WO2011151890A1 - Adhesive composition, bonding method, and laminate - Google Patents

Adhesive composition, bonding method, and laminate Download PDF

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Publication number
WO2011151890A1
WO2011151890A1 PCT/JP2010/059252 JP2010059252W WO2011151890A1 WO 2011151890 A1 WO2011151890 A1 WO 2011151890A1 JP 2010059252 W JP2010059252 W JP 2010059252W WO 2011151890 A1 WO2011151890 A1 WO 2011151890A1
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WIPO (PCT)
Prior art keywords
mass
adhesive composition
resin
acid
layer
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PCT/JP2010/059252
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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
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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/JP2010/059252 priority Critical patent/WO2011151890A1/en
Priority to JP2012518402A priority patent/JPWO2011152404A1/en
Priority to EP20110789807 priority patent/EP2578650A4/en
Priority to CN2011800268289A priority patent/CN103038299A/en
Priority to PCT/JP2011/062499 priority patent/WO2011152404A1/en
Priority to KR20127033493A priority patent/KR20130142882A/en
Priority to US13/701,304 priority patent/US10590299B2/en
Publication of WO2011151890A1 publication Critical patent/WO2011151890A1/en

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    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • 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
    • 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
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • 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
    • B32B2307/536—Hardness
    • 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
    • B32B2307/54—Yield strength; Tensile strength
    • 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
    • B32B2457/00—Electrical equipment
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • 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
    • B32B2551/00—Optical elements
    • 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
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for

Definitions

  • the present invention relates to an adhesive composition, a bonding method, and a laminate, and in particular, soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel sheet; polyolefin resin or olefin modified with a polar group-containing compound and a polar group.
  • the present invention relates to an adhesive composition excellent in adhesiveness with a layer of a containing compound; magnesium; an acrylonitrile-butadiene-styrene copolymer; a polyester resin; or an acrylic resin.
  • the present invention also relates to a method for bonding the adhesive composition to the layers. Furthermore, this invention relates to the laminated body of the said adhesive composition and each said layer.
  • 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.
  • Soft and hard vinyl chloride resin polystyrene; polycarbonate; glass; aluminum; steel plate; polyolefin resin modified with polar group-containing compound or copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer
  • the balance of coalescence, polyester resin; or acrylic resin layer, and transparency, surface smoothness, flexibility, and impact resistance were not sufficient.
  • An object of the present invention is an adhesive composition having excellent adhesion to polar resins, ceramics, metals, etc., and having a good balance of transparency, surface smoothness, flexibility, and impact resistance, and adhesion using the same It is to provide a method and a laminate.
  • 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) Compound having a cyclic structure and one ethylenically unsaturated group 30 to 60% 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 comprising 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 urethane (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 adherend of the adhesive composition is a soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; a polyolefin resin modified with a polar group-containing compound or a copolymer of an olefin and a polar group-containing compound
  • the adhesive composition as described in any one of 1 to 10 above, which is magnesium; acrylonitrile-butadiene-styrene copolymer; polyester resin; or acrylic resin.
  • Step I (A) Vinyl ester resin or unsaturated polyester resin 10 to 40% by mass (B) Compound having a cyclic structure and one ethylenically unsaturated group 30 to 60% by mass (C) modifying agent 5-40% by mass, (However, the total of the components (a) to (c) is 100% by mass) And (d) an initiator, a step of mixing 0.1 to 15 parts by mass with respect to a total of 100 parts by mass of the components (a) to (c) to prepare an adhesive composition, Step II: Soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; polyolefin resin modified with polar group-containing compound or copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer A step of laminating the adhesive composition obtained in Step I above on the surface of the layer (B1) of polyester resin; or acrylic resin; and forming the layer (A)
  • Soft and hard vinyl chloride resin polystyrene; polycarbonate; glass; aluminum; steel plate; polyolefin resin modified with polar group-containing compound or copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer A laminate formed by contacting the layer (B1) with the layer (B1) of the polyester resin; or the acrylic
  • the adhesive composition of the present invention contains the components (a), (b), (c) and (d) with a specific quantitative relationship, polar resins, ceramics, metals, etc.
  • Soft and hard vinyl chloride resin polystyrene; polycarbonate; glass; aluminum; steel plate (for example, cold-rolled steel plate, hot-rolled steel plate, etc.); polyolefin resin or olefin modified with polar group-containing compound and polar group-containing compound Copolymer; magnesium; acrylonitrile-butadiene-styrene copolymer; polyester resin; or excellent adhesion to acrylic resin layers; transparency, surface smoothness, flexibility, impact resistance Excellent balance.
  • the bonding method of the present invention comprises a layer (A) of an adhesive composition containing the components (a), (b), (c) and (d) in a specific quantitative relationship, and soft and hard vinyl chloride.
  • Resin Polystyrene; Polycarbonate; Glass; Aluminum; Steel plate; Polyolefin resin modified with polar group-containing compound or copolymer of olefin and polar group-containing compound; Magnesium; Acrylonitrile-butadiene-styrene copolymer; Polyester resin; Alternatively, since the acrylic resin layers (B1) and (B2) are laminated in a specific process order, the adhesion of the three layers becomes strong.
  • a laminate according to one aspect of the present invention comprises a layer (A) of an adhesive composition containing the components (a), (b), (c) and (d) in a specific quantitative relationship, and a soft layer. And rigid vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; polyolefin resin modified with a polar group-containing compound or copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer; Polyester resin; or a laminate with an acrylic resin layer (B1). Since the layer (A) of the adhesive composition has an excellent balance of transparency, surface smoothness, flexibility and impact resistance, it advantageously acts as a primer layer for the layer (B1).
  • a laminate according to another aspect of the present invention comprises a layer (A) of an adhesive composition containing the components (a), (b), (c) and (d) in a specific quantitative relationship, and a soft layer.
  • rigid vinyl chloride resin polystyrene; polycarbonate; glass; aluminum; steel plate; polyolefin resin modified with a polar group-containing compound or copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer; Since it is a laminate of polyester resin; or acrylic resin layers (B1) and (B2), the adhesiveness between layers (A), (B1) and (B2) is excellent. Moreover, it is excellent in the balance of transparency, surface smoothness, flexibility and impact 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 specifically selected from a urethane (meth) acrylate resin, an epoxy (meth) acrylate resin, and a polyester (meth) acrylate resin, and more preferably has excellent flexibility and impact resistance.
  • urethane (meth) acrylate resins that are excellent in adhesion between different materials can be used.
  • 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) 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)
  • the component (b) examples include monomers having an N-vinyl group in terms of excellent adhesion to metals, engineering plastics and ceramics.
  • monomers having an N-vinyl group in terms of excellent adhesion to metals, engineering plastics and ceramics.
  • N-vinylcaprolactam is preferable in terms of excellent metal adhesion, viscosity-reducing properties, safety, impact resistance, and flexibility.
  • Such a monomer having an N-vinyl group serves as a reactive diluent and improves the curing rate of the composition by blending an appropriate amount.
  • Denaturant Component (c) used in the present invention is a denaturant.
  • the modifying agent (c) include (i) a polyol (c-1) having a hydroxyl value of 40 to 330 mg KOH / g.
  • the hydroxyl value of component (c) is determined by the adherend (soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate (for example, SPCC); polyolefin resin modified with a polar group-containing compound. Or a copolymer of an olefin and a polar group-containing compound; magnesium; an acrylonitrile-butadiene-styrene copolymer; a polyester resin; or an acrylic resin).
  • adherend soft and hard vinyl chloride resin
  • polystyrene polycarbonate
  • glass aluminum
  • steel plate for example, SPCC
  • polyolefin resin modified with a polar group-containing compound or a copolymer of an olefin and a polar group-containing compound
  • magnesium an acrylonitrile-butadiene-styrene copolymer
  • polyester resin or an acrylic resin
  • 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. Any type of adherend (soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; polyolefin resin or olefin modified with a polar group-containing compound and a polar group-containing compound) Copolymer, magnesium, acrylonitrile-butadiene-styrene copolymer, polyester resin, or acrylic resin).
  • the hydroxyl value is preferably 40 to 330 mgKOH / g from the viewpoint of the selective adhesive strength, and more preferably 150 to 300 mgKOH / g.
  • polyol (c-1) having a hydroxyl value of 40 to 330 mg KOH / g an adherend (soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; polyolefin resin modified with a polar group-containing compound) Or a copolymer of an olefin and a polar group-containing compound; magnesium; an acrylonitrile-butadiene-styrene copolymer; a polyester resin; or an acrylic resin).
