JP2008069307A - Radically polymerizable resin composition for coating and adhering - Google Patents

Radically polymerizable resin composition for coating and adhering Download PDF

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JP2008069307A
JP2008069307A JP2006250810A JP2006250810A JP2008069307A JP 2008069307 A JP2008069307 A JP 2008069307A JP 2006250810 A JP2006250810 A JP 2006250810A JP 2006250810 A JP2006250810 A JP 2006250810A JP 2008069307 A JP2008069307 A JP 2008069307A
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resin composition
resin
vinyl chloride
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radically polymerizable
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JP2008069307A5 (en
JP4180626B2 (en
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O Shibata
欧 柴田
Sachiko Fujita
幸子 藤田
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DH Material Inc
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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
    • 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

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

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radically polymerizable resin composition exhibiting excellent adhesion particularly to a soft polyvinylchloride resin, a structure formed using the resin composition and a vinylchloride resin, a coating material composed of the resin composition as an essential constituent, and a method for adhering a vinyl chloride resin using the resin composition. <P>SOLUTION: The radically polymerizable resin composition includes: a urethane resin (A) containing a polycarbonate skeleton having a methacryloyl group prepared by the steps of reacting a polycarbonate diol (A1) with a diisocyanate compound (A2) to prepare an isocyanate group-containing compound (A3), and thereafter reacting the compound (A3) with a methacryl compound (A4) having one hyroxy group; and a radically polymerizable unsaturated monomer (B). The structure comprises a substrate provided with a vinyl chloride resin layer through the resin composition. The coating material is composed of the resin composition as an essential constituent. The method for adhering the vinyl chloride resin to the substrate comprises using the resin composition. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、（メタ）アク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、特に塩化ビニル樹脂との接着性に優れた被覆接着用ラジカル重合性樹脂組成物、係る樹脂組成物及び塩化ビニル樹脂を使用した構造物、係る樹脂組成物を主成分とする被覆材、並びに係る樹脂組成物を使用する塩化ビニル樹脂の接着方法に関するものである。   The present invention relates to a radically polymerizable resin composition for coating adhesion comprising a polycarbonate skeleton-containing urethane resin containing a (meth) acryloyl group and a radically polymerizable unsaturated monomer having a specific skeleton, particularly with a vinyl chloride resin. Radical polymerizable resin composition for coating adhesion excellent in adhesiveness, structure using such resin composition and vinyl chloride resin, coating material mainly composed of such resin composition, and chlorination using such resin composition The present invention relates to a method for bonding vinyl resin.

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）アク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）。
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ニル樹脂用接着剤とすることが知られている（特許文献２参照）。
特開２００４−２３８５５７号公報 特開昭６３−１１８３８８号公報 A (meth) acryloyl group-containing urethane resin having a polyether and / or polyester skeleton in the main skeleton is rich in flexibility and is used as a base resin for adhesives to various substrates, and is useful as an adhesive for fiber-reinforced plastics. It is known that there is (see Patent Document 1).
Furthermore, it is known that an adhesive for soft vinyl chloride resin is obtained by mixing this with an epoxy resin (see Patent Document 2).
JP 2004-238557 A JP 63-118388 A

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く、特に、農業関連、下水道関連において、現在、幅広く使用されている塩化ビニ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いない。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、軟質塩化ビニル樹脂に対し接着できる樹脂はなく、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。   However, these base resins for adhesives are not excellent in adhesion to all plastic base materials, and in particular, when used alone for vinyl chloride resins that are widely used in agriculture and sewerage. Adhesive performance has not been obtained. Further, there is no resin that can be bonded to a so-called soft vinyl chloride resin containing a plasticizer, in particular, the radical polymerizable resin, and the actual situation is that it is bonded by surface sanding or heat fusion. Moreover, the adhesive using an organic solvent has a problem that it is not preferable from the viewpoint of the problem of solvent volatilization.

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り、特に軟質塩化ビニ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、係る樹脂組成物及び塩化ビニル樹脂を使用した構造物、係る樹脂組成物を主成分とする被覆材、並びに係る樹脂組成物を使用する塩化ビニル樹脂の接着方法を提供することにある。   An object of the present invention is to develop an adhesive that can be used without selecting an object to be bonded in a radical polymerizable resin that has conventionally had a problem of selecting an object to be bonded when used for bonding. A radically polymerizable resin composition exhibiting excellent adhesion performance particularly to a soft vinyl chloride resin, a structure using such a resin composition and a vinyl chloride resin, a coating material comprising such a resin composition as a main component, and An object of the present invention is to provide a method for bonding a vinyl chloride resin using such a resin composition.

