 187 mgKOH / mg, viscosity 3000 to 5000 mPa · s / 25 ° C., AC-008 (hydroxyl value 180 mgKOH / mg, viscosity 1600 mPa · s / 25 ° C.), AC-009 (hydroxyl value 225 mgKOH / mg, viscosity 1500 mPa -It can obtain from Ito Oil Co., Ltd. as s / 25 degreeC.
　（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのポリブタジエン系ポリオール（ｃ－１－２）について説明する。 (I) A polybutadiene-based polyol (c-1-2) having a hydroxyl value of 40 to 330 mgKOH / g will be described.
　本発明で使用されるポリブタジエン系ポリオールとしては、例えば、１，２－ポリブタジエンポリオール、１，４－ポリブタジエンポリオール等のホモポリマー、ポリ（ペンタジエン・ブタジエン）ポリオール、ポリ（ブタジエン・スチレン）ポリオール、ポリ（ブタジエン・アクリロニトリル）ポリオール等のコポリマー、それらポリオールに水素を付加した水素添加ポリブタジエン系ポリオールが挙げられる。
　ポリブタジエン系ポリオールは市販されており、例えば、出光興産（株）製の「Ｐｏｌｙ ｂｄ Ｒ－１５ＨＴ（水酸基価１０２．７ｍｇＫＯＨ／ｍｇ、Ｍｗ１２００）」、「Ｐｏｌｙ ｂｄ Ｒ－４５ＨＴ（水酸基価４６．６ｍｇＫＯＨ／ｍｇ、Ｍｗ２８００）」等が挙げられる。
　また、本発明の効果の点から（ｃ－１－２）ポリブタジエン系ポリオールの水酸基価は４０～３３０ｍｇＫＯＨ／ｇであるのが好ましく、４０～１１０ｍｇＫＯＨ／ｇであるのがさらに好ましい。
　（ｃ－１－２）ポリブタジエン系ポリオールの重量平均分子量（ＧＰＣ法）は、５０～３０００であるのが好ましく、８００～１５００であるのがさらに好ましい。 Examples of the polybutadiene-based polyol used in the present invention include homopolymers such as 1,2-polybutadiene polyol and 1,4-polybutadiene polyol, poly (pentadiene-butadiene) polyol, poly (butadiene-styrene) polyol, poly ( Examples thereof include copolymers such as butadiene / acrylonitrile) polyols, and hydrogenated polybutadiene-based polyols obtained by adding hydrogen to these polyols.
Polybutadiene-based polyols are commercially available. For example, “Poly bd R-15HT (hydroxyl value 102.7 mgKOH / mg, Mw1200)” and “Poly bd R-45HT (hydroxyl value 46.6 mgKOH / manufactured by Idemitsu Kosan Co., Ltd.) are available. mg, Mw2800) "and the like.
In view of the effects of the present invention, the hydroxyl value of the (c-1-2) polybutadiene-based polyol is preferably 40 to 330 mgKOH / g, more preferably 40 to 110 mgKOH / g.
(C-1-2) The weight average molecular weight (GPC method) of the polybutadiene-based polyol is preferably 50 to 3000, and more preferably 800 to 1500.
（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのポリイソプレン系ポリオールまたはその水素添加物（ｃ－１－３）について説明する。 (I) A polyisoprene-based polyol having a hydroxyl value of 40 to 330 mgKOH / g or a hydrogenated product thereof (c-1-3) will be described.
　このような成分（ｃ－１－３）としては、例えば出光社のPoly ip（登録商標）（水酸基末端液状ポリイソプレン）が挙げられる。「Poly ip（登録商標）」（水酸基価４６．６ｍｇＫＯＨ／ｍｇ、Ｍｎ２５００）は、分子末端に反応性の高い水酸基を備えたポリイソプレンタイプの液状ポリマーである。
　水素添加物としては、出光社のエポール（登録商標）（水酸基末端液状ポリオレフィン）が挙げられる。「エポール（登録商標）」（水酸基価５０．５ｍｇＫＯＨ／ｍｇ、Ｍｎ２５００）は、「Poly ip（登録商標）」に水添して得られる液状のポリオレフィンである。分子内に二重結合はほとんど残っていない。 Examples of such component (c-1-3) include Polyip (registered trademark) (hydroxyl-terminated liquid polyisoprene) manufactured by Idemitsu. “Poly ip (registered trademark)” (hydroxyl value 46.6 mg KOH / mg, Mn 2500) is a polyisoprene type liquid polymer having a highly reactive hydroxyl group at the molecular end.
An example of the hydrogenated product is Epole (registered trademark) (hydroxyl-terminated liquid polyolefin) manufactured by Idemitsu. “Epol®” (hydroxyl value 50.5 mg KOH / mg, Mn 2500) is a liquid polyolefin obtained by hydrogenating “Poly ip®”. Almost no double bonds remain in the molecule.
（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのエポキシポリオール樹脂（ｃ－１－４）について説明する。 (I) The epoxy polyol resin (c-1-4) having a hydroxyl value of 40 to 330 mgKOH / g will be described.
　本発明において使用される（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのエポキシポリオール樹脂（ｃ－１－４）は、エポキシ樹脂に活性水素化合物を反応させて得られるものである。 (I) The epoxy polyol resin (c-1-4) having a hydroxyl value of 40 to 330 mgKOH / g used in the present invention is obtained by reacting an epoxy resin with an active hydrogen compound.
　ここで使用されるエポキシ樹脂としては、例えば、ハイドロキノン、レゾルシン、ピロカテコール、フロログルシノール等の単核多価フェノール化合物のポリグリシジルエーテル化合物；ジヒドロキシナフタレン、ビフェノール、メチレンビスフェノール（ビスフェノールＦ）、メチレンビス（オルトクレゾール）、エチリデンビスフェノール、イソプロピリデンビスフェノール（ビスフェノールＡ）、イソプロピリデンビス（オルトクレゾール）、テトラブロモビスフェノールＡ、１，３－ビス（４－ヒドロキシクミルベンゼン）、１，４－ビス（４－ヒドロキシクミルベンゼン）、１，１，３－トリス（４－ヒドロキシフェニル）ブタン、１，１，２，２－テトラ（４－ヒドロキシフェニル）エタン、チオビスフェノール、スルホビスフェノール、オキシビスフェノール、フェノールノボラック、オルソクレゾールノボラック、エチルフェノールノボラック、ブチルフェノールノボラック、オクチルフェノールノボラック、レゾルシンノボラック、ビスフェノールＡノボラック、ビスフェノールＦノボラック、テルペンジフェノール等の多核多価フェノール化合物のポリグリジルエーテル化合物；上記単核多価フェノール化合物あるいは多核多価フェノール化合物のエチレンオキシド及び／又はプロピレンオキシド付加物のポリグリシジルエーテル化合物；上記単核多価フェノール化合物の水添物のポリグリシジルエーテル化合物；エチレングリコール、プロピレングリコール、ブチレングリコール、ヘキサンジオール、ポリグリコール、チオジグリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、ソルビトール、ビスフェノールＡ－エチレンオキシド付加物等の多価アルコール類のポリグリシジルエーテル；マレイン酸、フマル酸、イタコン酸、コハク酸、グルタル酸、スベリン酸、アジピン酸、アゼライン酸、セバシン酸、ダイマー酸、トリマー酸、フタル酸、イソフタル酸、テレフタル酸、トリメリット酸、トリメシン酸、ピロメリット酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、エンドメチレンテトラヒドロフタル酸等の脂肪族、芳香族又は脂環族多塩基酸のグリシジルエステル類及びグリシジルメタクリレートの単独重合体又は共重合体；Ｎ，Ｎ－ジグリシジルアニリン、ビス（４－（Ｎ－メチル－Ｎ－グリシジルアミノ）フェニル）メタン等のグリシジルアミノ基を有するエポキシ化合物；ビニルシクロヘキセンジエポキシド、ジシクロペンタンジエンジエポキサイド、３，４－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、３，４－エポキシ－６－メチルシクロヘキシルメチル－６－メチルシクロヘキサンカルボキシレート、ビス（３，４－エポキシ－６－メチルシクロヘキシルメチル）アジペート等の環状オレフィン化合物のエポキシ化物；エポキシ化ポリブタジエン、エポキシ化スチレン－ブタジエン共重合物等のエポキシ化共役ジエン重合体、トリグリシジルイソシアヌレート等の複素環化合物が挙げられる。また、これらのエポキシ樹脂は、末端イソシアネートのプレポリマーによって内部架橋されたものでもよい。 Examples of the epoxy resin used here include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis ( Orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4- Hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobis Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as enol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, bisphenol A novolak, bisphenol F novolak, terpene diphenol; Polyglycidyl ether compound of ethylene oxide and / or propylene oxide adduct of the above mononuclear polyhydric phenol compound or polynuclear polyphenol compound; polyglycidyl ether compound of hydrogenated mononuclear polyhydric phenol compound; ethylene glycol, propylene glycol , Butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, Polyglycidyl ethers of polyhydric alcohols such as methylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacin Acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, aliphatic such as endomethylenetetrahydrophthalic acid, aromatic or Homopolymers or copolymers of glycidyl esters of alicyclic polybasic acids and glycidyl methacrylate; glycidyl such as N, N-diglycidylaniline, bis (4- (N-methyl-N-glycidylamino) phenyl) methane Has an amino group Epoxy compounds; vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxy Epoxidized products of cyclic olefin compounds such as bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymer, triglycidyl isocyanate And heterocyclic compounds such as nurate. In addition, these epoxy resins may be internally crosslinked by a prepolymer of terminal isocyanate.
　これらのエポキシ樹脂の中でも、ビフェノール、メチレンビスフェノール（ビスフェノールＦ）、メチレンビス（オルトクレゾール）、エチリデンビスフェノール（ビスフェノールＡＤ）、イソプロピリデンビスフェノール（ビスフェノールＡ）、イソプロピリデンビス（オルトクレゾール）、テトラブロモビスフェノールＡ、１，３－ビス（４－ヒドロキシクミルベンゼン）、１，４－ビス（４－ヒドロキシクミルベンゼン）等のポリグリシジルエーテル化合物等のビスフェノール型エポキシ樹脂を使用すると、接着性が高めるため好ましい。 Among these epoxy resins, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol (bisphenol AD), isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, Use of a bisphenol type epoxy resin such as a polyglycidyl ether compound such as 1,3-bis (4-hydroxycumylbenzene) and 1,4-bis (4-hydroxycumylbenzene) is preferable because of improving adhesiveness.
（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのエポキシポリオール樹脂（ｃ－１－４）は、上記エポキシ樹脂のエポキシ基と、カルボン酸化合物、ポリオール、アミノ化合物等の活性水素化合物とを反応して得られるものである。 (I) An epoxy polyol resin (c-1-4) having a hydroxyl value of 40 to 330 mgKOH / g is obtained by reacting an epoxy group of the epoxy resin with an active hydrogen compound such as a carboxylic acid compound, a polyol or an amino compound. It is what
　上記カルボン酸化合物としては、酢酸、プロピオン酸、２，２－ジメチロールプロピオン酸、１２－ヒドロキシステアリン酸、乳酸、酪酸、オクチル酸、リシノール酸、ラウリン酸、安息香酸、トルイル酸、桂皮酸、フェニル酢酸、シクロヘキサンカルボン酸等の脂肪族、芳香族又は脂環式モノカルボン酸、マレイン酸、フマル酸、イタコン酸、コハク酸、グルタル酸、アジピン酸、ダイマー酸、フタル酸、イソフタル酸、テレフタル酸、ヘキサヒドロ酸、ヒドロキシポリカルボン酸等が挙げられる。 Examples of the carboxylic acid compound include acetic acid, propionic acid, 2,2-dimethylolpropionic acid, 12-hydroxystearic acid, lactic acid, butyric acid, octylic acid, ricinoleic acid, lauric acid, benzoic acid, toluic acid, cinnamic acid, phenyl Aliphatic, aromatic or cycloaliphatic monocarboxylic acids such as acetic acid and cyclohexanecarboxylic acid, maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, adipic acid, dimer acid, phthalic acid, isophthalic acid, terephthalic acid, Examples include hexahydro acid and hydroxypolycarboxylic acid.
