WO2008032677A1 - Radical-polymerizable resin composition for coating or adhesive - Google Patents

Radical-polymerizable resin composition for coating or adhesive Download PDF

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Publication number
WO2008032677A1
WO2008032677A1 PCT/JP2007/067594 JP2007067594W WO2008032677A1 WO 2008032677 A1 WO2008032677 A1 WO 2008032677A1 JP 2007067594 W JP2007067594 W JP 2007067594W WO 2008032677 A1 WO2008032677 A1 WO 2008032677A1
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WIPO (PCT)
Prior art keywords
resin composition
resin
meth
parts
radically polymerizable
Prior art date
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PCT/JP2007/067594
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French (fr)
Japanese (ja)
Inventor
Ou Shibata
Yukiko Fujita
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Dh Material Inc.
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Application filed by Dh Material Inc. filed Critical Dh Material Inc.
Publication of WO2008032677A1 publication Critical patent/WO2008032677A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00

Definitions

  • the present invention relates to a radically polymerizable resin composition for coating adhesion, which comprises a polycarbonate skeleton-containing urethane resin containing a (meth) atalyloyl group and a radically polymerizable unsaturated monomer having a specific skeleton.
  • the present invention relates to an adhesion method and an adhesive for butyl resin.
  • Urethane resins containing a (meth) atallyloyl group having a polyether and / or polyester skeleton in the main skeleton are highly flexible and are used as base resins for adhesives to various substrates, and are adhesives for fiber-reinforced plastics. It is known that it is useful as (see Patent Document 1).
  • Patent Document 1 JP 2004-238557 A
  • Patent Document 2 JP-A 63-118388
  • these base resins for adhesives are not only excellent in adhesion to all plastic base materials, but are currently widely used in agriculture and sewage systems. Excellent adhesion performance when used alone! / ,!
  • the radical polymerizable resin is bonded to the so-called soft chlorinated resin containing a plasticizer in particular by surface sanding, heat fusion, or the like.
  • the adhesive using an organic solvent has a problem that it is not preferable from the viewpoint of solvent volatilization.
  • An object of the present invention is to provide an adhesive that can be used without selecting an adherend in a radically polymerizable resin that has conventionally had a problem of selecting an adherend when used for bonding. It is in the development of agents.
  • a radical polymerizable resin composition exhibiting excellent adhesion performance to a soft chlorinated resin, a structure using the resin composition and a chlorinated resin, a coating material mainly composed of the resin composition, and the resin
  • the polycarbonate diol (A1) and the diisocyanate compound (A2) are reacted to obtain an isocyanate group-containing compound (A3), and then the above (A3) and one hydroxide
  • a urethane polymerizable resin having a polycarbonate skeleton having a (meth) acryloyl group obtained by reacting a (meth) acrylic compound containing a group (A) and a radically polymerizable unsaturated monomer having a dicyclopentyl group
  • the present invention provides a radically polymerizable resin composition for coating adhesion, comprising (B).
  • the present invention also provides a structure characterized in that a salted bull resin layer is provided on a substrate via the above-mentioned radically polymerizable resin composition for coating adhesion.
  • the present invention also provides a method for adhering a chlorinated bull resin to a substrate, characterized by using the radically polymerizable resin composition for coating adhesion.
  • the present invention also provides a coating material comprising the radically polymerizable resin composition for coating adhesion as a main component.
  • the present invention also provides an adhesive comprising the radically polymerizable resin composition for coating adhesion as a main component.
  • a hard chloride resin and a soft chloride resin, or a polychlorinated resin it is possible to bond a hard chloride resin and a soft chloride resin, or a polychlorinated resin to a substrate with excellent adhesion performance. It can also be used as a coating material (primer, paint, sealing material, note) of poly (vinyl chloride) resin.
  • (A) has at least one (meth) atalyloyl group in the molecule.
  • Such resins are poly
  • the carbonate diol (Al) and the diisocyanate compound (A2) are preferably reacted so that the equivalent ratio of the isocyanate group to the hydroxyl group (NCO / OH) is 1.5 to 2 to obtain the isocyanate group-containing compound (A3).
  • the (A3) and the (meth) acrylic compound (A4) containing one hydroxyl group preferably have an equivalent ratio (NCO / OH) of the isocyanate group to the hydroxyl group substantially the same. It is obtained by reacting each compound as follows.
  • the polycarbonate diol (A1) here is, for example, an ester exchange reaction between an aliphatic chain diol and / or an alicyclic diol and a carbonate such as dimethyl carbonate or jetyl carbonate, or a cyclic carbonate having an alkylene group.
  • a ring opening reaction of phosgene and an aliphatic chain diol and / or an alicyclic diol, etc. preferably a number average molecular weight of 300 to 3000, particularly preferably ⁇ (or in the range of 500 to 2000).
  • the molecular weight is in the range of 300 to 3000, preferably S. If it is less than 300, the characteristics derived from the carbonate will be weak, and if it is greater than 3000, it will react with the polyisocyanate. The viscosity of the obtained compound is increased and it is difficult to work practically.
  • the aliphatic chain diol and / or alicyclic diol used as a raw material for the production of carbonate diol (A1) has an arbitrary structure.
  • carbonate diol (A1) Conventionally known polyoxypropylene di-diol, polytetramethylene glycol Polyesterol polyols such as lime-ximethylene di-nore, or polyester polyols, which are condensates of polyhydric alcohols and polybasic carboxylic acids, can also be used in combination with polycarbonate diols to react with diisocyanate compounds ( ⁇ 2).
  • (A1) is contained in an amount of 60% by mass or more, more preferably 90% by mass or more.
  • the diisocyanate compound ( ⁇ 2) is a compound having an isocyanate group in the molecule. It refers to what you have.
  • diisocyanate compound (A2) examples include 2,4-tolylene diisocyanate, its isomer or a mixture of these isomers (hereinafter abbreviated as TDI), diphenylmethane diisocyanate, hexamethylene diiso- sane. Cyanate, isophorone diisocyanate (hereinafter abbreviated as IPDI), xylylene diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexyl. These can be used alone or in combination of two or more. Of the diisocyanate compound (A2), an aliphatic compound having two isocyanate groups is particularly preferred from the viewpoint of the weather resistance discoloration obtained.
  • TDI 2,4-tolylene diisocyanate, its isomer or a mixture of these isomers
  • IPDI isophorone diisocyanate
  • xylylene diisocyanate hydrogenated xylylene diisocyan
  • a hydroxyl group-containing (meth) acrylic ester is preferably used.
  • the polymerizable unsaturated monomer (B) used in the present invention is a radically polymerizable unsaturated monomer having a dicyclopentyl group in the skeleton.
  • force S including dicyclopentuoxychetyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and other radical polymerizable monomers
  • a hydroxyl group-containing allyl ether compound is used in combination with the (meth) acrylic compound (A4) containing one hydroxyl group for the purpose of preventing curability inhibition by air during curing. It can also be used.
  • the radical polymerizable resin composition of the present invention contains the polycarbonate skeleton-containing urethane resin (A) and the polymerizable unsaturated monomer (B).
  • the polycarbonate skeleton-containing urethane resin (A) 90 to 10 parts by mass and the polymerizable unsaturated monomer (B) 10 to 90 parts by mass are preferably dissolved together.
  • a polymerization inhibitor to the resin composition of the present invention.
  • the polymerization inhibitor include trihydroquinone, hydroquinone, 1,4-naphthoquinone, parabenzoquinone, and tonolhydride. Mouth non, p tert butynole power teconore, 2, 6 tert butynole 4-methylphenol and the like.
  • the amount of the polymerization inhibitor used is preferably 10 to 1000 ppm in the resin composition.
  • the resin composition of the present invention is usually cured by adding a known curing agent that generates radicals.
  • the curing agent that can be added include one or more selected from ultraviolet curing agents, electron beam curing agents, photocuring agents, and thermosetting agents.
  • the amount of the curing agent used is preferably 0.;! To 10 parts by mass with respect to 100 parts by mass of the resin composition; more preferably 5 to 5 parts by mass.
  • the ultraviolet curing agent is a photosensitizing substance.
  • benzoin ethers such as benzoin alkyl ethers
  • benzophenones such as benzophenone and methyl orthobenzoylbenzoate
  • benzyl dimethyl ketal 2,2 diethoxyacetophenone, 2 hydroxy-2 methyl
  • Acetophenones such as propiophenone, 4-isopropyl-1-hydroxy-1-2-methylpropiophenone, 1,1-dichloroacetophenone; 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, etc.
  • thixanthone series examples of the electron beam curing agent include halogenated alkylbenzenes and disulfide compounds.
  • Examples of the photocuring agent include hydroxyalkylphenone compounds, alkylthioxanthone compounds, sulfonium salt compounds, and acylphosphine oxide compounds.
  • thermosetting agent examples include organic peroxides. Specifically, for example, known peroxy peroxides, peroxyesters, hydride peroxides, dialkyl peroxides, ketone peroxides, peroxyketals, alkyl peresters, percarbonates, etc. Can be used and is appropriately selected depending on kneading conditions, curing temperature, and the like.
  • the resin composition of the present invention may be used in combination with a known accelerator such as an organic metal salt such as cobalt naphthenate or otetenate, an amine or ⁇ -diketone as a curing accelerator.
  • a known accelerator such as an organic metal salt such as cobalt naphthenate or otetenate, an amine or ⁇ -diketone as a curing accelerator.
  • the resin composition of the present invention includes generally known unsaturated polyester resins, bururetan resins, burester urethane resins, polyisocyanates, polyepoxides, talyl resins, alkyd resins, urea resins. , Melamine resins, poly (butyl acetate), vinyl acetate copolymers, polygen elastomers, saturated polyesters, saturated polyethers; senorelose derivatives such as nitrosenorose and senorerose acetate butyrate; Other conventional natural and synthetic polymer compounds such as oils such as tung oil, soybean oil, castor oil, epoxidized oil and the like can be added as long as the effects of the present invention are not impaired.
  • glass fiber, carbon fiber, organic fiber, metal fiber and the like can be added to the resin composition of the present invention as a reinforcing material in an amount of 5 to 70 mass%.
  • the resin composition of the present invention contains a filler such as calcium carbonate, talc, my strength, clay, silica powder, colloidal silica, barium sulfate, aluminum hydroxide, glass powder, glass beads, and crushed sand. Can be used as a sealing agent, paint, or coating material. It is also effective as a material for impregnating and reinforcing cloth and kraft paper. Furthermore, other known additives such as zinc stearate, titanium white, zinc white, various other pigments, dyes, stabilizers, flame retardants and the like can be added. [0024]
  • the radically polymerizable resin composition for coating adhesion of the present invention is preferably used for a portion having polychlorinated bulls.
  • Forces suitable for applications requiring coating adhesion, such as film laminating material, putty, paste, adhesive resin using fiber reinforcing material, and ink vehicle are not particularly limited thereto.
  • the base material is a soft chloride resin, a hard chloride resin, or metal, fiber, paper, leather, and plastic, and particularly for applications in which the chloride resin and the substrate are firmly bonded and coated. It can be used.
  • the resin composition of the present invention exhibits excellent adhesion performance even to a chlorinated resin, particularly a soft chlorinated chloric resin, for which a conventional adhesive could not exhibit good adhesion performance. Therefore, the structure of the present invention in which the chlorinated resin layer is provided on the base material through the resin composition of the present invention is a material that makes use of this excellent adhesion performance. It is stably immobilized on the top.