即ち、本発明は、ポリカーボネートジオール（Ａ１）とジイソシアネート化合物（Ａ２）とを反応させてイソシアネート基含有化合物（Ａ３）を得、次いで前記（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（Ａ）と、ジシクロペンテニ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。
また、本発明は、係る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を提供するものである。
また、本発明は、係る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ニル樹脂の基材への接着方法を提供するものである。
また、本発明は、係る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。 That is, in the present invention, a polycarbonate diol (A1) and a diisocyanate compound (A2) are reacted to obtain an isocyanate group-containing compound (A3), and then the (A3) and a (meth) acrylic compound containing one hydroxyl group. And a polycarbonate skeleton-containing urethane resin (A) having a (meth) acryloyl group obtained by reacting with a radically polymerizable unsaturated monomer (B) having a dicyclopentenyl group. A radical polymerizable resin composition for coating adhesion is provided.
Moreover, this invention provides the structure characterized by providing a vinyl chloride resin layer in a base material through the radically polymerizable resin composition for coating | cover adhesion | attachment.
The present invention also provides a method for adhering a vinyl chloride resin to a substrate, characterized by using the radically polymerizable resin composition for coating adhesion.
Moreover, this invention provides the coating | covering material characterized by using the radically polymerizable resin composition for coating | cover adhesion | attachment as a main component.

本発明により、特に硬質塩化ビニル樹脂および軟質塩化ビニル樹脂同士を、あるいはポリ塩化ビニ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、ポリ塩化ビニル樹脂の被覆材（プライマー、塗料、シーリング材、パテ）として使用できる。   According to the present invention, particularly, a hard vinyl chloride resin and a soft vinyl chloride resin can be bonded to each other, or a polyvinyl chloride resin can be bonded to a substrate with excellent bonding performance. Moreover, it can be used as a covering material (primer, paint, sealing material, putty) of polyvinyl chloride resin.

本発明において、（メタ）アク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（Ａ）は、分子中に少なくとも１個の（メタ）アクリロイル基を有するものである。かかる樹脂は、カーボネートジオール（Ａ１）とジイソシアネート化合物（Ａ２）とを、好ましくはイソシア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アネート基含有化合物（Ａ３）を得、次いで前記（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、好ましくはイソシア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ものである。   In the present invention, the carbonate skeleton-containing urethane resin (A) having a (meth) acryloyl group has at least one (meth) acryloyl group in the molecule. Such a resin is obtained by reacting a carbonate diol (A1) and a diisocyanate compound (A2) so that an equivalent ratio (NCO / OH) of an isocyanate group to a hydroxyl group is preferably 1.5 to 2. (A3) is obtained, and then the (A3) and the (meth) acrylic compound (A4) containing one hydroxyl group, preferably the equivalent ratio (NCO / OH) of the isocyanate group to the hydroxyl group is substantially the same. Thus, it is obtained by reacting each compound.

ここでいうポリカーボネートジオール（Ａ１）とは、例えば、脂肪族２価アルコール及び／又は脂環式２価アルコールと炭酸ジメチル、炭酸ジエ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２価アルコールとの反応等により得られるもので、好ましくは数平均分子量が３００〜３０００、特に好ましくは５００〜２０００の範囲のものである。例えば、１，６−ヘキサンカーボネートジオール等の脂肪族カーボネートジオール、１，４−シクロヘ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の範囲が好ましく、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、ポリイソシア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２価アルコールとしては、任意な構造を有するものが挙げられ、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ル、１，２−プロピレングリコール、ジエチレングリコール、ジプロピレングリコール、ネオペンチルグリコール、１，３−ブタンジオール、１，４−ブタンジオール、１，６−ヘキサンジオール、１，９−ノナンジオール、１，１０−デカンジオール、シクロヘキサンジメチロール、１，４−シクロヘ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オール、ポリテトラメチレングリコール、ポリオキシメチレンジオール等のポリエーテルポリオール、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が、ジイソシアネート化合物（Ａ２）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。 The polycarbonate diol (A1) here means, for example, an ester exchange reaction between an aliphatic dihydric alcohol and / or an alicyclic dihydric alcohol and a carbonate such as dimethyl carbonate or diethyl carbonate, or a cyclic carbonate having an alkylene group. The number average molecular weight is preferably in the range of 300 to 3,000, particularly preferably in the range of 500 to 2,000. Examples thereof include aliphatic carbonate diols such as 1,6-hexane carbonate diol, and alicyclic carbonate diols such as 1,4-cyclohexane carbonate diol. The number average molecular weight is preferably in the range of 300 to 3000. If the number average molecular weight is less than 300, the characteristics derived from the carbonate are weakened. If it is more than 3000, the reaction with the polyisocyanate and the viscosity of the obtained compound are increased. Difficult to work. Examples of the raw material dihydric alcohol used in the production of the carbonate diol (A1) include those having an arbitrary structure. For example, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol Diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, cyclohexanedimethylol, Examples include 1,4-cyclohexanediol.
Also, a carbonate diol (A1) and a conventionally known polyether polyol such as polyoxypropylene diol, polytetramethylene glycol, polyoxymethylene diol, or a condensate of a polyhydric alcohol and a polybasic carboxylic acid. Although a certain polyester polyol can be used in combination, the diol to be reacted with the diisocyanate compound (A2) preferably contains 60% by mass or more, more preferably 90% by mass or more of the polycarbonate diol (A1).