　上記ポリオールとしては、例えば、エチレングリコール、ジエチレングリコール、１，２－プロピレングリコール、１，３－プロピレングリコール、２－メチル－１，３－プロピレングリコール、２，２－ジメチル－１，３－プロピレングリコール、１，２－ブタンジオール、１，３－ブタンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、２，２，４－トリメチル－１，５－ペンタンジオール、１，６－ヘキサンジオール、２－エチル－１，６－ヘキサンジオール、１，２－オクタンジオール、１，８－オクタンジオール、２－メチル－１，８－オクタンジオール、１，９－ノナンジオール、１，１０－デカンジオール、１，１２－オクタデカンジオール、グリセリン、トリメチロールプロパン、ペンタエリスリトール等の低分子ポリオールが挙げられる。 Examples of the polyol include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2-methyl-1,3-propylene glycol, 2,2-dimethyl-1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2,4-trimethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 1,2-octanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol, glycerin, trimethylolpropane, pentaerythritol Like low molecular weight polyols is.
上記アミノ化合物としては、ジブチルアミン、ジオクチルアミン等のジアルキルアミン化合物；メチルエタノールアミン、ブチルエタノールアミン、ジエタノールアミン、ジイソプロパノールアミン、ジメチルアミノプロピルエタノールアミン等のアルカノールアミン化合物；モルホリン、ピペリジン、４－メチルピペラジン等の複素環式アミン化合物が挙げられる。 Examples of the amino compounds include dialkylamine compounds such as dibutylamine and dioctylamine; alkanolamine compounds such as methylethanolamine, butylethanolamine, diethanolamine, diisopropanolamine, and dimethylaminopropylethanolamine; morpholine, piperidine, 4-methylpiperazine And heterocyclic amine compounds such as
　上記活性水素化合物の中でも、ジエタノールアミン等のアルカノールアミン化合物が好ましい。 Among the above active hydrogen compounds, alkanolamine compounds such as diethanolamine are preferable.
　また、モノエタノールアミン、モノイソプロパノールアミン等の活性水素基を２個以上有する化合物で、エポキシ樹脂を鎖延長することもできる。 Also, the epoxy resin can be chain-extended with a compound having two or more active hydrogen groups such as monoethanolamine and monoisopropanolamine.
　上記エポキシ樹脂に上記活性水素化合物を反応させる際には、エポキシ樹脂に活性水素化合物を付加させる通常の方法を採用することができ、例えば、三級アミン化合物、ホスホニウム塩等の周知の触媒の存在下に、両者を６０～２００℃に加熱し、３～１０時間反応させる方法を用いることができる。 When the active hydrogen compound is reacted with the epoxy resin, a normal method of adding the active hydrogen compound to the epoxy resin can be employed. For example, the presence of a known catalyst such as a tertiary amine compound or a phosphonium salt. Below, a method in which both are heated to 60 to 200 ° C. and reacted for 3 to 10 hours can be used.
（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのエポキシポリオール樹脂（ｃ－１－４）の好ましい水酸基価は本発明の効果の点から１００～１４０ｍｇＫＯＨ／ｇである。 (I) A preferable hydroxyl value of the epoxy polyol resin (c-1-4) having a hydroxyl value of 40 to 330 mgKOH / g is 100 to 140 mgKOH / g from the viewpoint of the effect of the present invention.
　上記（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのエポキシポリオール樹脂（ｃ－１－４）の例としてはＤＩＣ株式会社製ＥＰＩＣＬＯＮ　Ｕ－１２５－６０ＢＴ（水酸基価１００～１４０ｍｇＫＯＨ／ｇ）が挙げられる。 Examples of the epoxy polyol resin (c-1-4) having (i) a hydroxyl value of 40 to 330 mgKOH / g include EPICLON U-125-60BT (hydroxyl value 100 to 140 mgKOH / g) manufactured by DIC Corporation.
　（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇであり、かつ(ii)酸価が２～２０ｍｇＫＯＨ／ｇであるポリオール（ｃ－２）について説明する。 (I) A polyol (c-2) having a hydroxyl value of 40 to 330 mgKOH / g and (ii) an acid value of 2 to 20 mgKOH / g will be described.
　（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇであり、かつ(ii)酸価が２～２０ｍｇＫＯＨ／ｇであるポリオール（ｃ－２）としては、芳香族系、脂肪族系、あるいはヒマシ油系であっても(i)の水酸基価、(ii)の酸価を満たすことにより接着性が向上する。
　（ｉ）の水酸基価は、２３０～３００ｍｇＫＯＨ／ｇであるのがさらに好ましい。
　(ii)の酸価は、４～１５ｍｇＫＯＨ／ｇであるのがさらに好ましい。 The polyol (c-2) having a hydroxyl value of 40 to 330 mg KOH / g and (ii) an acid value of 2 to 20 mg KOH / g is aromatic, aliphatic or castor oil-based. However, the adhesiveness is improved by satisfying the hydroxyl value of (i) and the acid value of (ii).
The hydroxyl value of (i) is more preferably 230 to 300 mgKOH / g.
The acid value of (ii) is more preferably 4 to 15 mg KOH / g.
　（ｉ）かつ(ii)を満たす場合は、
　（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇであり、かつ(ii)酸価が２～２０ｍｇＫＯＨ／ｇであるポリオール（ｃ－２）としては、
（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇであり、かつ(ii)酸価が２～２０ｍｇＫＯＨ／ｇであるヒマシ油系ポリオール（ｃ－２－１）
が例示される。 If (i) and (ii) are satisfied,
As the polyol (c-2) having a hydroxyl value of 40 to 330 mgKOH / g and (ii) an acid value of 2 to 20 mgKOH / g,
(I) a castor oil-based polyol (c-2-1) having a hydroxyl value of 40 to 330 mgKOH / g and (ii) an acid value of 2 to 20 mgKOH / g
Is exemplified.
　（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇであり、かつ(ii)酸価が２～２０ｍｇＫＯＨ／ｇであるヒマシ油系ポリオール（ｃ－２－１）は、ヒマシ油由来のポリオールであり、例えば、特開２００５－８９７１２号公報に開示されているように、リシノレイン酸から誘導されたヒマシ油系ポリオールと、全炭素数が１２以上の酸性リン酸エステル化合物と、必要に応じてテルペンフェノール類を含有するポリオール組成物も使用することができる。これらは例えば商品名ＵＲＩＣ　Ｈ－１２６２、Ｈ２１５１Ｕとして伊藤製油（株）から入手できる。 (I) A castor oil-based polyol (c-2-1) having a hydroxyl value of 40 to 330 mg KOH / g and (ii) an acid value of 2 to 20 mg KOH / g is a polyol derived from castor oil. As disclosed in JP-A-2005-89712, it contains a castor oil-based polyol derived from ricinoleic acid, an acidic phosphate ester compound having a total carbon number of 12 or more, and, if necessary, terpene phenols Polyol compositions can also be used. These can be obtained from Ito Refinery under the trade names URIC H-1262 and H2151U, for example.
　上記伊藤製油　ＵＲＩＣ　Ｈ－１２６２は、ヒマシ油系ポリオールと全炭素数が１２以上の酸性リン酸エステル化合物を含むポリオール（粘度：３，５００～８，５００ｍＰａ・ｓ／２５℃、水酸基価：２４０～２９０（単位ｍｇＫＯＨ／ｇ）、酸価：４～１５（単位ｍｇＫＯＨ／ｇ））であり、接着性、耐加水分解性に優れる。
　また、上記伊藤製油　ＵＲＩＣ　Ｈ－２１５１Ｕは、ヒマシ油系ポリオールと全炭素数が１２以上の酸性リン酸エステル化合物とテルペンフェノール類を含有するポリオール　（粘度：３，５００～８，５００ｍＰａ・ｓ／２５℃、水酸基価：２４０～２９０（単位ｍｇＫＯＨ／ｇ）、酸価：４～１５（単位ｍｇＫＯＨ／ｇ））であり、接着性、耐加水分解性に優れる。 The Ito Oil URIC H-1262 is a polyol containing a castor oil-based polyol and an acidic phosphate ester compound having a total carbon number of 12 or more (viscosity: 3,500 to 8,500 mPa · s / 25 ° C., hydroxyl value: 240 to 290 (unit mgKOH / g), acid value: 4 to 15 (unit mgKOH / g)), and excellent in adhesion and hydrolysis resistance.
The Ito Oil URIC H-2151U is a polyol containing a castor oil-based polyol, an acidic phosphate compound having a total carbon number of 12 or more, and a terpene phenol (viscosity: 3,500 to 8,500 mPa · s / 25). ° C, hydroxyl value: 240 to 290 (unit mgKOH / g), acid value: 4 to 15 (unit mgKOH / g)), and excellent in adhesion and hydrolysis resistance.
　変性ゴム（ｃ－３）について説明する。
　本発明で使用される変性ゴム（ｃ－３）としては、（ｃ－３－１）液状のカルボキシル化ポリイソプレン及び（ｃ－３－２）カルボキシル化ポリブタジエンが挙げられる。 The modified rubber (c-3) will be described.
Examples of the modified rubber (c-3) used in the present invention include (c-3-1) liquid carboxylated polyisoprene and (c-3-2) carboxylated polybutadiene.
（ｃ－３－１）カルボキシル化ポリイソプレン
　本発明で使用されるカルボキシル化ポリイソプレン（ｃ－３－１）は、本発明の組成物を被着体と接着させる際に、主として被着体表面のぬれ性を向上させ、接着性を向上させる機能を果たす。
　成分（ｃ－３－１）としては、例えばマレイン化ポリイソプレンとしてクラレ社製のＬＩＲ－４２０が挙げられる。 (C-3-1) Carboxylated polyisoprene The carboxylated polyisoprene (c-3-1) used in the present invention is mainly used when adhering the composition of the present invention to an adherend. Improves wettability and improves the adhesion.
Examples of the component (c-3-1) include LIR-420 manufactured by Kuraray as maleated polyisoprene.
（ｃ－３－２）カルボキシル化ポリブタジエン
　本発明で使用されるカルボキシル化ポリブタジエン（ｃ）は、接着性を向上させる機能を果たす。
　成分（ｃ－３－２）は、ポリブタジエンにおける主鎖のミクロ構造がビニル１，２－結合型、トランス１，４－結合型、シス１，４－結合型からなる、室温において透明な液状の重合体である。ここで、ビニル１，２－結合は３０重量％以下であることが好ましく、ビニル１，２－結合が３０重量％を超えては、得られる組成物の貯蔵安定性が悪化するため好ましくない。また、シス１，４－結合は、４０重量％以上であることが好ましく、シス１，４－結合が４０重量％未満では、得られる組成物の接着性が低下するため好ましくない。 (C-3-2) Carboxylated polybutadiene The carboxylated polybutadiene (c) used in the present invention functions to improve adhesion.
Component (c-3-2) is a liquid liquid which is transparent at room temperature, and has a main chain microstructure of polybutadiene consisting of vinyl 1,2-bond type, trans 1,4-bond type, cis 1,4-bond type. It is a polymer. Here, the vinyl 1,2-bond is preferably 30% by weight or less, and if the vinyl 1,2-bond exceeds 30% by weight, the storage stability of the resulting composition is deteriorated. Further, the cis 1,4-bond is preferably 40% by weight or more. If the cis 1,4-bond is less than 40% by weight, the adhesiveness of the resulting composition is lowered, which is not preferable.