  • the method for adhering butyl chloride resin to a base material using the resin composition of the present invention is an excellent method which has not been conventionally used. As a bonding method at this time, a known method may be applied except that the resin composition of the present invention is used as an adhesive.
  • the structure of the present invention is formed by laminating the base material, the resin composition of the present invention, and a chlorinated resin in this order.
  • a known epoxy-based, urethane-based, isocyanate-based, acrylic-based or aqueous dispersion primer may be used between the substrate and the resin composition of the present invention.
  • the reaction was carried out at 90 ° C for 7 hours. Since NCO% was 0.3 mass% or less, 0.05 part of hydroquinone was added to obtain a polycarbonate skeleton-containing urethane resin having a methacryloyl group.
  • the adhesive performance of the resin composition was evaluated by using a chlorinated resin (hereinafter abbreviated as PVC) as a base material.
  • PVC chlorinated resin
  • a hard vinyl chloride resin (hard PVC, manufactured by Takiron, 3mm thickness, gray color) as a base material was cut into a vertical length of 100mm and a width of 25mm, and the surface was lightly degreased with acetone to remove dust. . Thereafter, the above-mentioned various resin compositions are applied to the two test pieces so that the adhesion area is 25 mm ⁇ 25 mm, and the adhesive part is shifted until the resin composition is cured, and the weight is placed on the test piece and cured. Further, the resin composition was completely cured by placing it in a dryer at 60 ° C. for 1 hour.
  • the adhesion evaluation test was conducted by a tensile shear (tensile speed 5 mm / min) test according to JIS-K 6850, and the shear strength and the state of the adhesion interface after the test were observed. The case where the hard PVC substrate was destroyed by the test was indicated as substrate failure. If it peels off at the substrate interface! /, The adhesive performance is inferior and the evaluation judgment is poor: X. If the adhesive strength is superior to the base material strength and the base material breaks, the evaluation judgment is made. Good: ⁇ .
  • Soft PVC is made by adding 50 parts of dioctyl phthalate as a plasticizer to 100 parts of vinyl chloride resin powder (Shinichi Dai-ichi Vinyl Co., Ltd. ZEST1000Z), and then adding 2 parts of powdered barium zinc-based stabilizer at room temperature to 170 ° C. The mixture was uniformly melt-kneaded for 5 minutes with a heating mixing roll, to obtain a soft PVC sheet having a thickness of about 1 mm.
  • the obtained flexible PVC sheet was cut into strips with a length of 200 mm and a width of 25 mm, and each of the above resin compositions was evenly applied to an area with a length of 150 mm and a width of 25 mm.
  • the test piece was piled up and held lightly while removing air bubbles, and the test piece was sandwiched between two glass plates to cure the resin composition. Thereafter, the test piece was sandwiched between glass plates and placed in a dryer at 60 ° C. for 1 hour to completely cure the resin composition.
  • the adhesion evaluation test was conducted in accordance with JIS-K-6854, and the 180 ° peel test (T-peel test, 10 mmZ min) was used to observe the line and peel strength and the state of the adhesive interface after the test. According to the test, when only one side of the adhesive is adhered and the interface peels off, it is judged as bad: X, and the adhesive layer itself is broken and adheres to both sides of the substrate. Was evaluated as good: ⁇ .
  • the resin composition of the present invention was excellent in adhesion between hard PVC base materials and between soft PVC base materials that could not be bonded with conventional adhesives. It was found to exhibit adhesive properties.
  • the surface of a cold-rolled steel plate (2 mm thick, JISG3141 SPCC—SD) used as a base material is degreased with acetone, and primer PD (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), a primer based on isocyanate, is applied to the brush. And then dried at room temperature for 1 hour.
  • primer PD trade name, manufactured by Dainippon Ink & Chemicals, Inc.
  • the resin composition to which the accelerator and the curing agent prepared previously were uniformly applied was applied to the surface of the steel plate, and immediately, the sheet-like soft salt-vinyl resin (used in the adhesive evaluation section) ( Soft PVC) was placed in a layer without air, allowed to stand at room temperature for 1 day, and cured to produce a structure comprising a soft vinyl chloride resin sheet resin composition Z steel plate substrate of the present invention.
  • Soft PVC sheet-like soft salt-vinyl resin
  • the soft salt vinyl resin sheet was integrated with the steel plate substrate by the resin composition of the present invention. . As a result, it could not be easily peeled off, and an integrated structure of a soft vinyl chloride resin sheet and a steel plate substrate was obtained.
  • primer PD (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), which is an isocyanate primer, was applied to the surface using a brush and dried at room temperature for 1 hour to prepare a concrete board.
  • the soft chloride resin sheet was integrated with the concrete board substrate by the resin composition of the present invention. As a result, it could not be easily peeled off, and an integrated structure of a soft chloride resin sheet and a concrete board substrate was obtained.
  • the resin composition film of the present invention was peeled off from the end of the bull chloride resin base material using a cutter blade, but it was sufficiently adhered to the base material and did not peel off. Together, I confirmed that!
  • the hard chloride resin and the conventional adhesive are excellent. It is useful because it can provide a radically polymerizable resin composition for coating adhesion that exhibits excellent adhesion performance even for soft chlorinated resin that could not be adhered. And since the resin composition of this invention can be apply
  • the present invention is particularly applicable to adhesion of various types of chlorinated resin to a substrate and covering of various types of chlorinated resin.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Laminated Bodies (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

A radical-polymerizable resin composition for a coating or adhesive, comprising an urethane resin (A) having a polycarbonate skeleton having a (meth)acryloyl group and a radical-polymerizable unsaturated monomer (B) having a dicyclopentenyl group, wherein the urethane resin (A) is produced by reacting a polycarbonate diol (A1) with a diisocyanate compound (A2) to produce a compound (A3) having an isocyanate group and then reacting the compound (A3) with a (meth)acrylic compound (A4) having one hydroxy group; a structural object using the resin composition and a vinyl chloride resin; a coating agent mainly comprising the resin composition; and a vinyl chloride resin adhesion method and an adhesive agent both using the resin composition.

Description

明 細 書  Specification
被覆接着用ラジカル重合性樹脂組成物  Radical polymerizable resin composition for coating adhesion
技術分野  Technical field
[0001] 本発明は、（メタ）アタリロイル基を含有するポリカーボネート骨格含有ウレタン樹脂 と特定の骨格を有するラジカル重合性不飽和単量体を含む被覆接着用ラジカル重 合性樹脂組成物で、特に塩化ビュル樹脂との接着性に優れた被覆接着用ラジカノレ 重合性樹脂組成物、この樹脂組成物及び塩化ビュル樹脂を使用した構造物、この 樹脂組成物を主成分とする被覆材、並びにこの樹脂組成物を使用する塩化ビュル 樹脂の接着方法及び接着剤に関するものである。  [0001] The present invention relates to a radically polymerizable resin composition for coating adhesion, which comprises a polycarbonate skeleton-containing urethane resin containing a (meth) atalyloyl group and a radically polymerizable unsaturated monomer having a specific skeleton. Radicanole for coating adhesion excellent in adhesion to Bulle resin Polymerizable resin composition, structure using the resin composition and Bulle chloride resin, coating material comprising the resin composition as a main component, and resin composition The present invention relates to an adhesion method and an adhesive for butyl resin.
背景技術  Background art
[0002] 主骨格にポリエーテル及び/又はポリエステル骨格を有する（メタ）アタリロイル基 含有ウレタン樹脂は、柔軟性に富み、各種基材への接着剤用ベース樹脂として用い られ、繊維強化プラスチック用接着剤として有用であることが知られている（特許文献 1参照)。  [0002] Urethane resins containing a (meth) atallyloyl group having a polyether and / or polyester skeleton in the main skeleton are highly flexible and are used as base resins for adhesives to various substrates, and are adhesives for fiber-reinforced plastics. It is known that it is useful as (see Patent Document 1).
さらに、これをエポキシ樹脂と混合することで軟質塩化ビュル樹脂用接着剤とするこ とが知られて!/、る (特許文献 2参照）。  Furthermore, it is known that this can be mixed with an epoxy resin to form an adhesive for soft chlorinated resin (see Patent Document 2).
特許文献 1 :特開 2004— 238557号公報  Patent Document 1: JP 2004-238557 A
特許文献 2：特開昭 63— 118388号公報  Patent Document 2: JP-A 63-118388
[0003] しかしながら、これら接着剤用ベース樹脂は、全てのプラスチック基材への接着性 が優れるのではなぐ特に、農業関連、下水道関連において、現在、幅広く使用され て!/、る塩化ビュル樹脂に対する単独使用での優れた接着性能は得られて!/、な!/、。ま た、ラジカル重合性樹脂には、特に可塑剤を含有した所謂、軟質塩化ビュル樹脂に 対し接着できる樹脂はなぐ表面サンディング、或いは、熱融着等により接着している のが実情であった。また有機溶剤を用いる接着剤では、溶剤の揮発の問題等におい て、環境上、好ましくないという問題点があった。 [0003] However, these base resins for adhesives are not only excellent in adhesion to all plastic base materials, but are currently widely used in agriculture and sewage systems. Excellent adhesion performance when used alone! / ,! In fact, the radical polymerizable resin is bonded to the so-called soft chlorinated resin containing a plasticizer in particular by surface sanding, heat fusion, or the like. In addition, the adhesive using an organic solvent has a problem that it is not preferable from the viewpoint of solvent volatilization.
発明の開示  Disclosure of the invention
発明が解決しょうとする課題 [0004] 本発明の課題は、従来、接着に使用する際、被接着物を選択しなければならない という問題点のあったラジカル重合性樹脂において、被接着物を選択することなく使 用できる接着剤の開発にある。特に軟質塩化ビュル樹脂に対して優れた接着性能を 示すラジカル重合性樹脂組成物、この樹脂組成物及び塩化ビュル樹脂を使用した 構造物、この樹脂組成物を主成分とする被覆材、並びにこの樹脂組成物を使用する 塩化ビュル樹脂の接着方法を提供することにある。 Problems to be solved by the invention [0004] An object of the present invention is to provide an adhesive that can be used without selecting an adherend in a radically polymerizable resin that has conventionally had a problem of selecting an adherend when used for bonding. It is in the development of agents. In particular, a radical polymerizable resin composition exhibiting excellent adhesion performance to a soft chlorinated resin, a structure using the resin composition and a chlorinated resin, a coating material mainly composed of the resin composition, and the resin It is an object of the present invention to provide a method for bonding a chlorinated resin.
課題を解決するための手段  Means for solving the problem
[0005] 即ち、本発明は、ポリカーボネートジオール (A1)とジイソシァネート化合物 (A2)と を反応させてイソシァネート基含有化合物 (A3)を得、次!/、で前記 (A3)と 1個の水酸 基を含有する（メタ）アクリル化合物とを反応させて得られる（メタ）アタリロイル基を有 するポリカーボネート骨格含有ウレタン樹脂 (A)と、ジシクロペンテュル基を有するラ ジカル重合性不飽和単量体 (B)とを含むことを特徴とする被覆接着用ラジカル重合 性樹脂組成物を提供するものである。 That is, in the present invention, the polycarbonate diol (A1) and the diisocyanate compound (A2) are reacted to obtain an isocyanate group-containing compound (A3), and then the above (A3) and one hydroxide A urethane polymerizable resin having a polycarbonate skeleton having a (meth) acryloyl group obtained by reacting a (meth) acrylic compound containing a group (A) and a radically polymerizable unsaturated monomer having a dicyclopentyl group The present invention provides a radically polymerizable resin composition for coating adhesion, comprising (B).