  • 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) having a hydroxyl value of 40 to 330 mgKOH / g in terms of improving the toughness (impact resistance), flexibility, and adhesion to different materials of the adhesive layer. -1-1) is preferred. 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.).
  • adducts obtained by adding polyalkylene glycol and bisphenol A to ricinoleic acid are soft and hard vinyl chloride resins; polystyrene; polycarbonate; glass; aluminum; steel plates; polyolefin resins or olefins modified with polar group-containing compounds and polar Adhesiveness to a group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer; polyester resin; or acrylic resin is preferable.
  • it can be represented by 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
  • bisphenol type epoxy resins such as polyglycidyl ether compounds such as 1,3-bis (4-hydroxycumylbenzene) and 1,4-bis (4-hydroxycumylbenzene) It is preferable because an excellent coating film can be formed.
  • 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 adherend soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; polar group-containing compound
  • Modified polyolefin resin or copolymer of olefin and polar group-containing compound magnesium; acrylonitrile-butadiene-styrene copolymer; polyester resin; or acrylic resin) (especially between different materials) Adhesive strength) is improved.
  • 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)), soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; polyolefin modified with polar group-containing compound Resin or copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer; polyester resin; or excellent adhesion to the acrylic resin layer, especially metal adhesion and hydrolysis resistance Excellent in properties.
  • the Ito Oil URIC H-2151U is a polyol containing a castor oil-based polyol, an acidic phosphate compound having 12 or more carbon atoms and terpene phenols (viscosity: 3,500 to 8,500 mPa ⁇ s / 25).
  • 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 used for bonding the adhesive composition of the present invention to a metal substrate or a glass substrate. Primarily improves the wettability of the substrate surface and functions to improve 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 adhesive composition is deteriorated. Absent.
  • 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 adhesive property of the resulting adhesive composition is undesirably lowered.
  • 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, monomethyl maleate or monoethyl maleate.
  • 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 adhesive composition is lowered
  • it exceeds 120 (mgKOH / g) the viscosity of the obtained adhesive composition is increased and the workability is lowered. To do.
  • 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 adhesive composition obtained is rich in adhesiveness, and since the polarity is sufficiently imparted, the adhesive composition of the present invention can be made more flexible, easy to adjust the flexibility, and decorative. Excellent.
  • 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 obtained adhesive composition is excellent in terms of decorating properties.
  • 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 adhesive composition of the present invention include mononuclear polynuclear compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol.
  • Polyglycidyl ether compounds of dihydric phenol 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 Polynuclear polyhydric phenols such as 2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, terpene phenol Polygly
  • 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 the metal 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 has a fully saturated skeleton (epoxidized ethylene / propylene / ethylene / butylene-OH structure) having an epoxy equivalent of 590 g / mol, a hydroxyl equivalent of 7000 g / mol, and a glass transition temperature of ⁇ 53 ° C. It is a coalescence and is preferable from the viewpoint of metal adhesion as a reason for use in the present invention.
  • 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.
  • soft and hard vinyl chloride resin in less than 10% by mass, soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel sheet; polyolefin resin modified with a polar group-containing compound or copolymer of olefin and polar group-containing compound; magnesium; -Adhesion, flexibility, and impact resistance with a layer of butadiene-styrene copolymer; polyester resin; or acrylic resin are reduced.
  • the component (b) is blended in an amount of 30 to 60% by mass from the viewpoints of adhesiveness, flexibility and impact resistance.
  • a more preferable amount of component (b) is 40 to 55% by mass from the viewpoint of easy processing viscosity. If the blending amount of component (b) exceeds 60% by mass, the adhesiveness, flexibility and impact resistance are lowered. Moreover, if it is less than 30 mass%, adhesiveness, a softness
  • 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, and the adhesive strength also decreases.
  • it is less than 5% by mass adhesiveness, flexibility and impact resistance are lowered.
  • 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 adhesive composition of the present invention comprises, as an adherend, a soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel sheet; a polyolefin resin modified with a polar group-containing compound or an olefin and a polar group-containing compound.
  • Copolymer e.g, ethylene terephthalate (PET), polybutylene terephthalate, etc.); or Acrylic resin (eg, PMMA, etc.) (hereinafter referred to as a specific adherend layer)
  • Adhesiveness to (B1) or a specific adherend layer (B2)) is particularly good.
  • Adhesive compositions having good adhesion to these adherends are not disclosed in the prior art. Moreover, it is very excellent in the adhesiveness (adhesion between different materials) when different materials are used for B1 and B2 among the adherends.
  • the different materials specifically include hard vinyl chloride resin and glass, soft vinyl chloride resin and glass, polystyrene resin and aluminum, polycarbonate resin and aluminum, acrylonitrile-butadiene-styrene copolymer (ABS) and glass, Glass and aluminum, magnesium and polycarbonate resin, steel plate and acrylic resin (for example, polymethyl methacrylate (PMMA)), polyester (for example, polyethylene terephthalate) and acrylonitrile-butadiene-styrene copolymer (ABS), acrylic resin (for example, polymethacrylic acid) Methyl (PMMA)) and acrylonitrile-butadiene-styrene copolymer (ABS).
  • PMMA polymethyl methacrylate
  • the polyolefin resin modified with a polar group-containing compound is a polyolefin into which polar groups such as —OH, —NO 2 , —CO, —NH 2 , —NH, —OCH 3 , —SO 3 H and the like are introduced.
  • polar groups such as —OH, —NO 2 , —CO, —NH 2 , —NH, —OCH 3 , —SO 3 H and the like are introduced.
  • examples thereof include polyolefin resins grafted with at least one selected from maleic anhydride and glycidyl methacrylate, and specific examples include polyethylene and polypropylene grafted with maleic anhydride, and polyethylene and polypropylene grafted with glycidyl methacrylate. .
  • Copolymers of olefins and polar group-containing compounds include, for example, copolymers of ethylene and vinyl acetate (EVA), copolymers of ethylene and (meth) acrylic acid (EAA, EMA, etc.), ethylene and A copolymer (EEA etc.) with (meth) acrylic acid ester is mentioned.
  • the bonding method of the present invention In the bonding method of the present invention, as the step I, the components (a) to (d) and, if necessary, other fillers are mixed in an arbitrary order according to the blending ratio, and the adhesive of the present invention.
  • the composition is prepared, and then, as Step II, the adhesive composition is laminated on the layer (B1) of the specific adherend to form the adhesive composition layer (A).
  • Step II the adhesive composition is laminated on the layer (B1) of the specific adherend to form the adhesive composition layer (A).
  • a step of further laminating the layer (A) of the composition and the layer (B2) of the specific adherend According to the bonding method of the present invention, the bonding of the three layers (B1)-(A)-(B2) becomes strong.
  • 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.
  • it is excellent in transparency, the strength of the curvature of the resin molding by hardening shrinkage
  • Coating methods include: spin coating method, (doctor) knife coating method, micro gravure coating method, direct gravure coating method, offset gravure method, reverse gravure method, reverse roll coating method, (Meyer) bar coating method, die coating method
  • a method such as spray coating or dip coating can be preferably applied.
  • a manual spinner ASS-301 type manufactured by Able Co., Ltd.
  • 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.
  • 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 prepared by preparing the adhesive composition of the present invention as described above, laminating the adhesive composition on the specific adherend layer (B1), and then laminating the adhesive composition layer.
  • the laminated body of this invention laminates
  • the laminate of the present invention has good adhesion between the layers (B1) and (B2) of the specific adherend and the layer (A) of the adhesive composition, and has transparency, surface smoothness, flexibility and resistance. Excellent balance of impact.
  • the layer (A) of the adhesive composition acts advantageously as a primer layer of (B1).
  • the primer layer can further contribute to adhesion to a paint applied thereon depending on the application.
  • the layer of the specific 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 raw materials used in the examples and comparative examples are as follows.
  • Component (b) Compound having a cyclic structure and one ethylenically unsaturated group
  • 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
  • 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.
  • 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
  • Examples 1 to 21 and Comparative Examples 1 to 6 In the blending ratios (parts by mass) shown in Tables 1 to 8 below, the component (a) is placed in 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 an adhesive composition. The viscosity (mPa ⁇ s) at 25 ° C. of the obtained adhesive 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 8.
  • Example 9 is an example in which (ii) a thermal polymerization initiator was used for component (d) in Example 2.
  • a thermal polymerization initiator was used for component (d) in Example 2.