　カルボキシル化ポリブタジエン（ｃ－３－２）成分は、液状ポリブタジエンにカルボキシル基導入化合物を反応させて得られ、液状ポリブタジエンを構成する１，３－ブタジエンとカルボキシル基導入化合物との比率は、１，３－ブタジエン８０～９８重量％とカルボキシル基導入化合物２～２０重量％であることが好ましい。 The carboxylated polybutadiene (c-3-2) component is obtained by reacting liquid polybutadiene with a carboxyl group-introducing compound, and the ratio of 1,3-butadiene and carboxyl group-introducing compound constituting the liquid polybutadiene is 1,3. -80 to 98% by weight of butadiene and 2 to 20% by weight of the carboxyl group-introducing compound are preferred.
　反応に用いる液状ポリブタジエンは、数平均として分子量５００～１０，０００であることが好ましく、より好ましくは１，０００～７，０００であり、分子量分布は広いことが望ましい。また、液状ポリブタジエンは、ＤＩＮ５３２４１に準じ測定したヨウ素価、ヨウ素３０～５００ｇ／物質１００ｇを有することがより好ましい。さらに、液状ポリブタジエンは、シス－二重結合７０～９０％、トランス－二重結合１０～３０％及びビニル二重結合０～３％の分子構造を有するものであることが好ましい。 The liquid polybutadiene used in the reaction preferably has a number average molecular weight of 500 to 10,000, more preferably 1,000 to 7,000, and a wide molecular weight distribution. The liquid polybutadiene more preferably has an iodine value measured according to DIN 53241, iodine of 30 to 500 g / 100 g of substance. Furthermore, the liquid polybutadiene preferably has a molecular structure of 70 to 90% cis-double bonds, 10 to 30% trans-double bonds and 0 to 3% vinyl double bonds.
　カルボキシル基導入化合物としては、エチレン系不飽和ジカルボキシ化合物、例えば、エチレン系不飽和ジカルボン酸、その無水物又はモノエステルを使用することができる。具体的化合物としては、マレイン酸、フマル酸、イタコン酸、３，６－テトラヒドロフタル酸、無水イタコン酸、１，２－ジメチルマレイン酸無水物、マレイン酸モノメチルエステル又はマレイン酸モノエチルエステル等を挙げることができる。これらの中でも安全性、経済性及び反応性の理由から、無水マレイン酸が好ましい。（マレイン化ポリブタジエンが好ましい。） As the carboxyl group-introducing compound, an ethylenically unsaturated dicarboxy compound, for example, an ethylenically unsaturated dicarboxylic acid, its anhydride or monoester can be used. Specific examples of the compound include maleic acid, fumaric acid, itaconic acid, 3,6-tetrahydrophthalic acid, itaconic anhydride, 1,2-dimethylmaleic anhydride, maleic acid monomethyl ester and maleic acid monoethyl ester. be able to. Among these, maleic anhydride is preferable because of safety, economy and reactivity. (Maleed polybutadiene is preferred.)
　ポリブタジエンと無水マレイン酸からなるポリブタジエン／無水マレイン酸－付加生成物の製造は公知の方法で行うことができる。 Production of a polybutadiene / maleic anhydride-addition product comprising polybutadiene and maleic anhydride can be carried out by a known method.
　また、マレイン化液状ポリブタジエンのＤＩＮ  ＩＳＯ  ３６８２に準じた酸価は、５０～１２０（ｍｇＫＯＨ／ｇ）が好ましく、更に好ましくは７０～９０（ｍｇＫＯＨ／ｇ）である。酸価が５０（ｍｇＫＯＨ／ｇ）未満では、得られる組成物の接着性が低下し、１２０（ｍｇＫＯＨ／ｇ）を超えると、得られる組成物の粘度が高くなり作業性が低下する。 The acid value of maleated liquid polybutadiene according to DIN ISO 3682 is preferably 50 to 120 (mgKOH / g), more preferably 70 to 90 (mgKOH / g). When the acid value is less than 50 (mgKOH / g), the adhesiveness of the resulting composition is lowered, and when it exceeds 120 (mgKOH / g), the viscosity of the obtained composition is increased and workability is lowered.
　さらに、マレイン化液状ポリブタジエンのマレイン化率は粘度とのかねあいがあるが、６～２０％が好ましく、より好ましくは６～１５％、さらに好ましくは７～１０％である。 Furthermore, the maleation rate of the maleated liquid polybutadiene is related to the viscosity, but is preferably 6 to 20%, more preferably 6 to 15%, and still more preferably 7 to 10%.
　また、マレイン化液状ポリブタジエンのＤＩＮ５３２１４にて測定した粘度（２０℃）は、３～１６Ｐａ・ｓが好ましく、より好ましくは５～１３Ｐａ・ｓであり、さらに好ましくは６～９Ｐａ・ｓである。 Further, the viscosity (20 ° C.) of maleated liquid polybutadiene measured by DIN 53214 is preferably 3 to 16 Pa · s, more preferably 5 to 13 Pa · s, and further preferably 6 to 9 Pa · s.
　さらに、マレイン化液状ポリブタジエンのビニル－二重結合は３０％以下であり、シス－二重結合が上記範囲にあるものはシス－二重結合が上記下限未満である液状ポリブタジエンに比べて高い柔軟性と上記のような高いマレイン化率（酸価）を持つ。そのため得られる組成物は接着性に富み、充分に極性が付与されているため、より柔軟化が可能となり、また柔軟性の調整が容易である。
　シス－二重結合が上記下限未満である液状ポリブタジエンはマレイン化率上昇と共に急激に粘度が上昇するが、シス－二重結合が上記範囲にあるものは粘度上昇が少ない。粘度が上記範囲のように低いことから、反応性が高くなり作業性が向上する。また、得られる組成物は、低粘度発現性、接着性の点で優れる。 In addition, maleated liquid polybutadiene has a vinyl-double bond of 30% or less, and those having a cis-double bond in the above range have higher flexibility than liquid polybutadiene in which the cis-double bond is less than the above lower limit. And has a high maleation rate (acid value) as described above. Therefore, the obtained composition is rich in adhesiveness and sufficiently polarized, so that it can be made more flexible and the flexibility can be easily adjusted.
Liquid polybutadiene having a cis-double bond less than the above lower limit rapidly increases in viscosity as the maleation rate increases, but those having a cis-double bond in the above range have a small increase in viscosity. Since the viscosity is low as in the above range, the reactivity is increased and workability is improved. Moreover, the composition obtained is excellent in terms of low viscosity expression and adhesiveness.
　マレイン化液状ポリブタジエンの市販品としては、例えば、デグサ社製  ＰＯＬＹＶＥＳＴ　ＯＣ　８００Ｓ（登録商標）、１２００Ｓが挙げられる。 Examples of commercially available maleated liquid polybutadiene include Degussa's POLYVEST OC 800S (registered trademark) and 1200S.
　エポキシ当量が１５０～７００ｇ／モルである化合物（ｃ－４）について説明する。 The compound (c-4) having an epoxy equivalent of 150 to 700 g / mol will be described.
　本発明において使用されるエポキシ当量が１５０～７００ｇ／モルである化合物（ｃ－４）の一つの形態は、エポキシ当量が１５０～２５０ｇ／モルであるポリエポキシ化合物（ｃ－４－１）である。 One form of the compound (c-4) having an epoxy equivalent of 150 to 700 g / mol used in the present invention is a polyepoxy compound (c-4-1) having an epoxy equivalent of 150 to 250 g / mol. .
　本発明の組成物における、エポキシ当量が１５０～２５０ｇ／モルであるポリエポキシ化合物（ｃ－４－１）としては、例えば、ハイドロキノン、レゾルシン、ピロカテコール、フロログルクシノールなどの単核多価フェノール化合物のポリグリシジルエーテル化合物；ジヒドロキシナフタレン、ビフェノール、メチレンビスフェノール（ビスフェノールＦ）、メチレンビス（オルトクレゾール）、エチリデンビスフェノール、イソプロピリデンビスフェノール（ビスフェノールＡ）、イソプロピリデンビス（オルトクレゾール）、テトラブロモビスフェノールＡ、１，３－ビス（４－ヒドロキシクミルベンゼン）、１，４－ビス（４－ヒドロキシクミルベンゼン）、１，１，３－トリス（４－ヒドロキシフェニル）ブタン、１，１，２，２－テトラ（４－ヒドロキシフェニル）エタン、チオビスフェノール、スルホビスフェノール、オキシビスフェノール、フェノールノボラック、オルソクレゾールノボラック、エチルフェノールノボラック、ブチルフェノールノボラック、オクチルフェノールノボラック、レゾルシンノボラック、テルペンフェノールなどの多核多価フェノール化合物のポリグリジルエーテル化合物；エチレングリコール、プロピレングリコール、ブチレングリコール、ヘキサンジオール、ポリグリコール、チオジグリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、ソルビトール、ビスフェノールＡ－エチレンオキシド付加物などの多価アルコール類のポリグリシジルエーテル；マレイン酸、フマル酸、イタコン酸、コハク酸、グルタル酸、スベリン酸、アジピン酸、アゼライン酸、セバシン酸、ダイマー酸、トリマー酸、フタル酸、イソフタル酸、テレフタル酸、トリメリット酸、トリメシン酸、ピロメリット酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、エンドメチレンテトラヒドロフタル酸等の脂肪族、芳香族または脂環族多塩基酸のグリシジルエステル類およびグリシジルメタクリレートの単独重合体または共重合体；Ｎ，Ｎ－ジグリシジルアニリン、ビス（４－（Ｎ－メチル－Ｎ－グリシジルアミノ）フェニル）メタン、ジグリシジルオルトトルイジン等のグリシジルアミノ基を有するエポキシ化合物；ビニルシクロヘキセンジエポキシド、ジシクロペンタンジエンジエポキサイド、３，４－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、３，４－エポキシ－６－メチルシクロヘキシルメチル－６－メチルシクロヘキサンカルボキシレート、ビス（３，４－エポキシ－６－メチルシクロヘキシルメチル）アジペート等の環状オレフィン化合物のエポキシ化物；エポキシ化ポリブタジエン、エポキシ化スチレン－ブタジエン共重合物等のエポキシ化共役ジエン重合体、トリグリシジルイソシアヌレート等の複素環化合物などがあげられる。 Examples of the polyepoxy compound (c-4-1) having an epoxy equivalent of 150 to 250 g / mol in the composition of the present invention include mononuclear polyhydric phenols such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol. Polyglycidyl ether compounds of compounds: dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1 , 3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2, -Polynuclear polyphenol compounds such as tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, terpene phenol Polyglycidyl of polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct Ether; maleic acid, fumaric acid, itaconic acid, succinic acid, glu Phosphoric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, Homopolymers or copolymers of glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as endomethylenetetrahydrophthalic acid and glycidyl methacrylate; N, N-diglycidylaniline, bis (4- (N- Epoxy compounds having a glycidylamino group such as methyl-N-glycidylamino) phenyl) methane and diglycidylorthotoluidine; vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxy Cyclohexa Epoxidized products of cyclic olefin compounds such as polycarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; And epoxidized conjugated diene polymers such as epoxidized styrene-butadiene copolymer, and heterocyclic compounds such as triglycidyl isocyanurate.
　本発明で使用されるエポキシ当量が１５０～２５０ｇ／モルであるポリエポキシ化合物（ｃ－４－１）としては、例えば、ビフェノール、メチレンビスフェノール（ビスフェノールＦ）、メチレンビス（オルトクレゾール）、エチリデンビスフェノール、イソプロピリデンビスフェノール（ビスフェノールＡ）、イソプロピリデンビス（オルトクレゾール）、テトラブロモビスフェノールＡ、１，３－ビス（４－ヒドロキシクミルベンゼン）、１，４－ビス（４－ヒドロキシクミルベンゼン）、１，１，３－トリス（４－ヒドロキシフェニル）ブタン、１，１，２，２－テトラ（４－ヒドロキシフェニル）エタン、チオビスフェノール、スルホビスフェノール、オキシビスフェノール、テルペンジフェノール等のビスフェノール化合物のポリグリジルエーテルが接着性の点でさらに好ましい。 Examples of the polyepoxy compound (c-4-1) having an epoxy equivalent of 150 to 250 g / mol used in the present invention include biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropyl Ridenbisphenol (bisphenol A), isopropylidenebis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1, Polyphenols of bisphenol compounds such as 1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, terpene diphenol Glycidyl Jill ether is more preferable in terms of adhesion.