また、本発明は、前記被覆接着用ラジカル重合性樹脂組成物を介して、基材に塩 化ビュル樹脂層を設けてなることを特徴とする構造物を提供するものである。  The present invention also provides a structure characterized in that a salted bull resin layer is provided on a substrate via the above-mentioned radically polymerizable resin composition for coating adhesion.
また、本発明は、前記被覆接着用ラジカル重合性樹脂組成物を使用することを特 徴とする塩化ビュル樹脂の基材への接着方法を提供するものである。  The present invention also provides a method for adhering a chlorinated bull resin to a substrate, characterized by using the radically polymerizable resin composition for coating adhesion.
また、本発明は、前記被覆接着用ラジカル重合性樹脂組成物を主成分とすることを 特徴とする被覆材を提供するものである。  The present invention also provides a coating material comprising the radically polymerizable resin composition for coating adhesion as a main component.
また、本発明は、前記被覆接着用ラジカル重合性樹脂組成物を主成分とすることを 特徴とする接着剤を提供するものである。  The present invention also provides an adhesive comprising the radically polymerizable resin composition for coating adhesion as a main component.
発明の効果  The invention's effect
[0006] 本発明により、特に硬質塩化ビュル樹脂および軟質塩化ビュル樹脂同士を、ある いはポリ塩化ビュル樹脂を基材に対して、優れた接着性能で接着できる。また、ポリ 塩化ビュル樹脂の被覆材 (プライマー、塗料、シーリング材、ノ テ）として使用できる。 発明を実施するための最良の形態  [0006] According to the present invention, it is possible to bond a hard chloride resin and a soft chloride resin, or a polychlorinated resin to a substrate with excellent adhesion performance. It can also be used as a coating material (primer, paint, sealing material, note) of poly (vinyl chloride) resin. BEST MODE FOR CARRYING OUT THE INVENTION
[0007] 本発明において、（メタ）アタリロイル基を有するカーボネート骨格含有ウレタン樹脂 [0007] In the present invention, a carbonate skeleton-containing urethane resin having a (meth) ataryloyl group
(A)は、分子中に少なくとも 1個の (メタ）アタリロイル基を有する。かかる樹脂は、ポリ カーボネートジオール (Al)とジイソシァネート化合物 (A2)とを、好ましくはイソシァ ネート基と水酸基との当量比（NCO/OH)が 1. 5〜2となるように反応させてイソシ ァネート基含有化合物 (A3)を得、次レ、で前記 (A3)と 1個の水酸基を含有する（メタ )アクリル化合物 (A4)とを、好ましくはイソシァネート基と水酸基との当量比（NCO/ OH)がほぼ同じになるように各化合物を反応させて得られる。 (A) has at least one (meth) atalyloyl group in the molecule. Such resins are poly The carbonate diol (Al) and the diisocyanate compound (A2) are preferably reacted so that the equivalent ratio of the isocyanate group to the hydroxyl group (NCO / OH) is 1.5 to 2 to obtain the isocyanate group-containing compound (A3). In the next step, the (A3) and the (meth) acrylic compound (A4) containing one hydroxyl group preferably have an equivalent ratio (NCO / OH) of the isocyanate group to the hydroxyl group substantially the same. It is obtained by reacting each compound as follows.
[0008] ここでいうポリカーボネートジオール (A1)は、例えば、脂肪族鎖状ジオール及び/ 又は脂環式ジオールと炭酸ジメチル、炭酸ジェチル等の炭酸エステルとのエステル 交換反応、アルキレン基を有する環状炭酸エステルの開環反応、ホスゲンと脂肪族 鎖状ジオール及び/又は脂環式ジオールとの反応等により得られ、好ましくは数平 均分子量カ 300〜3000、特に好まし < (ま 500〜2000の範囲で る。 ί列え (ま、、 1 , 6 一へキサンカーボネートジオール等の脂肪族鎖状カーボネートジオール、 1 , 4ーシ クロへキサンカーボネートジオール等の脂環式カーボネートジオールが挙げられる。 この数平均分子量は、 300〜3000の範囲力 S好ましく、 300未満であるとカーボネー トに由来する特性が弱くなり、 3000より大きいと、ポリイソシァネートとの反応および得 られた化合物の粘度が上がり、実用上作業し難い。カーボネートジオール (A1)の製 造に使用される原料の脂肪族鎖状ジオール及び/又は脂環式ジオールとしては、 任意な構造を有するものが挙げられる。一例を挙げれば、エチレングリコール、 1 , 3 プロピレングリコーノレ、 1 , 2—プロピレングリコーノレ、ジエチレングリコーノレ、ジプロ ピレングリコーノレ、ネオペンチノレグリコーノレ、 1 , 3—ブタンジォーノレ、 1 , 4 ブタンジ オール、 1 , 6 へキサンジオール、 1 , 9ーノナンジオール、 1 , 10 デカンジオール 、シクロへキサンジメチロール、 1 , 4ーシクロへキサンジオール等が挙げられる。 また、カーボネートジオール (A1)と、従来より知られているポリオキシプロピレンジ 才ーノレ、ポリテトラメチレングリコーノレ、ポリ才キシメチレンジ才ーノレ等のポリエーテノレ ポリオール；或いは多価アルコールと多塩基性カルボン酸との縮合物であるポリエス テルポリオールとを併用することもできる。ジイソシァネート化合物 (Α2)と反応させる ジオールとして、ポリカーボネートジオール (A1)を 60質量％以上含むことが好ましく 、 90質量％以上含むことがより好ましい。 [0008] The polycarbonate diol (A1) here is, for example, an ester exchange reaction between an aliphatic chain diol and / or an alicyclic diol and a carbonate such as dimethyl carbonate or jetyl carbonate, or a cyclic carbonate having an alkylene group. A ring opening reaction of phosgene and an aliphatic chain diol and / or an alicyclic diol, etc., preferably a number average molecular weight of 300 to 3000, particularly preferably <(or in the range of 500 to 2000). (Organic chain carbonate diols such as 1,6-monohexane carbonate diol, and alicyclic carbonate diols such as 1,4-cyclohexane carbonate diol. Number average) The molecular weight is in the range of 300 to 3000, preferably S. If it is less than 300, the characteristics derived from the carbonate will be weak, and if it is greater than 3000, it will react with the polyisocyanate. The viscosity of the obtained compound is increased and it is difficult to work practically.The aliphatic chain diol and / or alicyclic diol used as a raw material for the production of carbonate diol (A1) has an arbitrary structure. For example, ethylene glycol, 1,3 propylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, neopentino glycol, 1,3-butanediol, 1 1, 4-butanediol, 1,6 hexanediol, 1,9-nonanediol, 1,10 decanediol, cyclohexane dimethylol, 1,4-cyclohexanediol, etc. Further, carbonate diol (A1), Conventionally known polyoxypropylene di-diol, polytetramethylene glycol Polyesterol polyols such as lime-ximethylene di-nore, or polyester polyols, which are condensates of polyhydric alcohols and polybasic carboxylic acids, can also be used in combination with polycarbonate diols to react with diisocyanate compounds (Α2). Preferably, (A1) is contained in an amount of 60% by mass or more, more preferably 90% by mass or more.
[0009] 本発明において、ジイソシァネート化合物 (Α2)とは、分子中にイソシァネート基を 2 個有するものを指す。 In the present invention, the diisocyanate compound (Α2) is a compound having an isocyanate group in the molecule. It refers to what you have.
前記ジイソシァネート化合物 (A2)としては、例えば、 2, 4—トリレンジイソシァネート 、その異性体又はこれら異性体の混合物（以下 TDIと略す）、ジフヱニルメタンジイソ シァネート、へキサメチレンジイソシァネート、イソホロンジイソシァネート（以下 IPDIと 略す）、キシリレンジイソシァネート、水添キシリレンジイソシァネート、ジシクロへキシ る。これらを単独で又は 2種以上併用して使用することができる。上記ジイソシァネー ト化合物 (A2)のうち、特にイソシァネート基を 2個有する脂肪族系の化合物が、得ら れる耐候性変色の観点から好ましレ、。  Examples of the diisocyanate compound (A2) include 2,4-tolylene diisocyanate, its isomer or a mixture of these isomers (hereinafter abbreviated as TDI), diphenylmethane diisocyanate, hexamethylene diiso- sane. Cyanate, isophorone diisocyanate (hereinafter abbreviated as IPDI), xylylene diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexyl. These can be used alone or in combination of two or more. Of the diisocyanate compound (A2), an aliphatic compound having two isocyanate groups is particularly preferred from the viewpoint of the weather resistance discoloration obtained.
[0010] 前記 1個の水酸基を含有する (メタ）アクリル化合物 (A4)としては、水酸基含有 (メ タ）アクリル酸エステルが好ましく用いられる。例えば、 2—ヒドロキシェチル (メタ）ァク ート等であり；更にポリエチレングリコールモノ（メタ）アタリレート、ポリプロピレングリコ ールモノ (メタ）アタリレート等の様な、水酸基を 2個有するアルコールのモノ (メタ）ァク リレート類；トリス（ヒドロキシェチル）イソシァヌル酸のジ（メタ）アタリレート、ペンタエリ スリトールトリ（メタ）アタリレート等の様な、 3個以上の水酸基を有するアルコールの部 分 (メタ）アタリレート等を少量併用することがで [0010] As the (meth) acrylic compound (A4) containing one hydroxyl group, a hydroxyl group-containing (meth) acrylic ester is preferably used. For example, 2-hydroxyethyl (meth) actate and the like; and further monohydric alcohols having two hydroxyl groups, such as polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate. (Meth) acrylates; partial (meth) acrylates of alcohols having 3 or more hydroxyl groups, such as di (meth) acrylate of tris (hydroxyethyl) isocyanuric acid, pentaerythritol tri (meth) acrylate A small amount of rate etc. can be used together
きる。  wear.