  • an adhesive composition was applied by spin coating (coating thickness 15-20 ⁇ m).
  • the laminate was prepared by subjecting to partial heat treatment and curing.
  • Each specific adherend (B1) used is as follows. ⁇ Hard vinyl chloride resin PVC (Riken Technos, trade name Riken PVC Compound RE-3844) -Soft vinyl chloride resin PVC (manufactured by Riken Technos, trade name Leonyl BZL6060N) ⁇ Polystyrene PS (Toyo Styrol GP G100C, manufactured by Toyo Styrene Co., Ltd.) ⁇ Polycarbonate PC (trade name Panlite L-1225L, manufactured by Teijin Chemicals Ltd.) ⁇ Acrylonitrile-butadiene-styrene copolymer ABS (manufactured by UMG, trade name UMG ABS EX114) ⁇ Glass (slide glass for microscope preparation) ⁇ Aluminum (H5052, Al-Mg) Magnesium (Osaka Fuji Kogyo Co., Ltd., AZ31B, Mg content 91% or more) ⁇ Steel (SPCC: Cold rolled steel) ⁇ PET: Unitika Unit
  • the obtained laminate was subjected to the following cross-cut tape test.
  • Adhesion test 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 tape test Cross-cut tape test (Cross-cut Test, coating thickness 15-20 ⁇ m (spin coating method)): A 1 ⁇ 1 mm square cross-cut using a cutter knife on the test surface (adhesive composition layer (A) side) Make a cut. Use the cutter guide.
  • the results are also shown in Tables 1 to 8.
  • Flexibility test method An adhesive composition was applied to a steel sheet of 25 mm width and 1 mm thickness by spin coating to a thickness of 15 to 20 ⁇ m, and after curing, a 90-degree bending test was performed and the following criteria were evaluated. ⁇ : Not peeled ⁇ : Partially peeled / cracked ⁇ : Whole surface peeled / crack
  • Transparency test In order to evaluate transparency, the haze of the molded articles (base glass) of Examples and Comparative Examples was measured using a haze meter (NDH2000: Nippon Denshoku) based on JIS-K7136: 2000. . In the evaluation, “ ⁇ ” indicates that the measured value is less than 1.0%, “ ⁇ ” indicates that the measured value is 1.0% or more and less than 2.0%, and “x” indicates 2.0% or more.
  • the measurement surface was a coating surface.
  • the adhesive composition contains the components (a), (b), (c) and (d) in a specific quantitative relationship. Therefore, it showed excellent adhesion to polar resins, ceramics, metals and the like.
  • Comparative Examples 1 and 2 the blending amounts of the components (a) and (b) are outside the range defined in the present invention, and the adhesion to polar resins, ceramics, metals, etc. is deteriorated. Moreover, impact resistance and flexibility were also deteriorated.
  • component (b) was less than the lower limit, the viscosity increased.
  • Comparative Example 3 does not contain component (c); in Comparative Example 4, the amount of component (c) exceeds the upper limit specified in the present invention, so the adhesion to polar resins, ceramics, metals, etc. deteriorates. ing. Moreover, impact resistance and flexibility were also deteriorated.
  • Comparative Example 5 since the blending amount of component (d) is less than the lower limit specified in the present invention, the adhesion to polar resins, ceramics, metals, and the like is deteriorated due to insufficient curing.
  • the compounding amount of the component (d) exceeds the upper limit defined in the present invention, so that the adhesion to polar resins, ceramics, metals, etc. is deteriorated. Moreover, impact resistance and flexibility were also deteriorated.
  • the adhesive composition of the present invention comprises a soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel sheet; a polyolefin resin modified with a polar group-containing compound or a copolymer of an olefin and a polar group-containing compound; An acrylonitrile-butadiene-styrene copolymer; a polyester resin; or an acrylic resin, and an excellent balance of transparency, surface smoothness, flexibility, and impact resistance. Therefore, it is suitable for forming a transparent primer layer on the surface of these specific adherends and adhering between the specific adherends (particularly between different materials). It is also useful in the fields of packaging materials, printing materials, display materials, electrical / electronic component materials, optical component materials, liquid crystal panels, and the like.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Disclosed is an adhesive composition comprising (a) 10 to 40% by mass of a vinyl ester resin or an unsaturated polyester resin, (b) 30 to 60% by mass of a compound having a cyclic structure and one ethylenic unsaturated group, (c) 5 to 40% by mass of a polyol (wherein the total amount of the components (a) to (c) is 100% by mass), and (d) an initiator in an amount of 0.1 to 15 parts by mass with respect to 100 parts by mass of the total amount of the components (a) to (c).

Description

接着剤組成物、接着方法および積層体Adhesive composition, adhesion method and laminate
　本発明は、接着剤組成物、接着方法および積層体に関し、特に、軟質および硬質塩化ビニル樹脂；ポリスチレン；ポリカーボネート；ガラス；アルミニウム；鋼板；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂の層との接着性に優れる接着剤組成物に関する。
　また本発明は、前記接着剤組成物と前記各層との接着方法に関する。
　さらに本発明は、前記接着剤組成物と前記各層との積層体に関する。 The present invention relates to an adhesive composition, a bonding method, and a laminate, and in particular, soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel sheet; polyolefin resin or olefin modified with a polar group-containing compound and a polar group. The present invention relates to an adhesive composition excellent in adhesiveness with a layer of a containing compound; magnesium; an acrylonitrile-butadiene-styrene copolymer; a polyester resin; or an acrylic resin.
The present invention also relates to a method for bonding the adhesive composition to the layers.
Furthermore, this invention relates to the laminated body of the said adhesive composition and each said layer.
　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、軟質および硬質塩化ビニル樹脂；ポリスチレン；ポリカーボネート；ガラス；アルミニウム；鋼板；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂の層との接着性、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. , Soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; polyolefin resin modified with polar group-containing compound or copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer The balance of coalescence, polyester resin; or acrylic resin layer, and transparency, surface smoothness, flexibility, and impact resistance were not sufficient.
特開平２－２９６８７９号公報JP-A-2-296879
　本発明の目的は、極性樹脂、セラミックス、金属等に対し優れた接着性を有し、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、これを用いた接着方法および積層体を提供することにある。 An object of the present invention is an adhesive composition having excellent adhesion to polar resins, ceramics, metals, etc., and having a good balance of transparency, surface smoothness, flexibility, and impact resistance, and adhesion using the same It is to provide a method and a laminate.
　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）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　３０～６０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
からなる接着剤組成物。
　２．前記成分（ａ）が、ウレタン（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．前記接着剤組成物の被着体が、軟質および硬質塩化ビニル樹脂；ポリスチレン；ポリカーボネート；ガラス；アルミニウム；鋼板；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂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．工程Ｉ：
（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）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　３０～６０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
を任意の順に混合し、接着剤組成物を調製する工程、
工程ＩＩ：
　軟質および硬質塩化ビニル樹脂；ポリスチレン；ポリカーボネート；ガラス；アルミニウム；鋼板；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂の層（Ｂ１）の表面に前記工程Ｉで得られた接着剤組成物を積層し、接着剤組成物の層（Ａ）を形成する工程、
工程ＩＩＩ：
　前記工程ＩＩで得られた積層体の接着剤組成物の層（Ａ）と、軟質および硬質塩化ビニル樹脂；ポリスチレン；ポリカーボネート；ガラス；アルミニウム；鋼板；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂の層（Ｂ２）をさらに積層する工程、
を工程Ｉ、工程ＩＩおよび工程ＩＩＩのこの順で行うことを特徴とする接着方法。
　１３．（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）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　３０～６０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
からなる接着剤組成物の層（Ａ）と、
（ただし、前記成分（ａ）～（ｄ）の合計は１００質量％である）
　軟質および硬質塩化ビニル樹脂；ポリスチレン；ポリカーボネート；ガラス；アルミニウム；鋼板；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂の層（Ｂ１）と
を前記層（Ａ）および層（Ｂ１）が接するようにして形成された積層体。
　１４．軟質および硬質塩化ビニル樹脂；ポリスチレン；ポリカーボネート；ガラス；アルミニウム；鋼板；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂の層（Ｂ１）と、
（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）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　３０～６０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
からなる接着剤組成物層（Ａ）と、
　軟質および硬質塩化ビニル樹脂；ポリスチレン；ポリカーボネート；ガラス；アルミニウム；鋼板；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂の層（Ｂ２）と、
を前記層（Ｂ１）、層（Ａ）および層（Ｂ２）の３層がこの順で接するようにして形成された積層体。 That is, the present invention is as follows.