　エポキシ当量が１５０～２５０ｇ／モルであるビスフェノール化合物のポリグリジルエーテルの例としては、アデカレジンＥＰ－４１００Ｅ（旭電化工業  製；ビスフェノールＡジグリシジルエーテル、エポキシ当量１９０）が例示される。 Examples of polyglycidyl ethers of bisphenol compounds having an epoxy equivalent of 150 to 250 g / mol include Adeka Resin EP-4100E (Asahi Denka Kogyo; bisphenol A diglycidyl ether, epoxy equivalent 190).
　本発明において使用されるエポキシ当量が１５０～７００ｇ／モルである化合物（ｃ－４）のもう一つの形態は、エポキシ当量が５００～７００ｇ／モルであるポリオレフィン系重合体（ｃ－４－２）である。好ましくは、片末端に水酸基を持ちかつエポキシ基を導入されたポリオレフィン系重合体である。さらに好ましくは液状である。 Another form of the compound (c-4) having an epoxy equivalent of 150 to 700 g / mol used in the present invention is a polyolefin polymer (c-4-2) having an epoxy equivalent of 500 to 700 g / mol. It is. A polyolefin polymer having a hydroxyl group at one end and having an epoxy group introduced is preferred. More preferably, it is liquid.
　エポキシ当量が１５０～７００ｇ／モルである重合体（ｃ－４）の具体的な例としてはクラレ社製Ｌ－２０７（ＫＲＡＴＯＮ　ＬＩＱＵＩＤ（商標）Ｌ－２０７ＰＯＬＹＭＥＲに同じ）である。Ｌ－２０７とは、エポキシ当量が５９０ｇ／モルであり、水酸基当量は７０００ｇ／モル、ガラス転移温度－５３℃である完全飽和骨格（エポキシ化エチレン・プロピレン－エチレン・ブチレン－ＯＨ構造）を持つ重合体であり、接着性の点で好ましい。 A specific example of the polymer (c-4) having an epoxy equivalent of 150 to 700 g / mol is Kuraray L-207 (same as KRATON LIQUID ™ L-207 POLYMER). L-207 is a heavy saturated skeleton (epoxidized ethylene / propylene / ethylene / butylene-OH structure) having an epoxy equivalent of 590 g / mol, a hydroxyl group equivalent of 7000 g / mol and a glass transition temperature of −53 ° C. It is a coalescence and is preferable in terms of adhesiveness.
（ｄ）開始剤
　本発明の接着剤組成物は、（ｄ）開始剤を必須成分とする。 (D) Initiator The adhesive composition of the present invention comprises (d) an initiator as an essential component.
　本発明の接着剤組成物は、オリゴマー成分（例えばビニルエステル樹脂や不飽和ポリエステル樹脂（ａ））が、（メタ）アクリロイル基等の二重結合を有するため、熱重合開始剤を添加すれば加熱により、また、光重合開始剤を添加すれば紫外線蛍光ランプあるいは高圧水銀灯等を用いた紫外線照射または電子線照射により容易に短時間で硬化させることが可能である。被着体および接着剤組成物の加熱を避けたい場合には紫外線照射が好ましい。 In the adhesive composition of the present invention, the oligomer component (for example, vinyl ester resin or unsaturated polyester resin (a)) has a double bond such as a (meth) acryloyl group. Further, if a photopolymerization initiator is added, it can be easily cured in a short time by ultraviolet irradiation or electron beam irradiation using an ultraviolet fluorescent lamp or a high-pressure mercury lamp. When it is desired to avoid heating the adherend and the adhesive composition, ultraviolet irradiation is preferred.
　本発明の接着剤組成物を加熱によって硬化させる場合には、常温～９０℃程度の加熱により硬化させることが可能である。
　熱重合開始剤としては、例えば、ベンゾイルパーオキサイド、ラウロイルパーオキサイド、コハク酸パーオキサイド、メチルエチルケトンパーオキサイド、２，５－ジメチル－２，５－ジ（ｔｅｒｔ－ブチルパーオキシ）ヘキサンおよびシクロヘキサノンパーオキサイド等が挙げられる。例えばパーオキサイド類の（１分）半減期温度が１００℃～１８０℃である場合は、８０℃×１０分～１６０℃×５分で十分な硬化性が得られる。 When the adhesive composition of the present invention is cured by heating, it can be cured by heating at about room temperature to 90 ° C.
Examples of the thermal polymerization initiator include benzoyl peroxide, lauroyl peroxide, succinic acid peroxide, methyl ethyl ketone peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, and cyclohexanone peroxide. Is mentioned. For example, when the (1 minute) half-life temperature of the peroxides is 100 ° C. to 180 ° C., sufficient curability can be obtained at 80 ° C. × 10 minutes to 160 ° C. × 5 minutes.
　光重合開始剤としては、例えば、ベンゾフェノン、２，４－ジヒドロキシベンゾフェノン、２－ヒドロキシ－４－メトキシベンゾフェノン、アセトフェノン、ベンゾイン、ベンゾインエチルエーテル、ベンゾイン－ｎ－プロピルエーテル、ベンゾインイソプロピルエーテル、ベンゾイン－ｎ－ブチルエーテル、ベンゾインイソブチルエーテル、ベンジル－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、２－ヒドロキシ－２－メチル１－フェニルプロパン－１－オン、ベンジルサルファイド、チオキサントン、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド、および２－クロロチキサント等が挙げられる。 Examples of the photopolymerization initiator include benzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, acetophenone, benzoin, benzoin ethyl ether, benzoin-n-propyl ether, benzoin isopropyl ether, benzoin-n- Butyl ether, benzoin isobutyl ether, benzyl-1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl 1-phenylpropan-1-one, benzyl sulfide, thioxanthone Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-chlorothixant and the like.
（接着剤組成物の配合割合）
　本発明の接着剤組成物において、成分（ａ）は、接着性、柔軟性、耐衝撃性の観点から、１０～４０質量％配合される。さらに好ましい成分（ａ）の配合割合は、加工しやすい粘度の点で１５～３５質量％である。
　成分（ａ）の配合量が４０質量％を超えると接着性が悪化し、また増粘により加工性が低下する。また、１０質量％未満では接着性、柔軟性、耐衝撃性が低下する。 (Blend ratio of adhesive composition)
In the adhesive composition of the present invention, the component (a) is blended in an amount of 10 to 40% by mass from the viewpoints of adhesiveness, flexibility and impact resistance. A more preferable blending ratio of the component (a) is 15 to 35% by mass in terms of a viscosity that is easy to process.
When the compounding amount of component (a) exceeds 40% by mass, the adhesiveness deteriorates, and the processability decreases due to the increase in viscosity. On the other hand, if it is less than 10% by mass, adhesiveness, flexibility and impact resistance are lowered.
　本発明の接着剤組成物において、成分（ｂ）は、接着性、柔軟性、耐衝撃性の観点から、３０～７０質量％配合される。さらに好ましい成分（ｂ）の配合量は、加工しやすい粘度の点で４０～６５質量％である。
　成分（ｂ）の配合量が７０質量％を超えると接着性、柔軟性、耐衝撃性、耐候性が低下する。また、３０質量％未満では接着性、柔軟性、耐衝撃性が悪化し、また増粘により加工性が低下する。 In the adhesive composition of the present invention, the component (b) is blended in an amount of 30 to 70% by mass from the viewpoints of adhesiveness, flexibility and impact resistance. A more preferable amount of component (b) is 40 to 65% by mass from the viewpoint of easy processing viscosity.
When the compounding amount of the component (b) exceeds 70% by mass, adhesiveness, flexibility, impact resistance, and weather resistance are lowered. Moreover, if it is less than 30 mass%, adhesiveness, a softness | flexibility, and impact resistance will deteriorate, and workability will fall by thickening.
　本発明の接着剤組成物において、成分（ｃ）は、接着性、柔軟性の観点から、５～４０質量％配合される。さらに好ましい成分（ｃ）の配合割合は、接着性、強靭性（耐衝撃性）、耐ブリード性の点で１０～３０質量％であり、とくに好ましくは１０～２５質量％である。
　成分（ｃ）の配合量が４０質量％を超えると耐ブリード性の悪化により強靭性（耐衝撃性）が低下し、接着力も低下し、耐水性、耐候性も悪化する。また、５質量％未満では接着性、柔軟性、耐衝撃性、耐候性が低下する。 In the adhesive composition of the present invention, the component (c) is blended in an amount of 5 to 40% by mass from the viewpoints of adhesiveness and flexibility. Further, the blending ratio of the component (c) is 10 to 30% by mass, particularly preferably 10 to 25% by mass in terms of adhesion, toughness (impact resistance) and bleed resistance.
When the compounding amount of the component (c) exceeds 40% by mass, the toughness (impact resistance) decreases due to the deterioration of the bleed resistance, the adhesive strength also decreases, and the water resistance and weather resistance also deteriorate. Moreover, if it is less than 5 mass%, adhesiveness, a softness | flexibility, impact resistance, and a weather resistance will fall.
　本発明の接着剤組成物において、成分（ｄ）は、実用的な光硬化時間（照射強さ５００ｍJ ／ｃｍ2で１０秒以下照射）の観点から、前記成分（ａ）～（ｃ）の合計１００質量に対し０．１～１５質量部配合される。さらに好ましい成分（ｄ）の配合量は、さらに実用的な光硬化時間（照射強さ５００ｍJ ／ｃｍ2で３秒以下照射）の点で１～１０質量部であり、とくに好ましくは２～５質量部である。
　成分（ｄ）の配合量が１５質量部を超えると柔軟性、接着性、耐衝撃性が低下する。また、０．１質量部未満では光硬化が不十分であることから接着性に劣る。なお、熱重合開始剤を使用する場合も、上記と同じ配合量でよい。 In the adhesive composition of the present invention, the component (d) is a total of the components (a) to (c) from the viewpoint of practical photocuring time (irradiation intensity of 500 mJ / cm 2 and irradiation for 10 seconds or less). 0.1 to 15 parts by mass is blended with respect to 100 parts by mass. The amount of the component (d) is more preferably 1 to 10 parts by weight, particularly preferably 2 to 5 parts by weight in terms of practical photocuring time (irradiation intensity of 500 mJ / cm 2 for 3 seconds or less). Part.
When the compounding amount of the component (d) exceeds 15 parts by mass, flexibility, adhesiveness and impact resistance are lowered. Moreover, if it is less than 0.1 mass part, since photocuring is inadequate, it is inferior to adhesiveness. In addition, also when using a thermal-polymerization initiator, the same compounding quantity as the above may be sufficient.
　本発明の接着剤組成物には、必要に応じて、充填材として一般に使用される、機能性フィラーなどを、本発明の目的を損なわない範囲で添加配合することができる。 In the adhesive composition of the present invention, if necessary, a functional filler or the like generally used as a filler can be added and blended as long as the object of the present invention is not impaired.
　剛性付与としては、例えば、タルク、マイカ等が挙げられ、これらは１種単独または２種以上の組み合せで使用される。 Examples of imparting rigidity include talc and mica, and these are used singly or in combination of two or more.
　熱伝導性付与としては、例えば、硫酸バリウム、酸化マグネシウム等が挙げられ、これらは１種単独または２種以上の組み合せで使用される。 Examples of thermal conductivity imparting include barium sulfate and magnesium oxide, and these are used alone or in combination of two or more.
　熱膨張性付与としては、例えば、熱膨張性マイクロカプセル等が挙げられる。
　レべリング性付与としては、例えば、シリコーン系レべリング剤等が挙げられる。 Examples of imparting thermal expansion include thermal expansion microcapsules.
Examples of the leveling property imparting include a silicone leveling agent.