[0011] 本発明で用いる重合性不飽和単量体 (B)は、骨格中にジシクロペンテュル基を有 するラジカル重合性不飽和単量体である。具体的には、例えば、ジシクロペンテュル ォキシェチル（メタ）アタリレート、ジシクロペンテュル（メタ）アタリレート、ジシクロペン タニル (メタ）アタリレート等が挙げられる力 S、他のラジカル重合性単量体との併用も可 能である。例えば、スチレン、ビュルトルエン、メチルスチレン、パラメチルスチレン、ク ロノレスチレン、ジクロノレスチレン、ビニノレナフタレン、ェチノレビニノレエーテノレ、メチノレビ ニール、ケトンメチル (メタ）アタリレート、ェチル (メタ）アタリレート、メチル (メタ）アタリ レート、アタリロニトリノレ、メタタリロニトリノレ、グリシジル（メタ）アタリレート、 2—ヒドロキシ ェチル（メタ）アタリレート、 2—ヒドロキシプロピル（メタ）アタリレート、 2—ェチルへキシ ノレ（メタ）アタリレート、 N—ビュルピロリドン、 1—ビュルイミダゾール、イソボルニル（メ タ）アタリレート、テトラヒドロフルフィリル（メタ）アタリレート、カルビトール（メタ）アタリレ ート、フエノキシェチル（メタ）アタリレート、 1 , 3—ブタンジ（メタ）アタリレート、 1 , 6 - へキサンジオールジ（メタ）アタリレート、ポリエチレングリコールジ（メタ）アタリレート、ヒ ドロキシビバリン酸エステルネオペンチルグリコールジ（メタ）アタリレート、トリメチロー ノレプロパントリ（メタ）アタリレート、ペンタエリスリトーノレトリ（メタ）アタリレート、ペンタエリ スリトールテトラ（メタ）アタリレート、ジペンタエリスリトールへキサ（メタ）アタリレート、ェ チレングリコールジ（メタ）アタリレート、ジエチレングリコールジ（メタ）アタリレート、トリ エチレングリコールジ（メタ）アタリレート、 1 , 3—ブチレングリコールジ（メタ）アタリレー ト、 1 , 4 ブタンジオールジ（メタ）アタリレート、ネオペンチルダリコールジ（メタ）アタリ レート、ジシクロペンテュルォキシェチル（メタ）アタリレート、ジシクロペンテュル（メタ） アタリレート、ジシクロペンタニル（メタ）アタリレート、ジペンタエリスリトールへキサ（メタ )アタリレート、ジペンタエリスリトールモノヒドロキシペンタ（メタ）アタリレート、ジトリメチ ロールプロパンテトラ (メタ)アタリレート、グリセロールジ（メタ）アタリレート、メトキシジェ チレングリコールジ (メタ)アタリレート、メトキシトリエチレングリコールジ (メタ)アタリレー ト、テトラエチレングリコールジ (メタ)アタリレート、トリプロピレングリコールジ（メタ）ァク リレート、 EO変性トリメチロールプロパントリ（メタ）アタリレート、 PO変性トリメチロール プロパントリ（メタ）アタリレートより選ばれる一種以上のものである。 [0011] The polymerizable unsaturated monomer (B) used in the present invention is a radically polymerizable unsaturated monomer having a dicyclopentyl group in the skeleton. Specifically, for example, force S including dicyclopentuoxychetyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and other radical polymerizable monomers Can be used in combination with For example, styrene, butyltoluene, methylstyrene, paramethylstyrene, chloronorstyrene, dichronolestyrene, vinylenonaphthalene, ethinolevinoleatenole, methinolevinyl, ketone methyl (meth) acrylate, ethyl (meth) acrylate, methyl (Meth) Atalylate, Atalilonitrinole, Metatalonitrinole, Glycidyl (Meth) Atylate, 2-Hydroxy Ethyl (Meth) Atylate, 2-Hydroxypropyl (Meth) Atarylate, 2-Ethyl Hexyl Nore (Meth) atarylate, N-Buylpyrrolidone, 1-Buylimidazole, Isobornyl ) Atarylate, Tetrahydrofurphyryl (meth) acrylate, Carbitol (meth) acrylate, Phenoxetyl (meth) acrylate, 1, 3-butanedi (meth) acrylate, 1, 6-hexanediol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxybivalate ester neopentyl glycol di (meth) acrylate, trimethylol propanepropane tri (meth) acrylate, pentaerythritol retriate (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol hex (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) ate-relay 1,3-Butyleneglycol di (meth) atrelate, 1,4 butanediol di (meth) atarylate, neopentyldalicol di (meth) talate, dicyclopentuloxychetyl (meth) atarylate , Dicyclopenturyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, ditrimethylolpropane tetra (meta ) Atarylate, Glycerol di (meth) acrylate, Methoxyethylene glycol di (meth) acrylate, Methoxytriethylene glycol di (meth) acrylate, Tetraethylene glycol di (meth) acrylate, Tripropylene glycol di (meth) Akurere DOO, EO-modified trimethylolpropane tri (meth) Atari rate, is more than one kind selected from the PO modified trimethylol propane tri (meth) Atari rate.
本発明のラジカル重合性組成物は、硬化させる際に空気による硬化性阻害を防ぐ 目的で、水酸基含有ァリルエーテル化合物を前記 1個の水酸基を含有する (メタ）ァ クリル化合物 (A4)と併用して用いることもできる。例えば、エチレングリコールモノァリ ノレエーテノレ、ジエチレングリコーノレモノァリノレエーテノレ、トリエチレングリコーノレモノァ リノレエーテノレ、ポリエチレングリコーノレモノァリノレエーテノレ、プロピレングリコーノレモノ ァリノレエーテノレ、ジプロピレングリコーノレモノァリノレエーテノレ、トリプロピレングリコーノレ モノァリノレエーテル、ポリプロピレングリコールモノァリノレエーテル、 1 , 2—ブチレング リコーノレモノァリノレエーテノレ、 1 , 3ーブチレングリコーノレモノァリノレエーテノレ、へキシ レングリコーノレモノァリノレエーテノレ、オタチレングリコーノレモノァリノレエーテノレ、 トリメチ ロールプロパンジァリルエーテル、グリセリンジァリルエーテル、ペンタエリスリトールト リアリルエーテル等の多価アルコール類のァリルエーテル化合物等が挙げられ、水 酸基を 1個有するァリルエーテル化合物が好まし!/、。 In the radical polymerizable composition of the present invention, a hydroxyl group-containing allyl ether compound is used in combination with the (meth) acrylic compound (A4) containing one hydroxyl group for the purpose of preventing curability inhibition by air during curing. It can also be used. For example, ethylene glycol monoethanolate, diethylene glycol monoethanolate, triethylene glycol monoethanolate, polyethylene glycol monoethanolate, propylene glycol monoreinoate, dipropylene glycol Nolemonolinoleatenore, Tripropylene glycolenole mononoreether, Polypropylene glycol mononoleoleether, 1,2-butylene Ricohone mononoleoatenore, 1,3-butylene glyconolemonolino Reethenole, Hexylene Glyconole Monolinole Ete Nore, Otatilen Glyconore Monolinole Ete Nore, Trimethylolpropane Diaryl Ether, Glycerin Diaryl Ether, Pentaerythritol Arirueteru compounds of polyvalent alcohols such as Realistic ether and the like, water Preference is given to aryl ether compounds having one acid group!
[0013] 本発明における、（メタ）アタリロイル基を有するポリカーボネート骨格含有ウレタン 樹脂 (A)の製造方法の一例を挙げる。先ずジイソシァネート化合物 (A2)と、好ましく は数平均分子量 300〜3000の範囲のポリカーボネートジオール (A1)とを、（A2) / (Al) = l . 5〜2モル比で反応させ、イソシァネート基含有化合物 (A3)を生成する。 次!/、でそれに 1個の水酸基を含有する（メタ）アクリル化合物 (A4)を、イソシァネート 基に対して水酸基がほぼ当量となるように反応させる。  [0013] An example of a method for producing a polycarbonate skeleton-containing urethane resin (A) having a (meth) attalyloyl group in the present invention will be given. First, a diisocyanate compound (A2) and a polycarbonate diol (A1) preferably having a number average molecular weight in the range of 300 to 3000 are reacted in a molar ratio of (A2) / (Al) = 1.5 to 2 to obtain an isocyanate group-containing compound. Generate (A3). Next, the (meth) acrylic compound (A4) containing one hydroxyl group is reacted with the isocyanate group so that the hydroxyl group is approximately equivalent to the isocyanate group.
[0014] 本発明のラジカル重合性樹脂組成物は、前記ポリカーボネート骨格含有ウレタン樹 脂 (A)と前記重合性不飽和単量体 (B)とを含む。中でも、前記ポリカーボネート骨格 含有ウレタン樹脂 (A) 90〜； 10質量部と、前記重合性不飽和単量体 (B) 10〜90質 量部とを相互溶解したものが好まし!/、。  [0014] The radical polymerizable resin composition of the present invention contains the polycarbonate skeleton-containing urethane resin (A) and the polymerizable unsaturated monomer (B). Among them, the polycarbonate skeleton-containing urethane resin (A) 90 to 10 parts by mass and the polymerizable unsaturated monomer (B) 10 to 90 parts by mass are preferably dissolved together.
[0015] 本発明の樹脂組成物には、重合禁止剤を添加するのが好ましぐ前記重合禁止剤 としては、例えば、トリハイドロキノン、ハイドロキノン、 1 , 4—ナフトキノン、パラべンゾ キノン、トノレハイド口ノン、 p tert ブチノレ力テコーノレ、 2, 6 tert ブチノレー 4ーメ チルフエノール等が挙げられる。重合禁止剤の使用量は、樹脂組成物中 10〜； 1000 ppmが好ましい。  [0015] It is preferable to add a polymerization inhibitor to the resin composition of the present invention. Examples of the polymerization inhibitor include trihydroquinone, hydroquinone, 1,4-naphthoquinone, parabenzoquinone, and tonolhydride. Mouth non, p tert butynole power teconore, 2, 6 tert butynole 4-methylphenol and the like. The amount of the polymerization inhibitor used is preferably 10 to 1000 ppm in the resin composition.
[0016] 本発明の樹脂組成物は、通常ラジカルを発生する公知の硬化剤を添加して硬化す る。添加し得る硬化剤としては、紫外線硬化剤、電子線硬化剤、光硬化剤、熱硬化 剤から選択される 1種類以上のものが挙げられる。硬化剤の使用量は、前記樹脂組 成物 100質量部に対して、 0. ；!〜 10質量部が好ましぐ；!〜 5質量部がより好ましい [0016] The resin composition of the present invention is usually cured by adding a known curing agent that generates radicals. Examples of the curing agent that can be added include one or more selected from ultraviolet curing agents, electron beam curing agents, photocuring agents, and thermosetting agents. The amount of the curing agent used is preferably 0.;! To 10 parts by mass with respect to 100 parts by mass of the resin composition; more preferably 5 to 5 parts by mass.
〇 Yes
[0017] 前記紫外線硬化剤とは、光増感性物質である。その具体的なものとしては、例えば 、ベンゾインアルキルエーテルのようなベンゾインエーテル系；ベンゾフエノン、メチル オルソベンゾィルベンゾエートなどのベンゾフエノン系；ベンジルジメチルケタール、 2 , 2 ジエトキシァセトフエノン、 2 ヒドロキシー2 メチルプロピオフエノン、 4 イソ プロピル一 2—ヒドロキシ一 2—メチルプロピオフエノン、 1 , 1—ジクロロアセトフエノン などのァセトフエノン系； 2—クロ口チォキサントン、 2—メチルチオキサントン、 2—イソ プロピルチォキサントンなどのチォキサントン系などが挙げられる。 [0018] 前記電子線硬化剤としては、例えば、ハロゲン化アルキルベンゼン、ジサルファイド 系化合物などが挙げられる。 [0017] The ultraviolet curing agent is a photosensitizing substance. Specific examples thereof include, for example, benzoin ethers such as benzoin alkyl ethers; benzophenones such as benzophenone and methyl orthobenzoylbenzoate; benzyl dimethyl ketal, 2,2 diethoxyacetophenone, 2 hydroxy-2 methyl Acetophenones such as propiophenone, 4-isopropyl-1-hydroxy-1-2-methylpropiophenone, 1,1-dichloroacetophenone; 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, etc. And thixanthone series. [0018] Examples of the electron beam curing agent include halogenated alkylbenzenes and disulfide compounds.