1. (A) Vinyl ester resin or unsaturated polyester resin 10 to 40% by mass
(B) Compound having a cyclic structure and one ethylenically unsaturated group 30 to 60% 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 comprising 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 urethane (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. The adherend of the adhesive composition is a soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; a polyolefin resin modified with a polar group-containing compound or a copolymer of an olefin and a polar group-containing compound The adhesive composition as described in any one of 1 to 10 above, which is magnesium; acrylonitrile-butadiene-styrene copolymer; polyester resin; or acrylic resin.
12 Step I:
(A) Vinyl ester resin or unsaturated polyester resin 10 to 40% by mass
(B) Compound having a cyclic structure and one ethylenically unsaturated group 30 to 60% by mass
(C) modifying agent 5-40% by mass,
(However, the total of the components (a) to (c) is 100% by mass)
And (d) an initiator, a step of mixing 0.1 to 15 parts by mass with respect to a total of 100 parts by mass of the components (a) to (c) to prepare an adhesive composition,
Step II:
Soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; polyolefin resin modified with polar group-containing compound or copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer A step of laminating the adhesive composition obtained in Step I above on the surface of the layer (B1) of polyester resin; or acrylic resin; and forming the layer (A) of adhesive composition;
Step III:
Layer (A) of the adhesive composition of the laminate obtained in the step II, and soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; polyolefin resin or olefin modified with a polar group-containing compound And a copolymer of a polar group-containing compound; magnesium; an acrylonitrile-butadiene-styrene copolymer; a polyester resin; or an acrylic resin layer (B2);
Is performed in this order of step I, step II and step III.
13. (A) Vinyl ester resin or unsaturated polyester resin 10 to 40% by mass
(B) Compound having a cyclic structure and one ethylenically unsaturated group 30 to 60% by mass
(C) modifying agent 5-40% by mass,
(However, the total of the components (a) to (c) is 100% by mass)
And (d) an initiator layer (A) of an adhesive composition comprising 0.1 to 15 parts by mass with respect to a total of 100 parts by mass of the components (a) to (c);
(However, the total of the components (a) to (d) is 100% by mass)
Soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; polyolefin resin modified with polar group-containing compound or copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer A laminate formed by contacting the layer (B1) with the layer (B1) of the polyester resin; or the acrylic resin;
14 Soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; polyolefin resin modified with polar group-containing compound or copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer A polyester resin; or an acrylic resin layer (B1);
(A) Vinyl ester resin or unsaturated polyester resin 10 to 40% by mass
(B) Compound having a cyclic structure and one ethylenically unsaturated group 30 to 60% by mass
(C) modifying agent 5-40% by mass,
(However, the total of the components (a) to (c) is 100% by mass)
And (d) an initiator, an adhesive composition layer (A) comprising 0.1 to 15 parts by mass with respect to a total of 100 parts by mass of the components (a) to (c);
Soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; polyolefin resin modified with polar group-containing compound or copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer A polyester resin; or an acrylic resin layer (B2);
A layered product formed by contacting the three layers of the layer (B1), the layer (A) and the layer (B2) in this order.
　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、極性樹脂、セラミックス、金属等、具体的には軟質および硬質塩化ビニル樹脂；ポリスチレン；ポリカーボネート；ガラス；アルミニウム；鋼板（例えば冷間圧延鋼板等、熱間圧延鋼板など）；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂の層に対し優れた接着性を有し、透明性、表面平滑性、柔軟性、耐衝撃性のバランスに優れる。
　本発明の接着方法は、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の層（Ａ）と、軟質および硬質塩化ビニル樹脂；ポリスチレン；ポリカーボネート；ガラス；アルミニウム；鋼板；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂の層（Ｂ１）および（Ｂ２）とを特定の工程順で積層する方法であるので、３層の接着が強固となる。
　本発明の一つの見地の積層体は、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の層（Ａ）と、軟質および硬質塩化ビニル樹脂；ポリスチレン；ポリカーボネート；ガラス；アルミニウム；鋼板；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂の層（Ｂ１）との積層体である。接着剤組成物の層（Ａ）は、透明性、表面平滑性、柔軟性、耐衝撃性のバランスに優れるので、前記層（Ｂ１）のプライマー層として有利に作用する。
　本発明の別の見地の積層体は、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の層（Ａ）と、軟質および硬質塩化ビニル樹脂；ポリスチレン；ポリカーボネート；ガラス；アルミニウム；鋼板；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂の層（Ｂ１）および（Ｂ２）との積層体であるので、層（Ａ）、（Ｂ１）および（Ｂ２）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。 Since the adhesive composition of the present invention contains the components (a), (b), (c) and (d) with a specific quantitative relationship, polar resins, ceramics, metals, etc. Soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate (for example, cold-rolled steel plate, hot-rolled steel plate, etc.); polyolefin resin or olefin modified with polar group-containing compound and polar group-containing compound Copolymer; magnesium; acrylonitrile-butadiene-styrene copolymer; polyester resin; or excellent adhesion to acrylic resin layers; transparency, surface smoothness, flexibility, impact resistance Excellent balance.
The bonding method of the present invention comprises a layer (A) of an adhesive composition containing the components (a), (b), (c) and (d) in a specific quantitative relationship, and soft and hard vinyl chloride. Resin; Polystyrene; Polycarbonate; Glass; Aluminum; Steel plate; Polyolefin resin modified with polar group-containing compound or copolymer of olefin and polar group-containing compound; Magnesium; Acrylonitrile-butadiene-styrene copolymer; Polyester resin; Alternatively, since the acrylic resin layers (B1) and (B2) are laminated in a specific process order, the adhesion of the three layers becomes strong.
A laminate according to one aspect of the present invention comprises a layer (A) of an adhesive composition containing the components (a), (b), (c) and (d) in a specific quantitative relationship, and a soft layer. And rigid vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; polyolefin resin modified with a polar group-containing compound or copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer; Polyester resin; or a laminate with an acrylic resin layer (B1). Since the layer (A) of the adhesive composition has an excellent balance of transparency, surface smoothness, flexibility and impact resistance, it advantageously acts as a primer layer for the layer (B1).
A laminate according to another aspect of the present invention comprises a layer (A) of an adhesive composition containing the components (a), (b), (c) and (d) in a specific quantitative relationship, and a soft layer. And rigid vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; polyolefin resin modified with a polar group-containing compound or copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer; Since it is a laminate of polyester resin; or acrylic resin layers (B1) and (B2), the adhesiveness between layers (A), (B1) and (B2) is excellent. Moreover, it is excellent in the balance of transparency, surface smoothness, flexibility and impact 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、より好ましくは柔軟性、耐衝撃性が特に優れ、かつ異材質間での接着性にも優れるウレタン（メタ）アクリレート樹脂が挙げられる。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 is a vinyl ester resin or an unsaturated polyester resin.
The vinyl ester resin is specifically selected from a urethane (meth) acrylate resin, an epoxy (meth) acrylate resin, and a polyester (meth) acrylate resin, and more preferably has excellent flexibility and impact resistance. In addition, urethane (meth) acrylate resins that are excellent in adhesion between different materials can be used. 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.
（ｂ）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）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) Compound having a cyclic structure and one ethylenically unsaturated group Component (b) 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及び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）としては一般的に金属、エンジニアリングプラスチックス、セラミックス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金属接着性、減粘特性、安全性、耐衝撃性、柔軟性に優れる点で好ましい。
　このようなＮ－ビニル基を有するモノマーは、反応性希釈剤となると共に、適当量配合することにより、組成物の硬化速度向上をはかれる。 Examples of the component (b) include monomers having an N-vinyl group in terms of excellent adhesion to metals, engineering plastics and ceramics. For example, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide. , N-vinylimidazole, N-vinylcarbazole and the like. Among these, N-vinylcaprolactam is preferable in terms of excellent metal adhesion, viscosity-reducing properties, safety, impact resistance, and flexibility.
Such a monomer having an N-vinyl group serves as a reactive diluent and improves the curing rate of the composition by blending an appropriate amount.
（ｃ）変性剤
　本発明で用いられる成分（ｃ）は、変性剤である。
　変性剤（ｃ）としては、例えば
（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのポリオール（ｃ－１）
と、
（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）
が挙げられる。 (C) Denaturant Component (c) used in the present invention is a denaturant.
Examples of the modifying agent (c) include (i) a polyol (c-1) having a hydroxyl value of 40 to 330 mg KOH / g.