　また、本発明の接着剤組成物の２５℃における粘度は特に限定されないが、３，０００ｍＰａ・ｓ以下、より好ましくは１００～２，０００ｍＰａ・ｓであるのがよい。粘度がこの範囲であれば、経時変化で分離しない安定な貯蔵安定性が得られ、気泡が発生しにくく、平滑な表面性を得ることができる。 なお、粘度は、Ｂ型粘度計により測定できる。 Further, the viscosity at 25 ° C. of the adhesive composition of the present invention is not particularly limited, but is preferably 3,000 mPa · s or less, more preferably 100 to 2,000 mPa · s. If the viscosity is within this range, stable storage stability that does not separate with time can be obtained, bubbles are not easily generated, and smooth surface properties can be obtained.粘度 The viscosity can be measured with a B-type viscometer.
　本発明の接着剤組成物の被着体は、ポリエステル系樹脂およびガラスである。ポリエステル系樹脂としては、例えばポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）が挙げられ、とくに接着性の点でＰＥＴが好ましい。ガラスとしては、とくに制限されないが、例えば、硬く、軽いソーダライムガラス、屈折率・透明度が高い石英ガラス、透明度は低いが硬くて軽いホウ珪酸ガラス等が挙げられる。 The adherend of the adhesive composition of the present invention is a polyester resin and glass. Examples of the polyester resin include polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), and PET is particularly preferable from the viewpoint of adhesiveness. The glass is not particularly limited, and examples thereof include hard and light soda lime glass, quartz glass having a high refractive index and transparency, and low but hard and light borosilicate glass.
　接着剤組成物の調製方法としては、例えば、攪拌機を備えた容器に、成分（ａ）に、反応性希釈剤として成分（ｂ）および（ｃ）を添加する。添加方法としては、まず成分（ａ）に成分（ｂ）を添加し、常温で十分に攪拌する。粘度が高すぎる場合は１００℃以下で加温しながら攪拌しても差し支えない。１００℃を超えると成分（ｂ）の蒸気発生が顕著になり作業環境上好ましくない。その後、成分（ｃ）を加え攪拌後、液温が常温になった時点で、成分（ｄ）を添加して、溶け残りがないように十分攪拌する。
　その他の成分を添加する場合は、最後に添加し、十分に攪拌する。
　攪拌して得られた接着剤組成物は、速やかに加工するか、冷暗所に保存する。 As a method for preparing the adhesive composition, for example, the components (b) and (c) are added as reactive diluents to the component (a) in a container equipped with a stirrer. As an addition method, first, the component (b) is added to the component (a) and sufficiently stirred at room temperature. If the viscosity is too high, stirring may be performed while heating at 100 ° C. or lower. If it exceeds 100 ° C., the vapor generation of the component (b) becomes remarkable, which is not preferable in the working environment. Thereafter, after adding component (c) and stirring, when the liquid temperature reaches room temperature, component (d) is added, and the mixture is sufficiently stirred so as not to remain undissolved.
When adding other components, add them at the end and stir well.
The adhesive composition obtained by stirring is quickly processed or stored in a cool and dark place.
（本発明の積層体）
　本発明の積層体は、前記接着剤組成物を介して、ポリエステル系樹脂の層と、ガラスの層とが積層されてなることを特徴とする。積層体の調製方法としては、前記のようにして本発明の接着剤組成物を調製し、続いて、被着体（Ｂ１）の層上に接着剤組成物を積層し、接着剤組成物の層（Ａ）を形成し、次に、接着剤組成物の層（Ａ）上に、被着体の層（Ｂ２）をさらに積層する。なお、前記被着体（Ｂ１）の層がポリエステル系樹脂である場合、前記被着体（Ｂ２）はガラスであり、前記被着体（Ｂ１）の層がガラスである場合、前記被着体（Ｂ２）はポリエステル系樹脂の層である。
　接着剤組成物の層（Ａ）（硬化塗膜）の厚みは、特に限定されないが２μｍ～５０μｍ 、好ましくは５μｍ～３０μｍ 、更に好ましくは８μｍ～２０μｍ程度である。（本発明の接着剤組成物は無溶剤（揮発性）で配合する場合は硬化時の収縮が少ないため塗布厚と硬化後の膜厚は大きく差異がない。）この塗膜厚みに調整することにより、接着性、透明性が向上する。塗工方法としては、スピンコート法、（ドクター）ナイフコート法、マイクログラビヤコート法、ダイレクトグラビヤコート法、オフセットグラビヤ法、リバースグラビヤ法、リバースロールコート法、（マイヤー） バーコート法、ダイコート法、スプレーコート法、ディップコート法等の方法が好ましく適用できる。例えばスピンコート法の装置としてマニュアルスピナー（(株)エイブル製ASS-301型））が挙げられる。
　本発明の積層体は、被着体の層（Ｂ１）および（Ｂ２）と接着剤組成物の層（Ａ）との接着性が良好であり、透明性、表面平滑性、柔軟性、耐衝撃性のバランスに優れる。
　なお、上記以外にも、被着体の層と接着剤組成物の層とは複数回交互に積層することもでき、これも本発明でいう積層体の範囲内である。 (Laminated body of the present invention)
The laminate of the present invention is characterized in that a polyester resin layer and a glass layer are laminated via the adhesive composition. As a method for preparing the laminate, the adhesive composition of the present invention is prepared as described above, and then the adhesive composition is laminated on the layer of the adherend (B1). A layer (A) is formed, and then an adherend layer (B2) is further laminated on the layer (A) of the adhesive composition. When the layer of the adherend (B1) is a polyester resin, the adherend (B2) is glass, and when the layer of the adherend (B1) is glass, the adherend (B2) is a polyester resin layer.
The thickness of the layer (A) (cured coating film) of the adhesive composition is not particularly limited, but is about 2 μm to 50 μm, preferably 5 μm to 30 μm, and more preferably about 8 μm to 20 μm. (When the adhesive composition of the present invention is blended without solvent (volatile), the coating thickness and the film thickness after curing are not significantly different because there is little shrinkage at the time of curing.) Thereby, adhesiveness and transparency are improved. Coating methods include spin coating, (doctor) knife coating, micro gravure coating, direct gravure coating, offset gravure, reverse gravure, reverse roll coating, (Meyer) bar coating, die coating, Methods such as spray coating and dip coating can be preferably applied. For example, a manual spinner (ASS-301 type manufactured by Able Co., Ltd.) can be cited as an apparatus for spin coating.
The laminate of the present invention has good adhesion between the adherend layers (B1) and (B2) and the adhesive composition layer (A), and has transparency, surface smoothness, flexibility, and impact resistance. Excellent balance of sex.
In addition to the above, the layer of the adherend and the layer of the adhesive composition can be alternately laminated a plurality of times, and this is also within the scope of the laminate referred to in the present invention.
　本発明の積層体は、透明性、表面平滑性、柔軟性、耐衝撃性、耐水性、耐候性がいずれも良好であるという観点から、窓ガラスとして有用である。窓ガラスとしては、とくに制限されず、一般住宅、ビルディング等の建物用窓ガラス、自動車、鉄道等の車両、飛行機や船舶等の乗物用窓ガラス、機械設備における覗き窓等が挙げられる。とくに本発明では、上記の各種特性が優れるという観点から、建物用窓ガラスが好ましい。
　なお、本発明における積層体には、とくに窓ガラスとして利用する際には、必要に応じて、ポリエステル系樹脂の層に、公知の各種機能性フィラー、例えば赤外線吸収材料、紫外線吸収材料、帯電防止材料および電磁波シールド材料等を添加することができる。
　赤外線吸収材料としては、例えばカーボンナノチューブ、酸化亜鉛、アルミニウムドープ酸化亜鉛、ガリウムドープ酸化亜鉛、セシウム含有酸化タングステン、ＡＴＯ（アンチモン－錫複合酸化物又はアンチモンドープ酸化錫）、ＩＴＯ（インジウム－錫複合酸化物）等が挙げられる。赤外線吸収材料の配合量は、所望の赤外線吸収性を考慮して適宜決定すればよいが、例えばポリエステル系樹脂の層中、０．１～３０質量％の範囲が挙げられる。
　紫外線吸収材料としては、例えば、サリシレート系、ベンゾフェノン系、ベンゾトリアゾール系、置換アクリロニトリル系、トリアジン系等の有機系化合物、前述したカーボンナノチューブ、酸化亜鉛、アルミニウムドープ酸化亜鉛、ガリウムドープ酸化亜鉛、二酸化チタン、酸化セリウム、二酸化チタン微粒子を酸化鉄で複合化処理してなるハイブリッド無機粉体、酸化セリウム微粒子の表面を非結晶性シリカでコーティングしてなるハイブリッド無機粉体等の無機系化合物が挙げられる。紫外線吸収材料の配合量は、所望の紫外線吸収性を考慮して適宜決定すればよいが、例えばポリエステル系樹脂の層中、０．１～３０質量％の範囲が挙げられる。
　帯電防止材料としては、例えば金属酸化物及び金属塩が挙げられ、該金属酸化物としては、例えば前述した酸化亜鉛、アルミニウムドープ酸化亜鉛、ガリウムドープ酸化亜鉛、ＡＴＯ、ＩＴＯ、酸化錫、五酸化アンチモン、酸化ジルコニウム、酸化チタン、酸化アルミニウム等が挙げられる。また、前述したカーボンナノチューブも利用できる。帯電防止材料の配合量は、所望の帯電防止性を考慮して適宜決定すればよいが、例えばポリエステル系樹脂の層中、０．１～３０質量％の範囲が挙げられる。
　電磁波シールド材料としては、導電性粒子が挙げられ、例えば （１）カーボン粒子ないし粉末； （２）ニッケル、インジウム、クロム、金、バナジウム、すず、カドミウム、銀、プラチナ、アルミ、銅、チタン、コバルト、鉛等の金属又は合金或いはこれらの導電性酸化物の粒子ないし粉末；（３）ポリスチレン、ポリエチレン等のプラスチック粒子の表面に上記（１）、（２）の導電性材料のコーティング層を形成したもの等が挙げられる。電磁波シールド材料の配合量は、所望の電磁波シールド性を考慮して適宜決定すればよいが、例えばポリエステル系樹脂の層中、６０～９０質量％の範囲が挙げられる。
　また、本発明の窓ガラスにおいて、ポリエステル系樹脂の層は、室外側、室内側のいずれであってもよい。 The laminate of the present invention is useful as a window glass from the viewpoint that transparency, surface smoothness, flexibility, impact resistance, water resistance, and weather resistance are all good. The window glass is not particularly limited, and examples thereof include window glass for buildings such as ordinary houses and buildings, vehicles such as automobiles and railways, window glass for vehicles such as airplanes and ships, and viewing windows in mechanical equipment. Especially in this invention, the window glass for buildings is preferable from a viewpoint that said various characteristics are excellent.
In the laminate of the present invention, when used as a window glass, various known functional fillers such as an infrared absorbing material, an ultraviolet absorbing material, and an antistatic material are optionally added to the polyester resin layer. Materials, electromagnetic shielding materials and the like can be added.
Examples of infrared absorbing materials include carbon nanotubes, zinc oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, cesium-containing tungsten oxide, ATO (antimony-tin composite oxide or antimony-doped tin oxide), ITO (indium-tin composite oxide). Thing) etc. are mentioned. The blending amount of the infrared absorbing material may be appropriately determined in consideration of a desired infrared absorptivity. For example, the range of 0.1 to 30% by mass in the polyester resin layer may be mentioned.
Examples of the ultraviolet absorbing material include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, triazine-based organic compounds, the carbon nanotubes described above, zinc oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, and titanium dioxide. Inorganic compounds such as hybrid inorganic powder obtained by complexing cerium oxide and titanium dioxide fine particles with iron oxide, and hybrid inorganic powder obtained by coating the surface of cerium oxide fine particles with amorphous silica. The blending amount of the ultraviolet absorbing material may be appropriately determined in consideration of the desired ultraviolet absorptivity, and examples thereof include a range of 0.1 to 30% by mass in the polyester resin layer.