[0019] 前記光硬化剤としては、例えば、ヒドロキシアルキルフエノン系化合物、アルキルチ ォキサントン系化合物、スルホ二ゥム塩系化合物、ァシルフォスフィンオキサイド系化 合物が挙げられる。 [0019] Examples of the photocuring agent include hydroxyalkylphenone compounds, alkylthioxanthone compounds, sulfonium salt compounds, and acylphosphine oxide compounds.
[0020] 前記熱硬化剤としては、有機過酸化物が挙げられる。具体的には例えば、ジァシ ルパーオキサイド系、パーォキシエステル系、ハイド口パーオキサイド系、ジアルキル パーオキサイド系、ケトンパーオキサイド系、パーォキシケタール系、アルキルパーェ ステル系、パーカーボネート系等の公知のものが使用でき、混練条件、養生温度等 で適宜選択される。  [0020] Examples of the thermosetting agent include organic peroxides. Specifically, for example, known peroxy peroxides, peroxyesters, hydride peroxides, dialkyl peroxides, ketone peroxides, peroxyketals, alkyl peresters, percarbonates, etc. Can be used and is appropriately selected depending on kneading conditions, curing temperature, and the like.
[0021] また、本発明の樹脂組成物に、硬化促進剤としてナフテン酸コバルト、オタテン酸コ ノ レトなどの有機金属塩、アミン系、 βージケトン類等の公知のものを併用することが 出来る。  [0021] In addition, the resin composition of the present invention may be used in combination with a known accelerator such as an organic metal salt such as cobalt naphthenate or otetenate, an amine or β-diketone as a curing accelerator.
[0022] 本発明の樹脂組成物には、一般に知られている不飽和ポリエステル樹脂、ビュルゥ レタン樹脂、ビュルエステルウレタン樹脂、ポリイソシァネート、ポリエポキシド、アタリ ル樹脂類、アルキッド樹脂類、尿素樹脂類、メラミン樹脂類、ポリ酢酸ビュル、酢酸ビ 二ル系共重合体、ポリジェン系エラストマ一、飽和ポリエステル類、飽和ポリエーテル 類；ニトロセノレローズ、セノレローズアセテートブチレートなどのセノレローズ誘導体；アマ 二油、桐油、大豆油、ヒマシ油、エポキシ化油等の油脂類など、他の慣用の天然およ び合成高分子化合物を本発明の効果を損なわない範囲で添加できる。  [0022] The resin composition of the present invention includes generally known unsaturated polyester resins, bururetan resins, burester urethane resins, polyisocyanates, polyepoxides, talyl resins, alkyd resins, urea resins. , Melamine resins, poly (butyl acetate), vinyl acetate copolymers, polygen elastomers, saturated polyesters, saturated polyethers; senorelose derivatives such as nitrosenorose and senorerose acetate butyrate; Other conventional natural and synthetic polymer compounds such as oils such as tung oil, soybean oil, castor oil, epoxidized oil and the like can be added as long as the effects of the present invention are not impaired.
[0023] また、本発明の樹脂組成物にガラス繊維、炭素繊維、有機繊維、金属繊維等を補 強材として 5〜70質量％添加できる。 [0023] Further, glass fiber, carbon fiber, organic fiber, metal fiber and the like can be added to the resin composition of the present invention as a reinforcing material in an amount of 5 to 70 mass%.
本発明の樹脂組成物には、例えば、炭酸カルシウム、タルク、マイ力、クレー、シリカ パウダー、コロイダルシリカ、硫酸バリウム、水酸化アルミニウム、ガラス粉、ガラスビー ズ、砕砂等の充填剤を配合してパテ、シーリング剤、塗料、被覆材として使用すること 力 Sできる。また布、クラフト紙への含浸補強を行う材料としても有効である。さらにステ アリン酸亜鉛、チタン白、亜鉛華、その他各種顔料、染料、安定剤、難燃剤等の公知 の他の添加剤を添加することもできる。 [0024] 本発明の被覆接着用ラジカル重合性樹脂組成物は、好ましくはポリ塩化ビュルを 有する部位に対して用いられる。ポリ塩化ビュル同士の接着剤あるいはポリ塩化ビニ ルの基材への接着剤、前記接着剤のベース樹脂、ポリ塩化ビュルに対して用いるプ ライマーや塗料、各種基材のポリ塩化ビュル樹脂に対する被覆材、フィルムラミネ一 ト材、パテ、ペースト、繊維強化材を用いた接着用樹脂、及びインキビヒクル等、被覆 接着を必要とする用途に好適である力 特にこれらに制限されるものではない。 本発明において基材とは、軟質塩化ビュル樹脂、硬質塩化ビュル樹脂、或いは金 属、繊維、紙、皮革、プラスチックであり、特に塩化ビュル樹脂と前記基材とを強固に 接着、被覆する用途に使用可能である。 The resin composition of the present invention contains a filler such as calcium carbonate, talc, my strength, clay, silica powder, colloidal silica, barium sulfate, aluminum hydroxide, glass powder, glass beads, and crushed sand. Can be used as a sealing agent, paint, or coating material. It is also effective as a material for impregnating and reinforcing cloth and kraft paper. Furthermore, other known additives such as zinc stearate, titanium white, zinc white, various other pigments, dyes, stabilizers, flame retardants and the like can be added. [0024] The radically polymerizable resin composition for coating adhesion of the present invention is preferably used for a portion having polychlorinated bulls. Adhesives between polychlorinated bulls or adhesives to polyvinyl chloride base materials, base resins of the adhesives, primers and paints used for polychlorinated bulls, and coating materials for polychlorinated bulle resins of various base materials Forces suitable for applications requiring coating adhesion, such as film laminating material, putty, paste, adhesive resin using fiber reinforcing material, and ink vehicle are not particularly limited thereto. In the present invention, the base material is a soft chloride resin, a hard chloride resin, or metal, fiber, paper, leather, and plastic, and particularly for applications in which the chloride resin and the substrate are firmly bonded and coated. It can be used.
[0025] 本発明の樹脂組成物は、従来の接着剤では良好な接着性能を示すことができなか つた塩化ビュル樹脂、特に軟質塩化ビュル樹脂に対しても、優れた接着性能を示す 。従って、本発明の樹脂組成物を介して、基材に塩化ビュル樹脂層を設けてなる本 発明の構造物は、この優れた接着性能を活力、したものであり、塩化ビュル樹脂層は 基材上に安定して固定化される。このように、本発明の樹脂組成物を使用する、塩化 ビュル樹脂の基材への接着方法は、従来にない優れた方法である。この時の接着方 法としては、接着剤として本発明の樹脂組成物を使用すること以外は、公知の方法を 適用すれば良い。本発明の構造物は、上記の通り、前記基材、本発明の樹脂組成 物及び塩化ビュル樹脂をこの順に積層してなるものである。前記基材と本発明の樹 脂組成物との間には、公知のエポキシ系、ウレタン系、イソシァネート系、アクリル系、 水性分散体等のプライマーを使用しても良い。  [0025] The resin composition of the present invention exhibits excellent adhesion performance even to a chlorinated resin, particularly a soft chlorinated chloric resin, for which a conventional adhesive could not exhibit good adhesion performance. Therefore, the structure of the present invention in which the chlorinated resin layer is provided on the base material through the resin composition of the present invention is a material that makes use of this excellent adhesion performance. It is stably immobilized on the top. As described above, the method for adhering butyl chloride resin to a base material using the resin composition of the present invention is an excellent method which has not been conventionally used. As a bonding method at this time, a known method may be applied except that the resin composition of the present invention is used as an adhesive. As described above, the structure of the present invention is formed by laminating the base material, the resin composition of the present invention, and a chlorinated resin in this order. A known epoxy-based, urethane-based, isocyanate-based, acrylic-based or aqueous dispersion primer may be used between the substrate and the resin composition of the present invention.
実施例  Example
[0026] 以下本発明を実施例によって更に詳細に説明する力 本発明はこれらの実施例に 限定されるものではない。また文章中「部」とあるのは、質量部を示すものである。  [0026] Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples. Also, “parts” in the text indicates mass parts.
[0027] (合成例 1) [Synthesis Example 1]
メタクリロイル基を有するポリカーボネート骨格含有ウレタン樹脂の調製  Preparation of polycarbonate skeleton-containing urethane resin having methacryloyl group
温度計、攪拌機、不活性ガス導入口、及び還流冷却器を備えた 1リットルの四つ口 フラスコに、ポリカーボネートジオール（宇部興産製 UH— CARB100、 1 , 6—へキ サンジオール系のポリカーボネートジオール、数平均分子量 1000)を 510部仕込み 、 IPDIを 222部加え発熱を抑制しながら 80°Cで 4時間反応させた。 NCO当量が理 論値とほぼ同じ 732となり安定したので 40°C迄冷却し、 2—ヒドロキシェチルメタクリレ ートを 137部加え、反応促進触媒としてスズ触媒を 0. 037部添加し、空気雰囲気下 90°Cで 7時間反応させた。 NCO%が 0· 3質量％以下となったので、ハイドロキノン 0 . 05部を加え、メタクリロイル基を有するポリカーボネート骨格含有ウレタン樹脂を得 た。 To a 1 liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser, polycarbonate diol (Ube Industries UH- CARB100, 1,6-hexadiol-based polycarbonate diol, Preparation of 510 parts of number average molecular weight 1000) Then, 222 parts of IPDI was added and reacted at 80 ° C for 4 hours while suppressing heat generation. The NCO equivalent was 732, which was almost the same as the theoretical value and stabilized. Cooled to 40 ° C, 137 parts of 2-hydroxyethyl methacrylate was added, 0.037 parts of tin catalyst was added as a reaction promoting catalyst, and air was added. The reaction was carried out at 90 ° C for 7 hours. Since NCO% was 0.3 mass% or less, 0.05 part of hydroquinone was added to obtain a polycarbonate skeleton-containing urethane resin having a methacryloyl group.
[0028] (合成例 2)  [0028] (Synthesis example 2)
メタクリロイル基を有するポリカーボネート骨格含有ウレタン樹脂の調製  Preparation of polycarbonate skeleton-containing urethane resin having methacryloyl group
実施例 1と全く同一の反応装置にポリカーボネートジオール (宇部興産製 UH— C ARB 100,数平均分子量 1000)を 510部仕込み、次に、 TDIを 174部加え、発熱に 注意しながら 80°Cで 4時間保持した。 NCO等量が理論値とほぼ同じ 684となり安定 したので 40°C迄冷却し、空気雰囲気下で 2—ヒドロキシェチルメタタリレート 137部を 加え、反応促進触媒としてスズ触媒を 0. 037部添加し、 90°Cで 5時間反応させた。  Charge 510 parts of polycarbonate diol (UH-C ARB 100, number average molecular weight 1000, manufactured by Ube Industries) to the same reactor as in Example 1, and then add 174 parts of TDI. Hold for 4 hours. Since the NCO equivalent was 684, which was almost the same as the theoretical value and stabilized, it was cooled to 40 ° C, and 137 parts of 2-hydroxyethyl methacrylate were added in an air atmosphere, and 0.037 part of tin catalyst was added as a reaction promoting catalyst. And reacted at 90 ° C for 5 hours.