When,
(I) a polyol having a hydroxyl value of 40 to 330 mg KOH / g and (ii) an acid value of 2 to 20 mg KOH / g (c-2)
Is mentioned.
（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、本発明の特徴である被着体（軟質および硬質塩化ビニル樹脂；ポリスチレン；ポリカーボネート；ガラス；アルミニウム；鋼板（例えばSPCC）；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂）に対する選択的接着力向上へ寄与する。 The hydroxyl value of component (c) is determined by the adherend (soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate (for example, SPCC); polyolefin resin modified with a polar group-containing compound. Or a copolymer of an olefin and a polar group-containing compound; magnesium; an acrylonitrile-butadiene-styrene copolymer; a polyester resin; or an acrylic resin).
　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（軟質および硬質塩化ビニル樹脂；ポリスチレン；ポリカーボネート；ガラス；アルミニウム；鋼板；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂）に対する選択的接着力は良好である。
　（ｉ）水酸基価は４０～３３０ｍｇＫＯＨ／ｇであるのが上記選択的接着力の点で好ましく、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. Any type of adherend (soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; polyolefin resin or olefin modified with a polar group-containing compound and a polar group-containing compound) Copolymer, magnesium, acrylonitrile-butadiene-styrene copolymer, polyester resin, or acrylic resin).
(I) The hydroxyl value is preferably 40 to 330 mgKOH / g from the viewpoint of the selective adhesive strength, 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（軟質および硬質塩化ビニル樹脂；ポリスチレン；ポリカーボネート；ガラス；アルミニウム；鋼板；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂）に対する選択的接着力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 polyol (c-1) having a hydroxyl value of 40 to 330 mg KOH / g, an adherend (soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; polyolefin resin modified with a polar group-containing compound) Or a copolymer of an olefin and a polar group-containing compound; magnesium; an acrylonitrile-butadiene-styrene copolymer; a polyester resin; or an acrylic resin).
(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、接着層の強靭性（耐衝撃性）、柔軟性、及び異材質との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) having a hydroxyl value of 40 to 330 mgKOH / g in terms of improving the toughness (impact resistance), flexibility, and adhesion to different materials of the adhesive layer. -1-1) is preferred. 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、軟質および硬質塩化ビニル樹脂；ポリスチレン；ポリカーボネート；ガラス；アルミニウム；鋼板；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂に対する接着性が好ましく、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, adducts obtained by adding polyalkylene glycol and bisphenol A to ricinoleic acid are soft and hard vinyl chloride resins; polystyrene; polycarbonate; glass; aluminum; steel plates; polyolefin resins or olefins modified with polar group-containing compounds and polar Adhesiveness to a group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer; polyester resin; or acrylic resin is preferable. For example, it can be represented by 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） (I) Epoxy polyol resin (c-1-4) having a hydroxyl value of 40 to 330 mgKOH / g
　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、接着力、加飾性等の優れた塗膜を形成し得るため好ましい。 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 bisphenol type epoxy resins such as polyglycidyl ether compounds such as 1,3-bis (4-hydroxycumylbenzene) and 1,4-bis (4-hydroxycumylbenzene) It is preferable because an excellent coating film can be formed.
（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本発明の特徴である被着体（軟質および硬質塩化ビニル樹脂；ポリスチレン；ポリカーボネート；ガラス；アルミニウム；鋼板；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂）に対する選択的接着力（特に異材質間の接着力）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 adherend (soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; polar group-containing compound) which is a feature of the present invention by satisfying the hydroxyl value of (i) and the acid value of (ii) Modified polyolefin resin or copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer; polyester resin; or acrylic resin) (especially between different materials) Adhesive strength) is improved.
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、軟質および硬質塩化ビニル樹脂；ポリスチレン；ポリカーボネート；ガラス；アルミニウム；鋼板；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂の層との接着性に優れ、特に金属接着性・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、軟質および硬質塩化ビニル樹脂；ポリスチレン；ポリカーボネート；ガラス；アルミニウム；鋼板；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂の層との接着性に優れ、特に金属接着性・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)), soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; polyolefin modified with polar group-containing compound Resin or copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer; polyester resin; or excellent adhesion to the acrylic resin layer, especially metal adhesion and hydrolysis resistance Excellent in properties.
The Ito Oil URIC H-2151U is a polyol containing a castor oil-based polyol, an acidic phosphate compound having 12 or more carbon atoms and terpene phenols (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)), soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; Copolymer of polyolefin resin modified with a containing compound or an olefin and a polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer; polyester resin; or excellent adhesion to an acrylic resin layer, especially Excellent metal 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、本発明の接着剤組成物を金属基材やガラス基材と接着させる際に、主として基材表面のぬれ性を向上させ、接着力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 used for bonding the adhesive composition of the present invention to a metal substrate or a glass substrate. Primarily improves the wettability of the substrate surface and functions to improve 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、本発明の接着剤組成物を金属基材やガラス基材と接着させる際に、主として基材表面のぬれ性を向上させ、接着力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、得られる接着剤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、得られる接着剤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 is mainly used when the adhesive composition of the present invention is bonded to a metal substrate or a glass substrate. Improves wettability and functions to improve adhesive strength.
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 adhesive composition is deteriorated. Absent. 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 adhesive property of the resulting adhesive composition is undesirably lowered.
　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で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, monomethyl maleate or monoethyl maleate. Can be mentioned. 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、得られる接着剤組成物の接着性が低下し、１２０（ｍｇＫＯＨ／ｇ）を超えると、得られる接着剤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 adhesive composition is lowered, and when it exceeds 120 (mgKOH / g), the viscosity of the obtained adhesive composition is increased and the workability is lowered. To do.
　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。そのため得られる接着剤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本発明の接着剤組成物はより柔軟化が可能、柔軟性の調整が容易であり、かつ加飾性に優れる。
　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、得られる接着剤組成物は加飾性の点で優れる。 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 adhesive composition obtained is rich in adhesiveness, and since the polarity is sufficiently imparted, the adhesive composition of the present invention can be made more flexible, easy to adjust the flexibility, and decorative. Excellent.
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 obtained adhesive composition is excellent in terms of decorating properties.
　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. .
　本発明の接着剤組成物における、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 adhesive composition of the present invention include mononuclear polynuclear compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol. Polyglycidyl ether compounds of dihydric phenol 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 Polynuclear polyhydric phenols such as 2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, terpene phenol Polyglycidyl ether compound of compound: polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct Polyglycidyl ethers; maleic acid, fumaric acid, itaconic acid, succinic acid Glutaric 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 Cyclo Epoxidized products of cyclic olefin compounds such as hexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized polybutadiene 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金属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 the metal 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、本発明に使用される理由として金属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 has a fully saturated skeleton (epoxidized ethylene / propylene / ethylene / butylene-OH structure) having an epoxy equivalent of 590 g / mol, a hydroxyl equivalent of 7000 g / mol, and a glass transition temperature of −53 ° C. It is a coalescence and is preferable from the viewpoint of metal adhesion as a reason for use in the present invention.
（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％未満では軟質および硬質塩化ビニル樹脂；ポリスチレン；ポリカーボネート；ガラス；アルミニウム；鋼板；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂の層との接着性、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. Also, in less than 10% by mass, soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel sheet; polyolefin resin modified with a polar group-containing compound or copolymer of olefin and polar group-containing compound; magnesium; -Adhesion, flexibility, and impact resistance with a layer of butadiene-styrene copolymer; polyester resin; or acrylic resin are reduced.
　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、３０～６０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４０～５５質量％である。
　成分（ｂ）の配合量が６０質量％を超えると接着性、柔軟性、耐衝撃性が低下する。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 60% by mass from the viewpoints of adhesiveness, flexibility and impact resistance. A more preferable amount of component (b) is 40 to 55% by mass from the viewpoint of easy processing viscosity.