Examples of the antistatic material include metal oxides and metal salts. Examples of the metal oxide include zinc oxide, aluminum doped zinc oxide, gallium doped zinc oxide, ATO, ITO, tin oxide, and antimony pentoxide described above. , Zirconium oxide, titanium oxide, aluminum oxide and the like. Moreover, the carbon nanotube mentioned above can also be utilized. The blending amount of the antistatic material may be appropriately determined in consideration of the desired antistatic property, and examples thereof include a range of 0.1 to 30% by mass in the polyester resin layer.
Examples of the electromagnetic shielding material include conductive particles such as (1) carbon particles or powder; (2) nickel, indium, chromium, gold, vanadium, tin, cadmium, silver, platinum, aluminum, copper, titanium, cobalt , Particles or powders of lead or other metals or alloys or conductive oxides thereof; (3) a coating layer of the conductive material (1) or (2) above is formed on the surface of plastic particles such as polystyrene or polyethylene; And the like. The blending amount of the electromagnetic shielding material may be appropriately determined in consideration of desired electromagnetic shielding properties. For example, a range of 60 to 90% by mass in the polyester resin layer may be mentioned.
In the window glass of the present invention, the polyester resin layer may be on the outdoor side or the indoor side.
　以下、本発明を実施例および比較例によりさらに説明するが、本発明は下記例に制限されない。 Hereinafter, the present invention will be further described with reference to examples and comparative examples, but the present invention is not limited to the following examples.
　実施例および比較例で使用した原料は以下の通りである。
成分（ａ－１）ビニルエステル樹脂
（ｉ）ウレタンアクリレート
　サートマー社製　CN963B80 ウレタンアクリレート（HDDAブレンド）、タイプ=ポリエステル、60℃粘度=1,100、官能基数=2
（ｉｉ）ポリエステルアクリレート
　サートマー社製　CN292 ポリエステルアクリレート、タイプ=脂肪族ポリエステル、25℃粘度=630、官能基数=4
（ｉｉｉ）エポキシアクリレート
　サートマー社製　CNUVE151 エポキシアクリレート、タイプ=ポリエステル、25℃粘度=150,000、官能基数=2
（ｉｖ）脂肪族ウレタンアクリレート
　サートマー社製　CN966J75 脂肪族ウレタンアクリレート（IBOAブレンド）、タイプ=ポリエステル、60℃粘度=4,240、25℃粘度=105,000、官能基数=2
成分（ａ－２）不飽和ポリエステル樹脂
　昭和高分子社製、ＲＩＧＯＬＡＣ　２１Ｅ－Ａ－２（商標） The raw materials used in the examples and comparative examples are as follows.
Component (a-1) Vinyl ester resin (i) Urethane acrylate Sartomer CN963B80 Urethane acrylate (HDDA blend), Type = Polyester, 60 ° C. viscosity = 1,100, Number of functional groups = 2
(Ii) Polyester acrylate CN292 polyester acrylate manufactured by Sartomer, type = aliphatic polyester, viscosity at 25 ° C. = 630, number of functional groups = 4
(Iii) Epoxy acrylate Sartomer CNUVE151 epoxy acrylate, type = polyester, viscosity at 25 ° C. = 150,000, number of functional groups = 2
(Iv) Aliphatic urethane acrylate manufactured by Sartomer CN966J75 Aliphatic urethane acrylate (IBOA blend), type = polyester, 60 ° C. viscosity = 4,240, 25 ° C. viscosity = 105,000, number of functional groups = 2
Component (a-2) Unsaturated polyester resin RIGOLAC 21E-A-2 (trademark) manufactured by Showa Polymer Co., Ltd.
成分（ｂ－１）　環状構造および１個のエチレン性不飽和基を有する化合物
（ｉ）ＢＡＳＦ社製、Ｎ－ビニルカプロラクタム
　沸点 117℃(10mm Hg)
　蒸気圧 <0.1 mm Hg (20℃)
　引火点 110℃
　融点 35℃
　粘度 3.5 cps (40℃)
成分（ｂ－２）ジアクリレートモノマー
　（ｉ）ＢＡＳＦ社製、ジプロピレングリコールジアクリレート（ＤＰＧＤＡ）
　（ｉｉ）ＢＡＳＦ社製、トリプロピレングリコールジアクリレート（ＴＰＧＤＡ） Component (b-1) Compound having a cyclic structure and one ethylenically unsaturated group (i) N-vinylcaprolactam boiling point 117 ° C. (10 mm Hg) manufactured by BASF
Vapor pressure <0.1 mm Hg (20 ℃)
Flash point 110 ° C
Melting point 35 ℃
Viscosity 3.5 cps (40 ° C)
Component (b-2) Diacrylate monomer (i) Dipropylene glycol diacrylate (DPGDA) manufactured by BASF
(Ii) BASF, tripropylene glycol diacrylate (TPGDA)
成分（ｃ）　変性剤
（ｃ－１－２）ポリブタジエン系ポリオール
出光興産社製、Ｐｏｌｙ　ｂｄ　Ｒ-１５ＨＴ
粘度：１．５Ｐａ・ｓ／３０℃、水酸基価：１０２．７ｍｇＫＯＨ／ｇ
（ｃ－１－１－１）芳香族系ヒマシ油系ポリオール
伊藤製油社製、ＵＲＩＣ（商標）ＡＣ－００６、前記式（４）で表されるヒマシ油由来のポリオール、粘度：０．７～１．５Ｐａ・ｓ／２５℃、水酸基価：１９４～２１４ｍｇＫＯＨ／ｇ
（ｃ－１－３）ポリイソプレン系ポリオール
出光興産社製、Poly ip（登録商標）分子末端に反応性の高い水酸基を備えたポリイソプレンタイプの液状ポリマー（水酸基価４６．６ｍｇＫＯＨ／ｍｇ、数平均分子量Ｍｎ＝２５００）
（ｃ－２－１）ヒマシ油系ポリオール
伊藤製油　ＵＲＩＣ　Ｈ－１２６２
ヒマシ油系ポリオールと全炭素数が１２以上の酸性リン酸エステル化合物を含むポリオール　粘度：３，５００～８，５００Ｐａ・ｓ／２５℃、酸価：４～１５（単位ｍｇＫＯＨ／ｇ）、水酸基価：２４０～２９０（単位ｍｇＫＯＨ／ｇ）
（ｃ－２－１）ヒマシ油系ポリオール
伊藤製油　ＵＲＩＣ　Ｈ－２１５１Ｕ
ヒマシ油系ポリオールと全炭素数が１２以上の酸性リン酸エステル化合物とテルペンフェノール類を含有するポリオール　粘度：３，５００～８，５００Ｐａ・ｓ／２５℃、酸価：４～１５（単位ｍｇＫＯＨ／ｇ）、水酸基価：２４０～２９０（単位ｍｇＫＯＨ／ｇ）
（ｃ－１－３）ポリイソプレン系ポリオールの水素添加物
出光興産社製　エポール（商標）水酸基末端液状ポリオレフィン
（粘度（Pa・s/30℃）75、水酸基価(mgKOH/g) 50.5、数平均分子量2500）
（ｃ－３－１）マレイン化ポリイソプレン
株式会社 クラレ　LIR-420  （酸価(mgKOH/g) 40）
（ｃ－３－２）マレイン酸変性ポリブタジエン
SARTOMER社製　Ricon130MA8  （粘度（Pa・s/30℃）6.5、酸価(mgKOH/g) 46、数平均分子量2700）
（ｃ－３－２）マレイン酸変性ポリブタジエン
EVONIK社製　POLYVEST（商標） OC 800 S  （ポリブタジエンにおける１，４－シス二重結合：７５％、１，４－トランス二重結合：２４％、ビニル結合：１％、マレイン化率：７．５％、数平均分子量：３３００（ＧＰＣ）、重量平均分子量：１３，６００（ＧＰＣ）、粘度（２０℃）：６～９Ｐａ・ｓ（ＤＩＮ５３２１４にて測定）、酸価：７０～９０ｍｇＫＯＨ／ｇ、ヨウ素価：３８０～４２０ｇ／１００ｇ、（チグラー－ナッタ触媒で重合））
（ｃ－１－４）エポキシポリオール樹脂
DIC株式会社　EPICLON（商標）U-125-60BT
（粘度（Pa・s/30℃）70、水酸基価(mgKOH/g) 120）
（ｃ－４－１）エポキシ当量が１５０～２５０ｇ／モルであるポリエポキシ化合物
アデカレジンＥＰ－４１００Ｅ（旭電化工業　製；ビスフェノールＡジグリシジルエーテル、エポキシ当量１９０）
（ｃ－４－２）エポキシ当量が５００～７００ｇ／モルである飽和骨格を持つ重合体
クラレ社製Ｌ－２０７（ＫＲＡＴＯＮ　ＬＩＱＵＩＤ（商標）Ｌ－２０７ＰＯＬＹＭＥＲに同じ）　（エポキシ当量が５９０ｇ／モルで、水酸基当量は７０００ｇ／モル、ガラス転移温度－５３℃、完全飽和骨格（エポキシ化エチレン・プロピレン－エチレン・ブチレン－ＯＨ構造）を持つ重合体） Component (c) Modifier (c-1-2) Polybutadiene polyol manufactured by Idemitsu Kosan Co., Ltd., Poly bd R-15HT
Viscosity: 1.5 Pa · s / 30 ° C., hydroxyl value: 102.7 mg KOH / g
(C-1-1-1) Aromatic castor oil-based polyol manufactured by Ito Oil Co., Ltd., URIC (trademark) AC-006, a polyol derived from castor oil represented by the above formula (4), viscosity: 0.7 to 1.5 Pa · s / 25 ° C., hydroxyl value: 194 to 214 mg KOH / g
(C-1-3) Polyisoprene-based polyol manufactured by Idemitsu Kosan Co., Ltd. Polyisoprene type liquid polymer having a highly reactive hydroxyl group at the molecular end (hydroxyl value 46.6 mgKOH / mg, number average) Molecular weight Mn = 2500)
(C-2-1) Castor oil-based polyol Ito Oil URIC H-1262
Polyol containing a castor oil-based polyol and an acidic phosphate ester compound having a total carbon number of 12 or more Viscosity: 3,500 to 8,500 Pa · s / 25 ° C., acid value: 4 to 15 (unit mgKOH / g), hydroxyl value : 240-290 (unit mgKOH / g)
(C-2-1) Castor oil-based polyol Ito Oil URIC H-2151U
A polyol containing a castor oil-based polyol, an acidic phosphate ester compound having 12 or more carbon atoms and terpene phenols Viscosity: 3,500 to 8,500 Pa · s / 25 ° C., acid value: 4 to 15 (unit: mgKOH / g), hydroxyl value: 240 to 290 (unit: mgKOH / g)
(C-1-3) Hydrogenated polyisoprene polyol manufactured by Idemitsu Kosan Co., Ltd. Epol (trademark) hydroxyl terminated liquid polyolefin (viscosity (Pa · s / 30 ° C) 75, hydroxyl value (mgKOH / g) 50.5, number average Molecular weight 2500)
(C-3-1) Maleinized polyisoprene Kuraray LIR-420 (acid value (mgKOH / g) 40)
(C-3-2) Maleic acid-modified polybutadiene
SARTOMER Ricon130MA8 (viscosity (Pa · s / 30 ° C) 6.5, acid value (mgKOH / g) 46, number average molecular weight 2700)
(C-3-2) Maleic acid-modified polybutadiene
POLYVEST ™ OC 800 S manufactured by EVONIK (1,4-cis double bond in polybutadiene: 75%, 1,4-trans double bond: 24%, vinyl bond: 1%, maleation ratio: 7.5 %, Number average molecular weight: 3300 (GPC), weight average molecular weight: 13,600 (GPC), viscosity (20 ° C.): 6 to 9 Pa · s (measured with DIN 53214), acid value: 70 to 90 mg KOH / g, iodine Value: 380 to 420 g / 100 g, (polymerized with Ziegler-Natta catalyst)
(C-1-4) Epoxy polyol resin
DIC Corporation EPICLON (trademark) U-125-60BT
(Viscosity (Pa · s / 30 ° C) 70, hydroxyl value (mgKOH / g) 120)
(C-4-1) Polyepoxy compound Adeka Resin EP-4100E having an epoxy equivalent of 150 to 250 g / mol (Asahi Denka Kogyo; bisphenol A diglycidyl ether, epoxy equivalent 190)
(C-4-2) Polymer having a saturated skeleton having an epoxy equivalent of 500 to 700 g / mol L-207 manufactured by Kuraray (same as KRATON LIQUID ™ L-207 POLYMER) (Epoxy equivalent is 590 g / mol, Hydroxyl equivalent weight is 7000 g / mol, glass transition temperature -53 ° C, polymer with fully saturated skeleton (epoxidized ethylene / propylene / ethylene / butylene-OH structure)
　各ポリオールの特性は、次のようにして測定した。
・粘度測定方法
　粘度計は、JIS K7117-1に従って、単一円筒型回転粘度計（B形TVC--5）を用いて測定。
　1.測定器に500mlビーカ（標準）を使用。
　2.標準ロータは、低・中粘度用としてのM1～M4ロータ、中・高粘度用としてのH1～H7ロータの2種から選択
・水酸基価測定方法
　水酸基価とは、試料1g中に含まれるOH基をアセチル化するために要する水酸化カリウムのmg数である。JIS K 1557-1に準じて、無水酢酸を用いて試料中のOH基をアセチル化し、使われなかった酢酸を水酸化カリウム溶液で滴定する。 The characteristics of each polyol were measured as follows.