NCO%が 0. 3質量％以下となったので、ハイドロキノン 0. 049部をカロえ、メタタリロイ ル基を有するポリカーボネート骨格含有ウレタン樹脂を得た。  Since NCO% was 0.3% by mass or less, 0.049 part of hydroquinone was removed to obtain a polycarbonate skeleton-containing urethane resin having a metathalylyl group.
[0029] (合成例 3) [0029] (Synthesis example 3)
ポリエーテル骨格含有ウレタンアタリレート樹脂組成物の調製  Preparation of polyether skeleton-containing urethane acrylate resin composition
ポリオールジオール（三井化学社製ァクトコール、数平均分子量 700)を 283部、 T DIを 144部仕込み、窒素雰囲気中で反応温度を 80°Cに保持し、 5時間後理論 NC O当量 516を確認した。 30°C迄冷却し、 2—ヒドロキシェチルメタアタリレートを 109部 仕込み、窒素雰囲気中において 80°Cで 4時間反応させた。 NCO%が 0. 3質量％以 下になつたので、ハイドロキノン 0. 08部をカロえ、ポリエーテル骨格含有ウレタンアタリ レート樹脂組成物を得た。  283 parts of polyol diol (actol made by Mitsui Chemicals, number average molecular weight 700) and 144 parts of TDI were charged, the reaction temperature was maintained at 80 ° C in a nitrogen atmosphere, and the theoretical NC O equivalent 516 was confirmed after 5 hours. . After cooling to 30 ° C, 109 parts of 2-hydroxyethyl methacrylate was charged and reacted at 80 ° C for 4 hours in a nitrogen atmosphere. Since NCO% was 0.3% by mass or less, 0.08 part of hydroquinone was removed to obtain a polyether skeleton-containing urethane acrylate resin composition.
[0030] (合成例 4) [0030] (Synthesis Example 4)
不飽和ポリエステルの調製  Preparation of unsaturated polyester
窒素ガス導入管、還流コンデンサ、攪拌機を備えた 2Lのガラス製フラスコに、プロ ピレンダリコール 608部、無水マレイン酸 392部、無水フタル酸 592部を仕込み、窒 素気流下、加熱を開始した。内温 200°Cにて、常法にて脱水縮合反応を行い、ガー ドナー粘度が Q〜R (ソリッド/スチレン = 70/30質量比率で希釈し、ソリッドの縮合 度を確認）、酸価が 24KOHmg/gになったところで、 180°Cまで冷却し、トルハイド ロキノン 0. 09部を添加した。さらに 150°Cまで冷却し、不飽和ポリエステルソリッドを 得た。 A 2 L glass flask equipped with a nitrogen gas inlet tube, a reflux condenser, and a stirrer was charged with 608 parts of propylene glycol, 392 parts of maleic anhydride, and 592 parts of phthalic anhydride, and heating was started under a nitrogen stream. Perform dehydration condensation reaction at an internal temperature of 200 ° C in the usual way, When the donor viscosity is Q to R (diluted at a solid / styrene = 70/30 mass ratio and the degree of condensation of the solid is confirmed) and the acid value reaches 24 KOHmg / g, the mixture is cooled to 180 ° C and toluhydroquinone 0. 09 parts were added. The mixture was further cooled to 150 ° C to obtain an unsaturated polyester solid.
[0031] (実施例 1) [Example 1]
合成例 1により得られたウレタン樹脂 100部をジシクロペンテュルォキシェチルメタ タリレート（日立化成社製） 186部に加熱溶解させ、ラジカル重合性樹脂組成物を得 た。更に促進剤として 8%オタテン酸コバルト 0. 6部を添加して均一になる様混合し、 ラジカル硬化剤 328E (商品名、化薬ァクゾ社製)を 3部添加、混合させた。下記接着 性評価法に従い、接着性評価を行った。得られた樹脂は、臭気も少ない樹脂組成物 であった。  100 parts of the urethane resin obtained in Synthesis Example 1 was heated and dissolved in 186 parts of dicyclopentuoxychetyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.) to obtain a radical polymerizable resin composition. Further, 0.6 part of 8% cobalt oxalate was added as an accelerator and mixed so as to be uniform, and 3 parts of radical curing agent 328E (trade name, manufactured by Kayaku Akuzo Co., Ltd.) was added and mixed. The adhesion was evaluated according to the following adhesion evaluation method. The obtained resin was a resin composition with little odor.
[0032] (実施例 2) [0032] (Example 2)
合成例 2により得られたウレタン樹脂 100部をジシクロペンテュルォキシェチルメタ タリレート（日立化成社製） 186部に加熱溶解させ、ラジカル重合性樹脂組成物を得 た。更に促進剤として 8%オタテン酸コバルト 0. 6部を添加して均一になる様混合し、 ラジカル硬化剤 328E (商品名、化薬ァクゾ社製)を 3部添加、混合させた。下記接着 性評価法に従い、接着性評価を行った。得られた樹脂は、臭気も少ない樹脂組成物 であった。  100 parts of the urethane resin obtained in Synthesis Example 2 was heated and dissolved in 186 parts of dicyclopentuoxychetyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.) to obtain a radical polymerizable resin composition. Further, 0.6 part of 8% cobalt oxalate was added as an accelerator and mixed so as to be uniform, and 3 parts of radical curing agent 328E (trade name, manufactured by Kayaku Akuzo Co., Ltd.) was added and mixed. The adhesion was evaluated according to the following adhesion evaluation method. The obtained resin was a resin composition with little odor.
[0033] (比較例 1) [0033] (Comparative Example 1)
合成例 3により得られたウレタン樹脂 200部をスチレン 108部に加熱溶解させ、ラジ カル重合性樹脂組成物を得た。更に促進剤として 8%オタテン酸コバルト 0. 6部を添 カロして均一になる様混合し、ラジカル硬化剤パーメック N (商品名、 日本油脂社製熱 硬化剤）を 3部添加、混合させた。下記接着性評価法に従い、接着性評価を行った。  200 parts of the urethane resin obtained in Synthesis Example 3 was dissolved in 108 parts of styrene by heating to obtain a radical polymerizable resin composition. In addition, 0.6 parts of 8% Cobalt Otateate was added as an accelerator and mixed in a uniform manner, and 3 parts of radical curing agent Parmek N (trade name, Nippon Oil & Fats Thermosetting Co., Ltd.) was added and mixed. . Adhesion evaluation was performed according to the following adhesive evaluation method.
[0034] (比較例 2) [0034] (Comparative Example 2)
合成例 3により得られたウレタン樹脂 100部をジシクロペンテュルォキシェチルメタ タリレート（日立化成社製） 186部に加熱溶解させ、ラジカル重合性樹脂組成物を得 た。更に促進剤として 8%オタテン酸コバルト 0. 6部を添加して均一になる様混合し、 ラジカル硬化剤 328E (商品名、化薬ァクゾ社製)を 3部添加、混合させた。下記接着 性評価法に従い、接着性評価を行った。 100 parts of the urethane resin obtained in Synthesis Example 3 was dissolved by heating in 186 parts of dicyclopentuoxychetyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.) to obtain a radical polymerizable resin composition. Further, 0.6 part of 8% cobalt oxalate was added as an accelerator and mixed so as to be uniform, and 3 parts of radical curing agent 328E (trade name, manufactured by Kayaku Akuzo Co., Ltd.) was added and mixed. Adhesion below The adhesiveness was evaluated according to the property evaluation method.
[0035] (比較例 3) [0035] (Comparative Example 3)
合成例 1により得られたウレタン樹脂 200部をスチレン 108部に加熱溶解させ、ラジ カル重合性樹脂組成物を得た。更に促進剤として 8%オタテン酸コバルト 0. 6部を添 カロして均一になる様混合し、ラジカル硬化剤パーメック N (商品名、 日本油脂社製）を 3部添加、混合させた。下記接着性評価法に従い、接着性評価を行った。  200 parts of the urethane resin obtained in Synthesis Example 1 was heated and dissolved in 108 parts of styrene to obtain a radical polymerizable resin composition. Further, 0.6 part of 8% cobalt oxalate was added as an accelerator and mixed so as to be uniform, and 3 parts of radical curing agent Parmec N (trade name, manufactured by NOF Corporation) was added and mixed. Adhesion evaluation was performed according to the following adhesive evaluation method.
[0036] (比較例 4) [0036] (Comparative Example 4)
合成例 4により得られた不飽和ポリエステルソリッド 100部をスチレン 167部に加熱 溶解させ、ラジカル重合性樹脂組成物を得た。更に促進剤として 8%オタテン酸コバ ルト 0. 4部を添加して均一になる様混合し、ラジカル硬化剤パーメック N (商品名、 日 本油脂社製)を 1. 5部添加、混合させた。下記接着性評価法に従い、接着性評価を 行った。  100 parts of unsaturated polyester solid obtained in Synthesis Example 4 was dissolved by heating in 167 parts of styrene to obtain a radical polymerizable resin composition. Furthermore, as an accelerator, 0.4 part of 8% otate acid cobalt was added and mixed so as to be uniform, and 1.5 parts of radical curing agent Parmec N (trade name, manufactured by Nippon Oil & Fats Co., Ltd.) was added and mixed. . The adhesion was evaluated according to the following adhesion evaluation method.
[0037] 上記樹脂組成物の接着性能につ!/、て、基材として塩化ビュル樹脂（以下、 PVCと 略す）を用い評価を行った。  [0037] The adhesive performance of the resin composition was evaluated by using a chlorinated resin (hereinafter abbreviated as PVC) as a base material.
(接着性評価：実施例；!〜 2、比較例；!〜 4)  (Adhesive evaluation: Examples;! To 2, Comparative examples;! To 4)
基材として市販の硬質塩化ビュル樹脂 (硬質 PVC、タキロン社製、 3mm厚、グレー 色）を、縦長さ 100mm、幅 25mmに切削し、表面を軽くアセトンにて脱脂して埃を取 り除いた。その後、 2枚の試験片に、接着面積が 25mmX 25mmとなる様に上記各 種樹脂組成物を塗布し、樹脂組成物が硬化するまで接着部分がずれなレ、様に重り を載せて硬化させ、さらに 60°Cの乾燥機に 1時間入れ、樹脂組成物を完全硬化させ た。  A hard vinyl chloride resin (hard PVC, manufactured by Takiron, 3mm thickness, gray color) as a base material was cut into a vertical length of 100mm and a width of 25mm, and the surface was lightly degreased with acetone to remove dust. . Thereafter, the above-mentioned various resin compositions are applied to the two test pieces so that the adhesion area is 25 mm × 25 mm, and the adhesive part is shifted until the resin composition is cured, and the weight is placed on the test piece and cured. Further, the resin composition was completely cured by placing it in a dryer at 60 ° C. for 1 hour.
接着性評価試験は、 JIS— K 6850に準じ、引張剪断（引張速度 5mm/分)試験 により行い、剪断強さ及び試験後の接着界面の状態を観察した。試験により硬質 PV C基材が破壊した場合を基材破壊と表記した。基材界面で剥離してしまって!/、る場 合は、接着性能が劣り、評価判定を不良： Xとし、接着力が基材強度に勝り、基材破 壊する場合は、評価判定を良好：〇とした。  The adhesion evaluation test was conducted by a tensile shear (tensile speed 5 mm / min) test according to JIS-K 6850, and the shear strength and the state of the adhesion interface after the test were observed. The case where the hard PVC substrate was destroyed by the test was indicated as substrate failure. If it peels off at the substrate interface! /, The adhesive performance is inferior and the evaluation judgment is poor: X. If the adhesive strength is superior to the base material strength and the base material breaks, the evaluation judgment is made. Good: ◯.