If the blending amount of component (b) exceeds 60% by mass, the adhesiveness, flexibility and impact 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、接着力も低下する。また、５質量％未満では接着性、柔軟性、耐衝撃性が低下する。 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, and the adhesive strength also decreases. On the other hand, if it is less than 5% 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（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は、被着体としてとくに軟質および硬質塩化ビニル樹脂；ポリスチレン；ポリカーボネート；ガラス；アルミニウム；鋼板；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂（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等）；またはアクリル系樹脂（例えばＰＭＭＡ等）（以下、特定被着体の層（Ｂ１）または特定被着体の層（Ｂ２）という）に対する接着性がとくに良好である。これらの被着体に対し良好な接着性を有する接着剤組成物は、従来技術には開示されていない。
　また、上記被着体のうちでＢ１とＢ２に異なる材質を使用した場合の接着性（異材質間の接着性）に極めて優れる。
　異材質間とは、具体的には、硬質塩化ビニル樹脂とガラス、軟質塩化ビニル樹脂とガラス、ポリスチレン系樹脂とアルミニウム、ポリカーボネート樹脂とアルミニウム、アクリロニトリル－ブタジエン－スチレン共重合体（ＡＢＳ）とガラス、ガラスとアルミニウム、マグネシウムとポリカーボネート樹脂、鋼板とアクリル樹脂（例えばポリメタクリル酸メチル（ＰＭＭＡ））、ポリエステル（例えばポリエチレンテレフタレート）とアクリロニトリル－ブタジエン－スチレン共重合体（ＡＢＳ）、アクリル樹脂（例えばポリメタクリル酸メチル（ＰＭＭＡ））とアクリロニトリル－ブタジエン－スチレン共重合体（ＡＢＳ）が挙げられる。
　なお、極性基含有化合物で変性されたポリオレフィン樹脂は、－ＯＨ、－ＮＯ2、－ＣＯ、－ＮＨ2、－ＮＨ、－ＯＣＨ3、－ＳＯ3Ｈ等の極性基が導入されたポリオレフィンであり、例えば無水マレイン酸、グリシジルメタクリレートから選ばれた少なくとも１種をグラフトしたポリオレフィン樹脂が挙げられ、具体的には、無水マレイン酸をグラフトしたポリエチレンやポリプロピレン、グリシジルメタクリレートをグラフトしたポリエチレンやポリプロピレンが挙げられる。また、オレフィンと極性基含有化合物との共重合体は、例えばエチレンと酢酸ビニルとの共重合体（ＥＶＡ）、エチレンと（メタ）アクリル酸との共重合体（ＥＡＡ、ＥＭＡ等）、エチレンと（メタ）アクリル酸エステルとの共重合体（ＥＥＡ等）が挙げられる。 The adhesive composition of the present invention comprises, as an adherend, a soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel sheet; a polyolefin resin modified with a polar group-containing compound or an olefin and a polar group-containing compound. Copolymer; Magnesium; Acrylonitrile-butadiene-styrene copolymer; Polyester resin (eg, polyethylene terephthalate (PET), polybutylene terephthalate, etc.); or Acrylic resin (eg, PMMA, etc.) (hereinafter referred to as a specific adherend layer) Adhesiveness to (B1) or a specific adherend layer (B2)) is particularly good. Adhesive compositions having good adhesion to these adherends are not disclosed in the prior art.
Moreover, it is very excellent in the adhesiveness (adhesion between different materials) when different materials are used for B1 and B2 among the adherends.
The different materials specifically include hard vinyl chloride resin and glass, soft vinyl chloride resin and glass, polystyrene resin and aluminum, polycarbonate resin and aluminum, acrylonitrile-butadiene-styrene copolymer (ABS) and glass, Glass and aluminum, magnesium and polycarbonate resin, steel plate and acrylic resin (for example, polymethyl methacrylate (PMMA)), polyester (for example, polyethylene terephthalate) and acrylonitrile-butadiene-styrene copolymer (ABS), acrylic resin (for example, polymethacrylic acid) Methyl (PMMA)) and acrylonitrile-butadiene-styrene copolymer (ABS).
The polyolefin resin modified with a polar group-containing compound is a polyolefin into which polar groups such as —OH, —NO 2 , —CO, —NH 2 , —NH, —OCH 3 , —SO 3 H and the like are introduced. Examples thereof include polyolefin resins grafted with at least one selected from maleic anhydride and glycidyl methacrylate, and specific examples include polyethylene and polypropylene grafted with maleic anhydride, and polyethylene and polypropylene grafted with glycidyl methacrylate. . Copolymers of olefins and polar group-containing compounds include, for example, copolymers of ethylene and vinyl acetate (EVA), copolymers of ethylene and (meth) acrylic acid (EAA, EMA, etc.), ethylene and A copolymer (EEA etc.) with (meth) acrylic acid ester is mentioned.
（本発明の接着方法）
　本発明の接着方法は、工程Ｉとして、前記成分（ａ）～（ｄ）、必要に応じて他の充填材を、任意の順番で、前記の配合割合にしたがって混合し、本発明の接着剤組成物を調製し、続いて工程ＩＩとして、特定被着体の層（Ｂ１）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、工程ＩＩＩとして、接着剤組成物の層（Ａ）と特定被着体の層（Ｂ２）とをさらに積層する工程を有する。このような本発明の接着方法によれば、前記（Ｂ１）－（Ａ）－（Ｂ２）の３層の接着が強固となる。
　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、透明性に優れ、硬化収縮による樹脂成形体の反りの強さを緩和し、またバインダー樹脂成分の未硬化による表面硬度の低下を防止することができる。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。
　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。 (Adhesion method of the present invention)
In the bonding method of the present invention, as the step I, the components (a) to (d) and, if necessary, other fillers are mixed in an arbitrary order according to the blending ratio, and the adhesive of the present invention. The composition is prepared, and then, as Step II, the adhesive composition is laminated on the layer (B1) of the specific adherend to form the adhesive composition layer (A). A step of further laminating the layer (A) of the composition and the layer (B2) of the specific adherend. According to the bonding method of the present invention, the bonding of the three layers (B1)-(A)-(B2) becomes strong.
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.) By this, it is excellent in transparency, the strength of the curvature of the resin molding by hardening shrinkage | contraction can be relieved, and the fall of the surface hardness by the uncured binder resin component can be prevented. Coating methods include: spin coating method, (doctor) knife coating method, micro gravure coating method, direct gravure coating method, offset gravure method, reverse gravure method, reverse roll coating method, (Meyer) bar coating method, die coating method A method such as spray coating or 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.
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、前記のようにして本発明の接着剤組成物を調製し、これを特定被着体の層（Ｂ１）上に接着剤組成物を積層し、接着剤組成物の層（Ａ）を形成して得られ、（Ｂ１）－（Ａ）からなる積層体である。また、別の形態によれば、本発明の積層体は、特定被着体の層（Ｂ１）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、さらに層（Ａ）上に特定被着体の層（Ｂ２）を積層して得られ、（Ｂ１）－（Ａ）－（Ｂ２）からなる積層体である。
　本発明の積層体は、特定被着体の層（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。
　また、（Ｂ１）－（Ａ）からなる積層体では、接着剤組成物の層（Ａ）が、（Ｂ１）のプライマー層として有利に作用する。該プライマー層は、例えば、用途に応じてさらにその上に塗布される塗料に対する接着性に寄与することができる。
　なお、上記以外にも、特定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 prepared by preparing the adhesive composition of the present invention as described above, laminating the adhesive composition on the specific adherend layer (B1), and then laminating the adhesive composition layer. A laminate obtained by forming (A) and comprising (B1)-(A). Moreover, according to another form, the laminated body of this invention laminates | stacks an adhesive composition on the layer (B1) of a specific adherend, forms the layer (A) of an adhesive composition, and also a layer It is a laminate comprising (B1)-(A)-(B2) obtained by laminating the layer (B2) of the specific adherend on (A).
The laminate of the present invention has good adhesion between the layers (B1) and (B2) of the specific adherend and the layer (A) of the adhesive composition, and has transparency, surface smoothness, flexibility and resistance. Excellent balance of impact.
Further, in the laminate comprising (B1)-(A), the layer (A) of the adhesive composition acts advantageously as a primer layer of (B1). For example, the primer layer can further contribute to adhesion to a paint applied thereon depending on the application.
In addition to the above, the layer of the specific 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.
　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）
成分（ａ－３）ビニルエステル樹脂
　昭和高分子社製、ＲＩＰＯＸＹ　ＶＲ－７７（商標）
　粘度：１，０００（ｄＰａ・ｓ／２５℃）
　分子量：５１０ 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.