・ Viscosity measurement method The viscometer is measured using a single cylindrical rotational viscometer (B type TVC--5) according to JIS K7117-1.
1. A 500ml beaker (standard) is used for the measuring instrument.
2. The standard rotor is selected from two types: M1 to M4 rotors for low and medium viscosity and H1 to H7 rotors for medium and high viscosity. Hydroxyl value measurement method Hydroxyl value is included in 1g of sample. This is the number of mg of potassium hydroxide required to acetylate the OH group. According to JIS K 1557-1, OH groups in the sample are acetylated using acetic anhydride, and acetic acid not used is titrated with potassium hydroxide solution.
Figure JPOXMLDOC01-appb-M000004
Figure JPOXMLDOC01-appb-M000004
A：空試験に用いた0.5mol/l水酸化カリウムエタノール溶液の量(ml)
B：滴定に用いた0.5mol/l水酸化カリウムエタノール溶液の量(ml)
f：ファクター A: Amount of 0.5 mol / l potassium hydroxide ethanol solution used for the blank test (ml)
B: 0.5mol / l potassium hydroxide ethanol solution used for titration (ml)
f: Factor
・酸価測定方法
　試料油１ｇに含まれる酸性成分を中和するのに要する水酸化カリウムのｍｇ数で表す。JIS K 1557-5に準じて、
(1)終点pHの測定
　200mLビーカに緩衝貯蔵液Bを10mL採取し、滴定溶剤を100mL加えて電極を浸け、30秒間で0.1pH以内の変化となったpHを緩衝の終点とする。
(2）酸価の測定
　1.試料20gを200mLビーカに正確に秤量する。
　2.トルエン・2-プロパノール・純水混合溶剤125mLを加え、0.1mol/L水酸化カリウム滴定液で滴定する。
（1）の結果 11.72 pHを終点として設定し、次式で酸価を求める。また、同手順でブランクを求める。
酸価（mgKOH/g）＝（D－B）×K×F×M/S
　D：滴定値（mL）
　B：ブランク（0.085mL）
　K：KOHの分子量（56.1）
　F：滴定液のファクタ（1.000）
　M：滴定液のモル濃度（0.1mol/L）
　S：試料採取量（g） -Acid value measuring method It represents with the mg number of potassium hydroxide required to neutralize the acidic component contained in 1g of sample oils. According to JIS K 1557-5,
(1) End-point pH measurement Take 10 mL of buffer stock solution B in a 200-mL beaker, add 100 mL of titration solvent, immerse the electrode, and use the pH that changes within 0.1 pH within 30 seconds as the buffer end point.
(2) Measurement of acid value 1. Weigh accurately 20 g of sample into a 200 mL beaker.
2. Add 125mL of toluene / 2-propanol / pure water mixed solvent and titrate with 0.1mol / L potassium hydroxide titrant.
Result of (1) 11.72 Set pH as the end point and calculate the acid value by the following formula. In addition, a blank is obtained in the same procedure.
Acid value (mgKOH / g) = (D−B) × K × F × M / S
D: Titration value (mL)
B: Blank (0.085mL)
K: Molecular weight of KOH (56.1)
F: Factor of titrant (1.000)
M: Molar concentration of titrant (0.1 mol / L)
S: Sampling amount (g)
成分（ｄ）成分　開始剤
（ｉ）光重合開始剤
ＣＩＢＡ社製、ＩＲＧＡＣＵＲＥ（商標）８１９、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド
（ｉｉ）熱重合開始剤
日油社製、パーヘキサ２５Ｂ（１分半減期：１７９℃）、２，５－ジメチル－２，５－ジ（ｔｅｒｔ－ブチルパーオキシ）ヘキサン Component (d) Component Initiator (i) Photopolymerization initiator CIBA, IRGACURE ™ 819, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (ii) Thermal polymerization initiator NOF Corporation Perhexa 25B (1 minute half-life: 179 ° C.), 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane
実施例１～２２、比較例１～６
　下記表１～７に示す配合割合（質量部）において、攪拌機を備えた容器中に成分（ａ）を入れ、続いて成分（ｂ）を添加し、常温で十分に攪拌し、その後、成分（ｃ）を加え攪拌後、液温が常温になった時点で、成分（ｄ）を添加して、溶け残りがないように十分攪拌し、組成物を得た。得られた組成物の２５℃における粘度（mPa・s）を測定した。 すなわち、ハンディタイプのデジタル粘度計TVC-7形粘度計（東機産業社）を用いて、粘度に合わせた適当なロータ（０号～５号）を用いて、２５℃粘度を測定した。結果を表１～７に併せて示す。 Examples 1 to 22, Comparative Examples 1 to 6
In the blending ratio (parts by mass) shown in Tables 1 to 7 below, the component (a) is put into a container equipped with a stirrer, then the component (b) is added, and the mixture is sufficiently stirred at room temperature. After adding c) and stirring, when the liquid temperature reached room temperature, the component (d) was added, and the mixture was sufficiently stirred so as not to remain undissolved to obtain a composition. The viscosity (mPa · s) at 25 ° C. of the obtained composition was measured. That is, using a handy type digital viscometer TVC-7 type viscometer (Toki Sangyo Co., Ltd.), the viscosity at 25 ° C. was measured using an appropriate rotor (No. 0 to No. 5) according to the viscosity. The results are also shown in Tables 1 to 7.
　次に、表１～７に示す各被着体（寸法：１５０ｍｍ×２５ｍｍ×厚さ１ｍｍ）上に、スピンコート法により組成物を塗布し（塗布厚１５～２０μｍ）、これを空気下で５００ｍＪ／ｃｍ2のエネルギーの紫外線を照射して硬化させ、積層体を調製した。また、熱重合開始剤を使用した場合は、必要に応じて組成物に６％ナフテンコバルトを０～０．０５質量部添加して、１００℃で３０分熱処理して硬化させ、積層体を調製した。 Next, on each adherend shown in Tables 1 to 7 (dimensions: 150 mm × 25 mm × thickness 1 mm), the composition was applied by spin coating (coating thickness 15 to 20 μm), and this was applied under air to 500 mJ. A laminate was prepared by irradiating with UV light having an energy of / cm 2 to be cured. When a thermal polymerization initiator is used, if necessary, 0 to 0.05 part by mass of 6% naphthenic cobalt is added to the composition and cured by heat treatment at 100 ° C. for 30 minutes to prepare a laminate. did.
　使用した各被着体は、次の通りである。
・ガラス（顕微鏡プレパラート用スライドグラス）
・ＰＥＴ：ユニチカ　ユニチカポリエステル樹脂MA-2103 Each adherend used is as follows.
・ Glass (slide glass for microscope preparation)
・ PET: Unitika Unitika polyester resin MA-2103
透明性試験
（ヘーズ値および全光線透過率の測定）
　被着体としてガラスを用いた積層体を用いて、日本電色工業社製の測定器（ 商品名「ＣＯＨ－３００Ａ」）を用いて測定を行った。 Transparency test (measurement of haze value and total light transmittance)
Using a laminate using glass as the adherend, measurement was performed using a measuring instrument (trade name “COH-300A”) manufactured by Nippon Denshoku Industries Co., Ltd.
碁盤目テープ試験
　得られた積層体について、以下の碁盤目テープ試験を行なった。
　日本工業規格Ｋ５４００に記載されている碁盤目テープ試験法に準拠して以下のように測定を行った。
　碁盤目テープ試験（Cross-cut  Test、塗布厚１５～２０μｍ（スピンコート法））：試験面（組成物の層側）にカッターナイフを用いて、1×1mm四方の碁盤目の切り傷を入れる。カッターガイドを使用する。碁盤目の数は、縦10個×横10個＝100個入れる。碁盤目を入れた所にセロハンテープを強く圧着させ、テープの端を45°の角度で急速に引き剥がし、碁盤目の状態（剥離しないで残った碁盤目の個数）を見る。 Cross cut tape test The resulting laminate was subjected to the following cross cut tape test.
The measurement was performed as follows in accordance with the cross cut tape test method described in Japanese Industrial Standard K5400.
Cross-cut test (Cross-cut Test, coating thickness 15-20 μm (spin coating method)): A 1 × 1 mm square cut is made on the test surface (the layer side of the composition) using a cutter knife. Use the cutter guide. The number of grids is 10 vertical x 10 horizontal = 100. Strongly press the cellophane tape into the grid, and peel off the end of the tape rapidly at an angle of 45 ° to see the grid pattern (number of grids remaining without peeling).
接着性試験
　寸法１５０ｍｍ×１ｍｍ厚×２５ｍｍ巾のポリエステル系樹脂（Ｂ１）上に、スピンコート法で上記組成物を塗布し（塗布厚１５～２０μｍ）、組成物の層（Ａ）を形成し、さらにその上に、表１～７に示す、上記（Ｂ１）と同じ寸法のガラス（Ｂ２）を圧着させ、層（Ｂ２）（ガラス）側からＵＶ照射（波長：３２５ｎｍ、積算照射強さ：５０mJ/cm2）してＵＶ硬化させ、積層体を調製した後、層（Ｂ２）を、組成物の層（Ａ）の接合面と平行な方向に引張り、破断時の引張強さを測定した。また、熱重合開始剤を使用した場合は、必要に応じて組成物に６％ナフテンコバルトを０～０．０５質量部添加して、１００℃で３０分熱処理して硬化させ、積層体を調製した。なお表１～７では、上記（Ｂ１）－（Ａ）－（Ｂ２）からなる積層体において、（Ｂ１）がＰＥＴであり、（Ｂ２）がガラスである。 Adhesion test On the polyester resin (B1) having dimensions of 150 mm × 1 mm thickness × 25 mm width, the composition was applied by spin coating (coating thickness: 15 to 20 μm) to form a composition layer (A), Further thereon, glass (B2) having the same dimensions as (B1) shown in Tables 1 to 7 is pressure-bonded, and UV irradiation (wavelength: 325 nm, integrated irradiation intensity: 50 mJ) from the layer (B2) (glass) side. / cm 2 ) and UV curing to prepare a laminate, the layer (B2) was pulled in a direction parallel to the bonding surface of the layer (A) of the composition, and the tensile strength at break was measured. When a thermal polymerization initiator is used, if necessary, 0 to 0.05 part by mass of 6% naphthenic cobalt is added to the composition and cured by heat treatment at 100 ° C. for 30 minutes to prepare a laminate. did. In Tables 1 to 7, in the laminate composed of (B1)-(A)-(B2), (B1) is PET and (B2) is glass.