次に、基材である軟質塩化ビュル樹脂（軟質 PVC)との接着性能評価法につ!/、て 、以下記す。 軟質 PVCは、塩化ビニル樹脂パウダー（新第一塩ビ社製 ZEST1000Z) 100部に 、可塑剤としてジォクチルフタレート 50部を添加し、粉末バリウム 亜鉛系安定剤 2 部を常温プレンド後、 170°Cの加熱ミキシングロールにて 5分間、均一に溶融練りを 行い、厚さ約 lmm厚の軟質 PVCシートを得た。得られた軟質 PVCシートを、長さ 20 0mm,幅 25mmの短冊状に切断し、上記各樹脂組成物を縦長さ 150mm X幅 25m mの面積に均一に塗布し、上力ゝら同短冊を重ねて試験片とし、気泡を抜きながら軽く 抑え、 2枚のガラス板に前記試験片を挟み、榭脂組成物を硬化させた。その後、前記 試験片をガラス板に挟んだまま、 60°Cの乾燥機に 1時間入れ、樹脂組成物を完全硬 化させた。 Next, a method for evaluating the adhesive performance with a soft vinyl chloride resin (soft PVC) as a base material is described below. Soft PVC is made by adding 50 parts of dioctyl phthalate as a plasticizer to 100 parts of vinyl chloride resin powder (Shinichi Dai-ichi Vinyl Co., Ltd. ZEST1000Z), and then adding 2 parts of powdered barium zinc-based stabilizer at room temperature to 170 ° C. The mixture was uniformly melt-kneaded for 5 minutes with a heating mixing roll, to obtain a soft PVC sheet having a thickness of about 1 mm. The obtained flexible PVC sheet was cut into strips with a length of 200 mm and a width of 25 mm, and each of the above resin compositions was evenly applied to an area with a length of 150 mm and a width of 25 mm. The test piece was piled up and held lightly while removing air bubbles, and the test piece was sandwiched between two glass plates to cure the resin composition. Thereafter, the test piece was sandwiched between glass plates and placed in a dryer at 60 ° C. for 1 hour to completely cure the resin composition.
接着性評価試験は、 JIS—K— 6854に準じ、 180度剥離試験 (T字剥離試験、 10 mmZ分）により行レヽ、剥離強さ及び試験後の接着界面の状態を観察した。試験によ り、一方の面のみに接着剤がつき、界面剥離してしまっている場合を不良： Xとし、接 着剤層自体が破壌され、基材の両面に付着し、接着強さが得られている場合を良好 :〇として評価した。  The adhesion evaluation test was conducted in accordance with JIS-K-6854, and the 180 ° peel test (T-peel test, 10 mmZ min) was used to observe the line and peel strength and the state of the adhesive interface after the test. According to the test, when only one side of the adhesive is adhered and the interface peels off, it is judged as bad: X, and the adhesive layer itself is broken and adheres to both sides of the substrate. Was evaluated as good: ◯.
以上の結果から、硬質 PVC基材及び軟質 PVC基材の両方に対する接着性の総 合判定を行い、両方の基材に対し良好に接着するものを良好：〇、そうでなレ、ものを 不良： Xとして評価した。結果を表 1及び 2に示す。  Based on the above results, the overall adhesion of both hard PVC substrate and soft PVC substrate was judged, and those that adhere well to both substrates were good: 〇, but those that were not good were bad. : Rated as X. The results are shown in Tables 1 and 2.
[表 1] [table 1]
Figure imgf000013_0001
[表 2] 比較例 1 比較例 2 比較例 3 実施例 4
Figure imgf000013_0001
[Table 2] Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 4
く硬質 PVC基材〉 界面剥離 界面剥離 界面剥離 界面剥離 剪断強さ (MPa) 3> 3> 3> 3> 接着性判定 X X X X く軟質 PVC基材〉 界面剥離 界面剥離 界面剥離 界面剥離 180度剥離強さ（MPa) 3> 3> 3> 3>  Hard PVC substrate> Interfacial delamination Interfacial delamination Interfacial delamination Interfacial delamination Shear strength (MPa) 3> 3> 3> 3> Adhesion test XXXX Soft PVC substrate> Interfacial delamination Interfacial delamination Interfacial delamination Interfacial delamination 180 degree delamination strength (MPa) 3> 3> 3> 3>
接着性判定 X X X X 総合判定 X X X X  Adhesion judgment X X X X Overall judgment X X X X
[0040] 上表より、本発明の樹脂組成物は、硬質 PVC基材同士、及び従来の接着剤では 接着し得な力 た軟質 PVC基材同士の接着性にぉレ、ても、優れた接着特性を示し ていることが判った。 [0040] From the above table, the resin composition of the present invention was excellent in adhesion between hard PVC base materials and between soft PVC base materials that could not be bonded with conventional adhesives. It was found to exhibit adhesive properties.
[0041] (実施例 3)  [Example 3]
合成例 1により得られたウレタン樹脂 100部をジシクロペンテニルォキシェチルメタ タリレート（日立ィ匕成社製) 186部に加熱溶解させ、ラジカル重合性樹脂組成物を得 た。促進剤として 8%ォクテン酸コパルト 0. 6部を添カ卩して均一になる様混合し、ラジ カル硬化剤 328E (商品名、化薬ァクゾ社製)を 3部添加、混合させた。基材として用 いる冷間圧延鋼板（2mm厚、 JISG3141 SPCC— SD)の表面をアセトン脱脂し、ィ ソシァネート系のプライマーであるプライマー PD (商品名、大日本インキ化学工業社 製)を、刷毛を用いて塗布し、常温で 1時間乾燥させた。その鋼板表面に、先に調製 した促進剤及ぴ硬化剤を添加した樹脂組成物を均一に塗布し、直ちに、前記接着 性評価の項で用レ、たシート状の軟質塩ィ匕ビエル樹脂 (軟質 PVC)を空気が入らなレヽ 様に載せ、常温で 1日放置、硬化させ、軟質塩化ビニル樹脂シート 本発明の樹脂 組成物 Z鋼板基材からなる構造物を作成した。  100 parts of the urethane resin obtained in Synthesis Example 1 was dissolved by heating in 186 parts of dicyclopentenyloxychetyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.) to obtain a radical polymerizable resin composition. As an accelerator, 0.6 part of 8% octenoic acid co-palt was added and mixed so as to be uniform, and 3 parts of radical curing agent 328E (trade name, manufactured by Kayaku Akuzo Co., Ltd.) was added and mixed. The surface of a cold-rolled steel plate (2 mm thick, JISG3141 SPCC—SD) used as a base material is degreased with acetone, and primer PD (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), a primer based on isocyanate, is applied to the brush. And then dried at room temperature for 1 hour. The resin composition to which the accelerator and the curing agent prepared previously were uniformly applied was applied to the surface of the steel plate, and immediately, the sheet-like soft salt-vinyl resin (used in the adhesive evaluation section) ( Soft PVC) was placed in a layer without air, allowed to stand at room temperature for 1 day, and cured to produce a structure comprising a soft vinyl chloride resin sheet resin composition Z steel plate substrate of the present invention.
完全硬化後、軟質塩ィ匕ビニル樹脂シートの角をカッターの刃を用いて剥がそうとし た力 軟質塩ィ匕ビニル樹脂シートは、本発明の樹脂組成物により鋼板基材と一体ィ匕 していた。その結果、容易に剥がすことができず、軟質塩化ビニル樹脂シ一トと鋼板 基材の一体構造物が得られた。  After complete curing, the force to peel off the corners of the soft salt vinyl resin sheet with a cutter blade. The soft salt vinyl resin sheet was integrated with the steel plate substrate by the resin composition of the present invention. . As a result, it could not be easily peeled off, and an integrated structure of a soft vinyl chloride resin sheet and a steel plate substrate was obtained.
[0042] (実施例 4)  [Example 4]
合成例 1により得られたウレタン榭脂 100部をジシクロペンテニルォキシェチルメタ タリレート（日立化成社製） 186部に加熱溶解させ、ラジカル重合性樹脂組成物を得 た。更に促進剤として 8%オタテン酸コバルト 0. 6部を添加して均一になる様混合し、 ラジカル硬化剤 328E (商品名、化薬ァクゾ社製）を 3部添加、混合させた。基材とし て、 30cm大、厚み 3cmの JIS準拠のコンクリート板の極表面を、ディスクサンダーで 平滑に削り、そのコンクリート板表面からエアーガンで削りかすを除去した。続いて、 その表面にイソシァネート系のプライマーであるプライマー PD (商品名、大日本イン キ化学工業社製)を、刷毛を用い塗布し、常温で 1時間乾燥させ、コンクリート板を調 製した。そのコンクリート板の上に、先に調製した促進剤及び硬化剤を添加した樹脂 組成物を均一に塗布し、直ちに、前記接着性評価の項で用いたシート状の軟質塩化 ビュル樹脂（軟質 PVC)を空気が入らない様に載せ、常温で 1日放置、硬化させ、軟 質塩化ビュル樹脂シート/本発明の樹脂組成物/ JIS準拠のコンクリート板基材から なる構造物を作成した。 100 parts of the urethane resin obtained in Synthesis Example 1 was mixed with dicyclopentenyloxychetylmeta It was dissolved by heating in 186 parts of talylate (manufactured by Hitachi Chemical Co., Ltd.) to obtain a radical polymerizable resin composition. Further, 0.6 part of 8% cobalt oxalate was added as an accelerator and mixed so as to be uniform, and 3 parts of radical curing agent 328E (trade name, manufactured by Kayaku Akuzo) was added and mixed. As the base material, the extreme surface of a JIS-compliant concrete plate 30 cm in size and 3 cm thick was cut smoothly with a disk sander, and the scraps were removed from the concrete plate surface with an air gun. Subsequently, primer PD (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), which is an isocyanate primer, was applied to the surface using a brush and dried at room temperature for 1 hour to prepare a concrete board. On the concrete board, uniformly apply the resin composition to which the accelerator and curing agent prepared above are added, and immediately, the sheet-like soft chlorinated butyl resin (soft PVC) used in the above-mentioned adhesive evaluation section. Was allowed to stand at room temperature for 1 day and cured to prepare a structure composed of a soft chlorinated chlorinated resin sheet / the resin composition of the present invention / JIS-compliant concrete board substrate.
完全硬化後、軟質塩化ビュル樹脂シートの角をカッターの刃を用いて剥がそうとし たが、本発明の樹脂組成物により、軟質塩化ビュル樹脂シートは、コンクリート板基 材と一体化していた。その結果、容易に剥がすことができず、軟質塩化ビュル樹脂シ ートとコンクリート板基材の一体構造物が得られた。  After complete curing, an attempt was made to peel off the corners of the soft chloride resin sheet using a cutter blade. However, the soft chloride resin sheet was integrated with the concrete board substrate by the resin composition of the present invention. As a result, it could not be easily peeled off, and an integrated structure of a soft chloride resin sheet and a concrete board substrate was obtained.