Component (a-3) Vinyl ester resin, manufactured by Showa Polymer Co., Ltd., RIPOXY VR-77 (trademark)
Viscosity: 1,000 (dPa · s / 25 ° C)
Molecular weight: 510
成分（ｂ）　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）日本触媒社製、Ｎ－ビニルピロリドン
分子量：１１１.１４
沸点 219℃
蒸気圧(24℃) 0.10mm Hg
引火点 98℃
粘度(25℃) 2 cps
融点 13℃
（ｉｉ）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℃) Component (b) Compound having a cyclic structure and one ethylenically unsaturated group (i) Nippon Shokubai Co., Ltd., N-vinylpyrrolidone Molecular weight: 111.14
Boiling point 219 ° C
Vapor pressure (24 ℃) 0.10mm Hg
Flash point 98 ° C
Viscosity (25 ° C) 2 cps
Melting point 13 ° C
(Ii) NSF-caprolactam boiling point 117 ° C (10mm Hg) manufactured by BASF
Vapor pressure <0.1 mm Hg (20 ℃)
Flash point 110 ° C
Melting point 35 ℃
Viscosity 3.5 cps (40 ° C)
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１～２１、比較例１～６
　下記表１～８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、接着剤組成物を得た。得られた接着剤組成物の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１～８に併せて示す。 Examples 1 to 21 and Comparative Examples 1 to 6
In the blending ratios (parts by mass) shown in Tables 1 to 8 below, the component (a) is placed in 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 an adhesive composition. The viscosity (mPa · s) at 25 ° C. of the obtained adhesive 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 8.
　次に、表１～８に示す各特定被着体（Ｂ１）（寸法：１５０ｍｍ×２５ｍｍ×厚さ１ｍｍ）上に、スピンコート法により接着剤組成物を塗布し（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, an adhesive composition was applied to each specific adherend (B1) (dimensions: 150 mm × 25 mm × thickness 1 mm) shown in Tables 1 to 8 by a spin coating method (application thickness 15 to 20 μm), This was cured by irradiation with ultraviolet rays having an energy of 500 mJ / cm 2 under air to prepare a laminate. 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.
　実施例９は、実施例２において成分（ｄ）に（ｉｉ）熱重合開始剤を使用した例である。
　表に示す各特定被着体（Ｂ１）（寸法：１５０ｍｍ×２５ｍｍ×厚さ１ｍｍ）上に、スピンコート法により接着剤組成物を塗布し（塗布厚１５～２０μｍ）、これを１００℃、１０分熱処理して硬化させ、積層体を調製した。 Example 9 is an example in which (ii) a thermal polymerization initiator was used for component (d) in Example 2.
On each specific adherend (B1) shown in the table (dimensions: 150 mm × 25 mm × thickness 1 mm), an adhesive composition was applied by spin coating (coating thickness 15-20 μm). The laminate was prepared by subjecting to partial heat treatment and curing.
　使用した各特定被着体（Ｂ１）は、次の通りである。
・硬質塩化ビニル樹脂ＰＶＣ（リケンテクノス社製、商品名Riken  PVC　Compound　RE-3844）
・軟質塩化ビニル樹脂ＰＶＣ（リケンテクノス社製、商品名Leonyl　BZL6060N）
・ポリスチレンＰＳ（東洋スチレン社製、商品名トーヨースチロールGP　G100C）
・ポリカーボネートＰＣ（帝人化成社製、商品名パンライトL-1225L）
・アクリロニトリル－ブタジエン－スチレン共重合体ＡＢＳ（UMG社製、商品名UMG  ABS　EX114）
・ガラス（顕微鏡プレパラート用スライドグラス）
・アルミニウム（Ｈ５０５２、Ａｌ－Ｍｇ系）
・マグネシウム（大阪富士工業社製、ＡＺ３１Ｂ、Ｍｇ含有量９１％以上）
・鋼板（ＳＰＣＣ：冷間圧延鋼板）
・ＰＥＴ：ユニチカ　ユニチカポリエステル樹脂MA-2103
・ＰＭＭＡ：三菱レイヨン　アクリペット　VH Each specific adherend (B1) used is as follows.
・ Hard vinyl chloride resin PVC (Riken Technos, trade name Riken PVC Compound RE-3844)
-Soft vinyl chloride resin PVC (manufactured by Riken Technos, trade name Leonyl BZL6060N)
・ Polystyrene PS (Toyo Styrol GP G100C, manufactured by Toyo Styrene Co., Ltd.)
・ Polycarbonate PC (trade name Panlite L-1225L, manufactured by Teijin Chemicals Ltd.)
・ Acrylonitrile-butadiene-styrene copolymer ABS (manufactured by UMG, trade name UMG ABS EX114)
・ Glass (slide glass for microscope preparation)
・ Aluminum (H5052, Al-Mg)
Magnesium (Osaka Fuji Kogyo Co., Ltd., AZ31B, Mg content 91% or more)
・ Steel (SPCC: Cold rolled steel)
・ PET: Unitika Unitika polyester resin MA-2103
・ PMMA: Mitsubishi Rayon Acrypet VH
　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。
（密着性試験：碁盤目テープ試験）
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（接着剤組成物の層（Ａ）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。
　結果を併せて表１～８に示す。 The obtained laminate was subjected to the following cross-cut tape test.
(Adhesion test: 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 tape test (Cross-cut Test, coating thickness 15-20 μm (spin coating method)): A 1 × 1 mm square cross-cut using a cutter knife on the test surface (adhesive composition layer (A) side) Make a cut. 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).
The results are also shown in Tables 1 to 8.
・異材質接着試験
　異材質間の接着試験を次に示すようなせん断接着力測定により行った。結果を表１～８に示す。
　寸法１５０ｍｍ×１ｍｍ厚×２５ｍｍ巾の特定被着体（Ｂ１）上に、スピンコート法で上記接着剤組成物を塗布し（塗布厚１５～２０μｍ）、接着剤組成物の層（Ａ）を形成し、さらにその上に、表１～８に示す、上記（Ｂ１）と同じ寸法の各特定被着体（Ｂ２）を圧着させ、透明な層側から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、特定被着体（Ｂ２）を、接着剤組成物の層（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。
　結果を表１～８に示す。なお表１～８では、上記（Ｂ１）－（Ａ）－（Ｂ２）からなる積層体を、（Ｂ１）ｖｓ（Ｂ２）のように示した。例えば、（Ｂ１）が硬質ＰＶＣであり、（Ｂ２）がガラスである場合は、「硬質ＰＶＣ ｖｓガラス」のように示した。 -Adhesion test between different materials An adhesion test between different materials was performed by measuring the shear adhesive strength as shown below. The results are shown in Tables 1-8.
On the specific adherend (B1) having dimensions of 150 mm × 1 mm thickness × 25 mm width, the above-mentioned adhesive composition is applied by spin coating (coating thickness: 15 to 20 μm) to form an adhesive composition layer (A). Further, the specific adherend (B2) having the same dimensions as (B1) shown in Tables 1 to 8 shown in Tables 1 to 8 is further bonded thereto, and UV irradiation (wavelength: 325 nm, integrated irradiation intensity) is performed from the transparent layer side. : 50 mJ / cm 2 ) and UV curing to prepare a laminate, and then the specific adherend (B2) is pulled in a direction parallel to the bonding surface of the layer (A) of the adhesive composition, Tensile strength was measured.
The results are shown in Tables 1-8. In Tables 1 to 8, the laminate composed of (B1)-(A)-(B2) is shown as (B1) vs (B2). For example, when (B1) is hard PVC and (B2) is glass, it is shown as “hard PVC vs 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 method: An adhesive composition was applied to a steel sheet of 25 mm width and 1 mm thickness by spin coating to a thickness of 15 to 20 μm, and after curing, a 90-degree bending test was performed and the following criteria were evaluated.
○: Not peeled △: Partially peeled / cracked ×: Whole surface peeled / crack
透明性試験
　透明性を評価するため、JIS-K7136： 2000に基づいて実施例及び比較例の成形体（基材ガラス）のヘーズを、ヘーズメーター（ＮＤＨ２０００：日本電色社）を用いて測定した。評価は、測定値が１．０％未満であったものを「◎」、１．０％以上２．０％未満であったものを「○」、２．０％以上「×」とした。なお、測定面は、塗膜面とした。 Transparency test In order to evaluate transparency, the haze of the molded articles (base glass) of Examples and Comparative Examples was measured using a haze meter (NDH2000: Nippon Denshoku) based on JIS-K7136: 2000. . In the evaluation, “◎” indicates that the measured value is less than 1.0%, “◯” indicates that the measured value is 1.0% or more and less than 2.0%, and “x” indicates 2.0% or more. The measurement surface was a coating surface.