耐衝撃試験
　試験方法：25mm巾、1mm厚の鋼板にスピンコート法で１５～２０μｍの厚みで接着剤組成物を塗布し、硬化後1m高さから1kgwの球状である重りを落下し以下の基準で評価を行った。
○：剥離しない
△：一部剥離・割れ
×：全面剥離・割れ Impact resistance test Test method: Adhesive composition is applied to a steel plate with a width of 25 mm and a thickness of 1 mm by spin coating to a thickness of 15-20 μm. After curing, a 1 kgw spherical weight is dropped from a height of 1 m and the following criteria are applied. Was evaluated.
○: not peeled △: partly peeled / cracked ×: whole face peeled / cracked
柔軟性試験
　試験方法：25mm巾、1mm厚の鋼板にスピンコート法で１５～２０μｍの厚みで接着剤組成物を塗布し、硬化後90度折り曲げ試験を行い以下の基準で評価を行った。
○：剥離しない
△：一部剥離・割れ
×：全面剥離・割れ Flexibility test Test method: An adhesive composition was applied to a steel sheet having a width of 25 mm and a thickness of 1 mm by spin coating to a thickness of 15 to 20 μm. After curing, a 90-degree bending test was performed and evaluation was performed according to the following criteria.
○: not peeled △: partly peeled / cracked ×: whole face peeled / cracked
耐水性試験
　各積層体に対して、サンプルを沸騰水中（純水） に１時間浸せきした後に室内で自然乾燥させ、組成物の層の外観の悪化の有無について目視観察した。
○：剥離やクラックの発生なし（１時間浸せき）
×：剥離やクラックの発生あり（１時間浸せき） Water Resistance Test Each laminate was immersed in boiling water (pure water) for 1 hour and then naturally dried indoors, and visually observed for deterioration of the appearance of the composition layer.
○: No peeling or cracking (immersion for 1 hour)
×: Peeling or cracking occurred (immersion for 1 hour)
耐候性試験
　各積層体に対して、サンシャインウエザーメータを用いてブラックパネル温度６３℃ で、降雨１２分、乾燥４８分のサイクルで１０００時間暴露後、外観の評価を行った。
○：外観変化なし
×：白化、黄変、剥離あり
　結果を表１～７に示す。 Weather resistance test Each laminate was exposed for 1000 hours in a cycle of 12 minutes of rain and 48 minutes of drying at a black panel temperature of 63 ° C. using a sunshine weather meter, and the appearance was evaluated.
○: No change in appearance ×: Whitening, yellowing, peeling occurred The results are shown in Tables 1-7.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
　表より明らかなように、本発明の実施例１～２２では、前記成分（ａ）、（ｂ）、（ｃ）および（ｄ）を特定の量的関係でもって含有しているので、ポリエステル系樹脂とガラスとの間に優れた接着性を付与することができ、透明性、表面平滑性、柔軟性、耐衝撃性、耐水性、耐候性のバランスに優れる。
　一方、比較例１は、成分（ｂ）の添加量が本発明で規定する上限を超えているので、接着性、耐衝撃性、柔軟性、耐候性が悪化した。
　比較例２は、成分（ａ）の添加量が本発明で規定する上限を超えているので、接着性が悪化した。
　比較例３は、成分（ｃ）を添加していないので、接着性、耐候性が悪化した。
　比較例４は、成分（ｃ）の添加量が本発明で規定する上限を超えているので、接着性、耐水性、耐候性が悪化した。
　比較例５は、成分（ｄ）の添加量が本発明で規定する下限未満であるので、組成物が硬化しなかった。
　比較例６は、成分（ｄ）の添加量が本発明で規定する上限を超えているので、接着性、耐衝撃性、柔軟性が悪化した。 As is apparent from the table, in Examples 1 to 22 of the present invention, the components (a), (b), (c) and (d) are contained in a specific quantitative relationship. Excellent adhesiveness can be imparted between the resin and the glass, and the balance of transparency, surface smoothness, flexibility, impact resistance, water resistance, and weather resistance is excellent.
On the other hand, since the addition amount of the component (b) exceeded the upper limit prescribed | regulated by this invention in the comparative example 1, adhesiveness, impact resistance, a softness | flexibility, and the weather resistance deteriorated.
In Comparative Example 2, since the amount of component (a) added exceeded the upper limit defined in the present invention, the adhesiveness deteriorated.
In Comparative Example 3, since the component (c) was not added, adhesion and weather resistance were deteriorated.
In Comparative Example 4, since the amount of component (c) added exceeded the upper limit defined in the present invention, the adhesion, water resistance, and weather resistance deteriorated.
In Comparative Example 5, since the amount of component (d) added was less than the lower limit specified in the present invention, the composition was not cured.
In Comparative Example 6, since the amount of component (d) added exceeded the upper limit specified in the present invention, the adhesion, impact resistance, and flexibility deteriorated.

Claims (13)

  1. （ａ）ビニルエステル樹脂または不飽和ポリエステル樹脂　１０～４０質量％
    （ｂ）ビニルモノマーおよび／または（メタ）アクリレートモノマー　３０～７０質量％
    （ｃ）変性剤　５～４０質量％、
    （ただし、前記成分（ａ）～（ｃ）の合計は１００質量％である）
    および
    （ｄ）開始剤　前記成分（ａ）～（ｃ）の合計１００質量部に対し０．１～１５質量部
    を含有する、ポリエステル系樹脂とガラスを接着させるための接着剤組成物。     (A) Vinyl ester resin or unsaturated polyester resin 10 to 40% by mass
    (B) Vinyl monomer and / or (meth) acrylate monomer 30 to 70% by mass
    (C) modifying agent 5-40% by mass,
    (However, the total of the components (a) to (c) is 100% by mass)
    And (d) initiator An adhesive composition for adhering a polyester resin and glass, containing 0.1 to 15 parts by mass with respect to 100 parts by mass in total of the components (a) to (c).
  2. 　前記成分（ａ）が、エポキシ（メタ）アクリレートであることを特徴とする請求項１に記載の接着剤組成物。 The adhesive composition according to claim 1, wherein the component (a) is an epoxy (meth) acrylate.
  3. 　前記成分（ｂ）が、Ｎ－ビニル基を有するモノマーであることを特徴とする請求項１または２に記載の接着剤組成物。 3. The adhesive composition according to claim 1 or 2, wherein the component (b) is a monomer having an N-vinyl group.
  4. 　前記成分（ｃ）が、水酸基価４０～３３０ｍｇＫＯＨ／ｇのポリオール（ｃ－１）；および水酸基価４０～３３０ｍｇＫＯＨ／ｇであり、かつ酸価が２～２０ｍｇＫＯＨ／ｇであるポリオール（ｃ－２）；変性ゴム（ｃ－３）；エポキシ当量が１５０～７００ｇ／モルである化合物（ｃ－４）からなる群から選択された少なくとも１種であることを特徴とする請求項１～３のいずれかに記載の接着剤組成物。 The component (c) is a polyol (c-1) having a hydroxyl value of 40 to 330 mgKOH / g; and a polyol (c-2) having a hydroxyl value of 40 to 330 mgKOH / g and an acid value of 2 to 20 mgKOH / g The modified rubber (c-3) is at least one selected from the group consisting of the compound (c-4) having an epoxy equivalent of 150 to 700 g / mol. The adhesive composition described in 1.
  5. 　前記成分（ｃ－１）が、水酸基価４０～３３０ｍｇＫＯＨ／ｇのヒマシ油系ポリオール（ｃ－１－１）；水酸基価４０～３３０ｍｇＫＯＨ／ｇのポリブタジエン系ポリオール（ｃ－１－２）；および水酸基価４０～３３０ｍｇＫＯＨ／ｇのポリイソプレン系ポリオールまたはその水素添加物（ｃ－１－３）からなる群から選択された少なくとも１種であることを特徴とする請求項４に記載の接着剤組成物。 The component (c-1) is a castor oil-based polyol (c-1-1) having a hydroxyl value of 40 to 330 mgKOH / g; a polybutadiene-based polyol (c-1-2) having a hydroxyl value of 40 to 330 mgKOH / g; 5. The adhesive composition according to claim 4, wherein the adhesive composition is at least one selected from the group consisting of a polyisoprene-based polyol having a value of 40 to 330 mg KOH / g or a hydrogenated product thereof (c-1-3). .
  6. 　前記成分（ｃ－１）が、水酸基価４０～３３０ｍｇＫＯＨ／ｇの芳香族系ヒマシ油系ポリオール（ｃ－１－１－１）であることを特徴とする請求項５に記載の接着剤組成物。 6. The adhesive composition according to claim 5, wherein the component (c-1) is an aromatic castor oil-based polyol (c-1-1-1) having a hydroxyl value of 40 to 330 mgKOH / g. .
  7. 　前記成分（ｃ－２）が、水酸基価４０～３３０ｍｇＫＯＨ／ｇであり、かつ酸価が２～２０ｍｇＫＯＨ／ｇであるヒマシ油系ポリオール（ｃ－２－１）であることを特徴とする請求項４に記載の接着剤組成物。 The component (c-2) is a castor oil-based polyol (c-2-1) having a hydroxyl value of 40 to 330 mgKOH / g and an acid value of 2 to 20 mgKOH / g. 5. The adhesive composition according to 4.
  8. 　前記成分（ｃ－３）が酸変性ポリブタジエンまたは酸変性ポリイソプレンであることを特徴とする請求項４に記載の接着剤組成物。 The adhesive composition according to claim 4, wherein the component (c-3) is acid-modified polybutadiene or acid-modified polyisoprene.
  9. 　前記成分（ｃ－４）がエポキシ当量が１５０～２５０ｇ／モルであるポリエポキシ化合物（ｃ－４－１）であることを特徴とする請求項４に記載の接着剤組成物。 The adhesive composition according to claim 4, wherein the component (c-4) is a polyepoxy compound (c-4-1) having an epoxy equivalent of 150 to 250 g / mol.
  10. 　前記成分（ｃ－４）がエポキシ当量が５００～７００ｇ／モルである飽和骨格を持つ重合体（ｃ－４－２）であることを特徴とする請求項４に記載の接着剤組成物。 The adhesive composition according to claim 4, wherein the component (c-4) is a polymer (c-4-2) having a saturated skeleton having an epoxy equivalent of 500 to 700 g / mol.
  11. 　前記ポリエステル系樹脂が、ポリエチレンテレフタレートであることを特徴とする請求項１～１０のいずれかに記載の接着剤組成物。 The adhesive composition according to any one of claims 1 to 10, wherein the polyester resin is polyethylene terephthalate.
  12. 　請求項１～１１のいずれかに記載の接着剤組成物を介して、ポリエステル系樹脂の層と、ガラスの層とが積層されてなることを特徴とする積層体。 A laminate comprising a polyester resin layer and a glass layer laminated via the adhesive composition according to any one of claims 1 to 11.
  13. 　請求項１２に記載の積層体からなることを特徴とする窓ガラス。 A window glass comprising the laminate according to claim 12.
PCT/JP2010/060888 2010-06-25 2010-06-25 Adhesive composition and laminate body WO2011161827A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018197328A (en) * 2017-05-25 2018-12-13 高圧ガス工業株式会社 Two-part main agent type acrylic adhesive

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63284213A (en) * 1987-04-14 1988-11-21 チバ−ガイギー　アクチエンゲゼルシヤフト Photopolymerizable material composition
JPH1025453A (en) * 1996-07-08 1998-01-27 Nippon Kayaku Co Ltd Adhesive for cathode ray tube and cured material thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63284213A (en) * 1987-04-14 1988-11-21 チバ−ガイギー　アクチエンゲゼルシヤフト Photopolymerizable material composition
JPH1025453A (en) * 1996-07-08 1998-01-27 Nippon Kayaku Co Ltd Adhesive for cathode ray tube and cured material thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018197328A (en) * 2017-05-25 2018-12-13 高圧ガス工業株式会社 Two-part main agent type acrylic adhesive

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