[0043] (比較例 5) [0043] (Comparative Example 5)
合成例 4により得られた不飽和ポリエステルソリッド 100部をスチレン 167部に加熱 溶解させ、ラジカル重合性樹脂組成物を得た。更に促進剤として 8%オタテン酸コバ ルト 0. 4部を添加して均一になる様混合し、ラジカル硬化剤パーメック N (商品名、 日 本油脂社製)を 1. 5部添加、混合させた。上記樹脂組成物を用いたこと以外は、実 施例 3と同様にして、軟質塩化ビュル樹脂シート/樹脂組成物/鋼板基材からなる 成形品を作成した。そして、実施例 3と同様にして、カッターの刃で軟質塩化ビュル シートの角を剥がそうとすると、樹脂組成物と軟質塩化ビュルシートとの界面で容易 に剥がれ、軟質塩化ビュル樹脂シートと鋼板基材の一体構造物は得られなかった。  100 parts of unsaturated polyester solid obtained in Synthesis Example 4 was dissolved by heating in 167 parts of styrene to obtain a radical polymerizable resin composition. Furthermore, as an accelerator, 0.4 part of 8% otate acid cobalt was added and mixed so as to be uniform, and 1.5 parts of radical curing agent Parmec N (trade name, manufactured by Nippon Oil & Fats Co., Ltd.) was added and mixed. . Except that the resin composition was used, a molded article composed of a soft chlorinated butyl resin sheet / resin composition / steel plate substrate was prepared in the same manner as in Example 3. Then, in the same manner as in Example 3, when the corner of the soft chloride bull sheet was peeled off with the cutter blade, it was easily peeled off at the interface between the resin composition and the soft chloride bull sheet, and the soft chloride bull resin sheet and the steel plate base were peeled off. A monolithic structure of material was not obtained.
[0044] (比較例 6) [0044] (Comparative Example 6)
合成例 4により得られた不飽和ポリエステルソリッド 100部をスチレン 167部に加熱 溶解させ、ラジカル重合性樹脂組成物を得た。更に促進剤として 8%オタテン酸コバ ルト 0· 4部を添加して均一になる様混合し、ラジカル硬化剤パーメック Ν (商品名、 日 本油脂社製)を 1. 5部添加、混合させた。上記樹脂組成物を用いたこと以外は、実 施例 4と同様にして、軟質塩化ビュル樹脂シート/樹脂組成物/コンクリート板基材 からなる成形品を作成した。そして、実施例 4と同様にして、カッターの刃で軟質塩化 ビュルシートの角を剥がそうとすると、樹脂組成物と軟質塩化ビュルシートとの界面で 容易に剥がれ、軟質塩化ビュル樹脂シートとコンクリート板基材の一体構造物は得ら れなかった。 100 parts of unsaturated polyester solid obtained in Synthesis Example 4 was dissolved by heating in 167 parts of styrene to obtain a radical polymerizable resin composition. In addition, as an accelerator, 8% 0.4 part of a filter was added and mixed so as to be uniform, and 1.5 parts of radical curing agent Parmek Ν (trade name, manufactured by Nippon Oil & Fats Co., Ltd.) was added and mixed. Except that the resin composition was used, a molded article composed of a soft chlorinated butyl resin sheet / resin composition / concrete board substrate was prepared in the same manner as in Example 4. Then, in the same manner as in Example 4, when the corner of the soft chloride bull sheet was peeled off with the cutter blade, it was easily peeled off at the interface between the resin composition and the soft chloride bull sheet, and the soft chloride bull resin sheet and the concrete plate were removed. A monolithic structure of the substrate could not be obtained.
[0045] (実施例 5) [0045] (Example 5)
合成例 1により得られたウレタン樹脂 100部をジシクロペンテュルォキシェチルメタ タリレート（日立化成社製） 186部に加熱溶解させ、ラジカル重合性樹脂組成物を得 た。更に促進剤として 8%オタテン酸コバルト 0. 6部を添加して均一になる様混合し、 ラジカル硬化剤 328Ε (商品名、化薬ァクゾ社製)を 3部添加、混合させた。実施例 1 〜2の接着性評価に用いた硬質及び軟質塩化ビュル樹脂の基材の上に、 0. 25mm のアプリケーターを用い、本発明の樹脂組成物を均一に塗布し、常温で硬化後、 60 °Cで 1時間完全硬化させ、本発明の樹脂組成物で被覆された硬質または軟質塩化 ビュル樹脂シート状被覆構造物を作成した。  100 parts of the urethane resin obtained in Synthesis Example 1 was heated and dissolved in 186 parts of dicyclopentuoxychetyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.) to obtain a radical polymerizable resin composition. Further, 0.6 part of 8% cobalt oxalate was added as an accelerator and mixed so as to be uniform, and 3 parts of a radical curing agent 328Ε (trade name, manufactured by Kayaku Akuzo Co., Ltd.) was added and mixed. Using a 0.25 mm applicator, the resin composition of the present invention was uniformly applied on the base material of the hard and soft chlorinated resin used in the adhesive evaluation of Examples 1 and 2, and cured at room temperature. It was completely cured at 60 ° C. for 1 hour to prepare a hard or soft chlorinated chlorinated resin sheet-like covering structure coated with the resin composition of the present invention.
硬化後、本発明の樹脂組成物被膜を、カッターの刃を用い、端部から塩化ビュル 樹脂基材から剥がそうとしたが、基材に対し十分密着しており、剥がれず、塩化ビニ ル樹脂と一体となって!/、ることを確認した。  After curing, the resin composition film of the present invention was peeled off from the end of the bull chloride resin base material using a cutter blade, but it was sufficiently adhered to the base material and did not peel off. Together, I confirmed that!
[0046] (比較例 7) [Comparative Example 7]
合成例 4により得られた不飽和ポリエステルソリッド 100部をスチレン 167部に加熱 溶解させ、ラジカル重合性樹脂組成物を得た。更に促進剤として 8%オタテン酸コバ ルト 0. 4部を添加して均一になる様混合し、ラジカル硬化剤パーメック N (商品名、 日 本油脂社製)を 1. 5部添加、混合させた。上記樹脂組成物を用いたこと以外は、実 施例 5と同様にして、樹脂組成物被膜を、カッターの刃を用い、端部から塩化ビュル 樹脂基材から剥がそうとすると、基材に対し密着性が不十分のため、容易に被膜が 剥がれ、塩化ビュル樹脂との一体被膜は得られなかった。  100 parts of unsaturated polyester solid obtained in Synthesis Example 4 was dissolved by heating in 167 parts of styrene to obtain a radical polymerizable resin composition. Furthermore, as an accelerator, 0.4 part of 8% otate acid cobalt was added and mixed so as to be uniform, and 1.5 parts of radical curing agent Parmec N (trade name, manufactured by Nippon Oil & Fats Co., Ltd.) was added and mixed. . Except for using the above resin composition, in the same manner as in Example 5, when the resin composition film was peeled off from the end portion of the resin chloride using a cutter blade, Since the adhesion was insufficient, the coating was easily peeled off, and an integral coating with chlorinated resin could not be obtained.
[0047] 以上のように、本発明により、硬質塩化ビュル樹脂、及び従来の接着剤では良好に 接着できなかった軟質塩化ビュル樹脂に対しても優れた接着性能を示す被覆接着 用ラジカル重合性樹脂組成物を提供でき、有用である。そして、本発明の樹脂組成 物を基材へ塗布し、塩化ビュル樹脂を被覆接着できるので、塩ビ鋼板、塩ビ化粧板 、塩ビ積層体等の製造に好適である。 [0047] As described above, according to the present invention, the hard chloride resin and the conventional adhesive are excellent. It is useful because it can provide a radically polymerizable resin composition for coating adhesion that exhibits excellent adhesion performance even for soft chlorinated resin that could not be adhered. And since the resin composition of this invention can be apply | coated to a base material and a chloride resin can be coat | covered and adhere | attached, it is suitable for manufacture of a vinyl chloride steel plate, a vinyl chloride decorative board, a vinyl chloride laminated body, etc.
産業上の利用可能性 Industrial applicability
本発明は、特に各種塩化ビュル樹脂の基材への接着、各種塩化ビュル樹脂の被 覆に利用可能である。  The present invention is particularly applicable to adhesion of various types of chlorinated resin to a substrate and covering of various types of chlorinated resin.

Claims

請求の範囲 The scope of the claims
[1] ポリカーボネートジオール (A1)とジイソシァネート化合物 (A2)とを反応させてイソ シァネート基含有化合物 (A3)を得、次!/、で前記 (A3)と 1個の水酸基を含有する（メ タ）アクリル化合物 (A4)とを反応させて得られる（メタ）アタリロイル基を有するポリ力 ーボネート骨格含有ウレタン樹脂 (A)と、  [1] A polycarbonate diol (A1) and a diisocyanate compound (A2) are reacted to obtain an isocyanate group-containing compound (A3), and then the above (A3) and one hydroxyl group are contained in ) Polyurethane-skeleton containing urethane resin (A) having a (meth) atallyloyl group obtained by reacting with an acrylic compound (A4),
ジシクロペンテュル基を有するラジカル重合性不飽和単量体 (B)とを含むことを特 徴とする被覆接着用ラジカル重合性樹脂組成物。  A radically polymerizable resin composition for coating adhesion, comprising a radically polymerizable unsaturated monomer (B) having a dicyclopentyl group.
[2] 前記ポリカーボネートジオール (A1)の数平均分子量が、 300〜3000である請求 項 1に記載の被覆接着用ラジカル重合性樹脂組成物。 [2] The radically polymerizable resin composition for coating adhesion according to claim 1, wherein the polycarbonate diol (A1) has a number average molecular weight of 300 to 3000.
[3] 前記ポリカーボネートジオール (A1)が、脂肪族又は脂環式カーボネートジオール である請求項 1又は 2に記載の被覆接着用ラジカル重合性樹脂組成物。 [3] The radically polymerizable resin composition for coating adhesion according to claim 1 or 2, wherein the polycarbonate diol (A1) is an aliphatic or alicyclic carbonate diol.
[4] 請求項 1に記載の被覆接着用ラジカル重合性樹脂組成物を介して、基材に塩化ビ ニル樹脂層を設けてなることを特徴とする構造物。 [4] A structure comprising a vinyl chloride resin layer provided on a base material via the radically polymerizable resin composition for covering adhesion according to claim 1.
[5] 請求項 1に記載の被覆接着用ラジカル重合性樹脂組成物を使用することを特徴と する塩化ビュル樹脂の基材への接着方法。 [5] A method for adhering a chlorinated bull resin to a substrate, comprising using the radically polymerizable resin composition for covering adhesion according to claim 1.
[6] 請求項 1に記載の被覆接着用ラジカル重合性樹脂組成物を主成分とすることを特 徴とする被覆材。 [6] A coating material comprising the radically polymerizable resin composition for coating adhesion according to claim 1 as a main component.
[7] 請求項 1に記載の被覆接着用ラジカル重合性樹脂組成物を主成分とすることを特 徴とする接着剤。  [7] An adhesive comprising the radically polymerizable resin composition for covering adhesion according to claim 1 as a main component.
PCT/JP2007/067594 2006-09-15 2007-09-10 Radical-polymerizable resin composition for coating or adhesive WO2008032677A1 (en)

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JP2006250810A JP4180626B2 (en) 2006-09-15 2006-09-15 Structure and method for bonding soft vinyl chloride resin to substrate
JP2006-250810 2006-09-15

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