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
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
　表より明らかなように、本発明の実施例１～２１では、接着剤組成物が、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、極性樹脂、セラミックス、金属等に対し優れた接着性を示した。
　一方、比較例１および２は成分（ａ）および（ｂ）の配合量が本発明で規定する範囲外であり、極性樹脂、セラミックス、金属等に対する接着性が悪化している。また、耐衝撃性および柔軟性も悪化した。成分（ｂ）が下限未満では粘度が上昇した。
　比較例３は成分（ｃ）を配合せず；比較例４は成分（ｃ）の配合量が本発明で規定する上限を超えているため、極性樹脂、セラミックス、金属等に対する接着性が悪化している。また、耐衝撃性および柔軟性も悪化した。
　比較例５は、成分（ｄ）の配合量が本発明で規定する下限未満であるので、硬化が不十分であることから極性樹脂、セラミックス、金属等に対する接着性が悪化している。
　比較例６は成分（ｄ）の配合量が本発明で規定する上限を超えているので、極性樹脂、セラミックス、金属等に対する接着性が悪化している。また、耐衝撃性および柔軟性も悪化した。 As is apparent from the table, in Examples 1 to 21 of the present invention, the adhesive composition contains the components (a), (b), (c) and (d) in a specific quantitative relationship. Therefore, it showed excellent adhesion to polar resins, ceramics, metals and the like.
On the other hand, in Comparative Examples 1 and 2, the blending amounts of the components (a) and (b) are outside the range defined in the present invention, and the adhesion to polar resins, ceramics, metals, etc. is deteriorated. Moreover, impact resistance and flexibility were also deteriorated. When component (b) was less than the lower limit, the viscosity increased.
Comparative Example 3 does not contain component (c); in Comparative Example 4, the amount of component (c) exceeds the upper limit specified in the present invention, so the adhesion to polar resins, ceramics, metals, etc. deteriorates. ing. Moreover, impact resistance and flexibility were also deteriorated.
In Comparative Example 5, since the blending amount of component (d) is less than the lower limit specified in the present invention, the adhesion to polar resins, ceramics, metals, and the like is deteriorated due to insufficient curing.
In Comparative Example 6, the compounding amount of the component (d) exceeds the upper limit defined in the present invention, so that the adhesion to polar resins, ceramics, metals, etc. is deteriorated. Moreover, impact resistance and flexibility were also deteriorated.
　本発明の接着剤組成物は、軟質および硬質塩化ビニル樹脂；ポリスチレン；ポリカーボネート；ガラス；アルミニウム；鋼板；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂と優れた接着性を有し、透明性、表面平滑性、柔軟性、耐衝撃性のバランスに優れる。したがって、これら特定被着体表面に透明なプライマー層を形成すること、及び上記特定被着体間（特に異材質間）を接着することに適しているが、それだけでなく各種、建装材料、包装材料、印刷材料、表示材料、電気電子部品材料、光学部品材料、液晶パネル等の分野においても有用なものである。 The adhesive composition of the present invention comprises a soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel sheet; a polyolefin resin modified with a polar group-containing compound or a copolymer of an olefin and a polar group-containing compound; An acrylonitrile-butadiene-styrene copolymer; a polyester resin; or an acrylic resin, and an excellent balance of transparency, surface smoothness, flexibility, and impact resistance. Therefore, it is suitable for forming a transparent primer layer on the surface of these specific adherends and adhering between the specific adherends (particularly between different materials). It is also useful in the fields of packaging materials, printing materials, display materials, electrical / electronic component materials, optical component materials, liquid crystal panels, and the like.

Claims (14)

  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）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　３０～６０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
    からなる接着剤組成物。     (A) Vinyl ester resin or unsaturated polyester resin 10 to 40% by mass
    (B) Compound having a cyclic structure and one ethylenically unsaturated group 30 to 60% 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 comprising 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、ウレタン（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 urethane (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. 　前記接着剤組成物の被着体が、軟質および硬質塩化ビニル樹脂；ポリスチレン；ポリカーボネート；ガラス；アルミニウム；鋼板；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂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 adherend of the adhesive composition is a soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; a polyolefin resin modified with a polar group-containing compound or a copolymer of an olefin and a polar group-containing compound The adhesive composition according to claim 1, wherein the adhesive composition is magnesium; acrylonitrile-butadiene-styrene copolymer; polyester resin; or acrylic resin.
  12. 工程Ｉ：
    （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）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　３０～６０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
    を任意の順に混合し、接着剤組成物を調製する工程、
    工程ＩＩ：
    　軟質および硬質塩化ビニル樹脂；ポリスチレン；ポリカーボネート；ガラス；アルミニウム；鋼板；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂の層（Ｂ１）の表面に前記工程Ｉで得られた接着剤組成物を積層し、接着剤組成物の層（Ａ）を形成する工程、
    工程ＩＩＩ：
    　前記工程ＩＩで得られた積層体の接着剤組成物の層（Ａ）と、軟質および硬質塩化ビニル樹脂；ポリスチレン；ポリカーボネート；ガラス；アルミニウム；鋼板；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂の層（Ｂ２）をさらに積層する工程、
    を工程Ｉ、工程ＩＩおよび工程ＩＩＩのこの順で行うことを特徴とする接着方法。     Step I:
    (A) Vinyl ester resin or unsaturated polyester resin 10 to 40% by mass
    (B) Compound having a cyclic structure and one ethylenically unsaturated group 30 to 60% by mass
    (C) modifying agent 5-40% by mass,
    (However, the total of the components (a) to (c) is 100% by mass)
    And (d) an initiator, a step of mixing 0.1 to 15 parts by mass with respect to a total of 100 parts by mass of the components (a) to (c) to prepare an adhesive composition,
    Step II:
    Soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; polyolefin resin modified with polar group-containing compound or copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer A step of laminating the adhesive composition obtained in Step I above on the surface of the layer (B1) of polyester resin; or acrylic resin; and forming the layer (A) of adhesive composition;
    Step III:
    Layer (A) of the adhesive composition of the laminate obtained in the step II, and soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; polyolefin resin or olefin modified with a polar group-containing compound And a copolymer of a polar group-containing compound; magnesium; an acrylonitrile-butadiene-styrene copolymer; a polyester resin; or an acrylic resin layer (B2);
    Is performed in this order of step I, step II and step III.
  13. （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）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　３０～６０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
    からなる接着剤組成物の層（Ａ）と、
    （ただし、前記成分（ａ）～（ｄ）の合計は１００質量％である）
    　軟質および硬質塩化ビニル樹脂；ポリスチレン；ポリカーボネート；ガラス；アルミニウム；鋼板；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂の層（Ｂ１）と
    を前記層（Ａ）および層（Ｂ１）が接するようにして形成された積層体。     (A) Vinyl ester resin or unsaturated polyester resin 10 to 40% by mass
    (B) Compound having a cyclic structure and one ethylenically unsaturated group 30 to 60% by mass
    (C) modifying agent 5-40% by mass,
    (However, the total of the components (a) to (c) is 100% by mass)
    And (d) an initiator layer (A) of an adhesive composition comprising 0.1 to 15 parts by mass with respect to a total of 100 parts by mass of the components (a) to (c);
    (However, the total of the components (a) to (d) is 100% by mass)
    Soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; polyolefin resin modified with polar group-containing compound or copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer A laminate formed by contacting the layer (B1) with the layer (B1) of the polyester resin; or the acrylic resin;
  14. 　軟質および硬質塩化ビニル樹脂；ポリスチレン；ポリカーボネート；ガラス；アルミニウム；鋼板；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂の層（Ｂ１）と、
    （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）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　３０～６０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
    からなる接着剤組成物層（Ａ）と、
    　軟質および硬質塩化ビニル樹脂；ポリスチレン；ポリカーボネート；ガラス；アルミニウム；鋼板；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂の層（Ｂ２）と、
    を前記層（Ｂ１）、層（Ａ）および層（Ｂ２）の３層がこの順で接するようにして形成された積層体。     Soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; polyolefin resin modified with polar group-containing compound or copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer A polyester resin; or an acrylic resin layer (B1);
    (A) Vinyl ester resin or unsaturated polyester resin 10 to 40% by mass
    (B) Compound having a cyclic structure and one ethylenically unsaturated group 30 to 60% by mass
    (C) modifying agent 5-40% by mass,
    (However, the total of the components (a) to (c) is 100% by mass)
    And (d) an initiator, an adhesive composition layer (A) comprising 0.1 to 15 parts by mass with respect to a total of 100 parts by mass of the components (a) to (c);
    Soft and hard vinyl chloride resin; polystyrene; polycarbonate; glass; aluminum; steel plate; polyolefin resin modified with polar group-containing compound or copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer A polyester resin; or an acrylic resin layer (B2);
    A layered product formed by contacting the three layers of the layer (B1), the layer (A) and the layer (B2) in this order.
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