本発明において、ジイソシアネート化合物（Ａ２）とは、分子中にイソシアネート基を２個有するものを指す。
前記ジイソシアネート化合物（Ａ２）としては、例えば、２，４−トリレンジイソシアネート、その異性体又はこれら異性体の混合物（以下ＴＤＩと略す）、ジフェニルメタンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート（以下ＩＰＤＩと略す）、キシリレンジイソシアネート、水添キシリレンジイソシアネート、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、等を挙げることができ、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。上記ジイソシアネート化合物（Ａ２）のうち、特にイソシアネート基を２個有する脂肪族系のものが、得られる耐候性変色の観点から好ましく用いられる。 In the present invention, the diisocyanate compound (A2) refers to a compound having two isocyanate groups in the molecule.
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 diisocyanate, and isophorone diisocyanate (hereinafter abbreviated as IPDI). , Xylylene diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, and the like. These can be used alone or in combination of two or more. Among the diisocyanate compounds (A2), an aliphatic compound having two isocyanate groups is particularly preferably used from the viewpoint of the weather resistance discoloration obtained.

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、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）アクリレート等であり、更に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）アクリレート等の様な、水酸基を２個有するアルコールのモノ（メタ）アクリレート類；トリス（ヒドロキシエチル）イソシアヌル酸のジ（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）アクリレート等を少量併用することができる。   As the (meth) acrylic compound (A4) containing one hydroxyl group, a hydroxyl group-containing (meth) acrylic acid ester is preferably used. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Mono (meth) acrylates of alcohols having two hydroxyl groups, such as acrylate, 3-hydroxybutyl (meth) acrylate, and polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and the like; A small amount of a partial (meth) acrylate of an alcohol having 3 or more hydroxyl groups, such as di (meth) acrylate of (hydroxyethyl) isocyanuric acid, pentaerythritol tri (meth) acrylate, and the like can be used in combination.

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ニル基を有するラジカル重合性のもので、具体的には、例えば、ジシクロペンテニルオキシエチル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート等が挙げられるが、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、ビニルトルエン、メチルスチレン、パラメチルスチレン、クロルスチレン、ジクロルスチレン、ビニルナフタレン、エチルビニルエーテル、メチルビニール、ケトンメチル（メタ）アクリレート、エチル（メタ）アクリレート、メチル（メタ）アクリレート、アクリロニトリル、メタクリロニトリル、グリシジル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、Ｎ−ビニルピロリドン、１−ビニルイミダゾール、イソボルニル（メタ）アクリレート、テトラヒドロフルフィリル（メタ）アクリレート、カルビトール（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、１，３−ブタンジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ヒドロキシピバリン酸エステルネオペンチルグリコールジ（メタ）アクリレート、トリメチロールプロパントリ（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、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、１，３−ブチレングリコールジ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールモノヒドロキシペンタ（メタ）アクリレート、ジトリメチロールプロパンテトラ(メタ)アクリレート、グリセロールジ（メタ）アクリレート、メトキシジエチレングリコールジ(メタ)アクリレート、メトキシトリエチレングリコールジ(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、ペンタエリスリトールテトラ（メタ）アクリレート、テトラエチレングリコールジ(メタ)アクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ＥＯ変性トリメチロールプロパントリ（メタ）アクリレート、ＰＯ変性トリメチロールプロパントリ（メタ）アクリレートより選ばれる一種以上のものである。   The polymerizable unsaturated monomer (B) used in the present invention is a radically polymerizable monomer having a dicyclopentenyl group in the skeleton. Specifically, for example, dicyclopentenyloxyethyl (meth) acrylate, Examples thereof include cyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and the like, but can be used in combination with other radical polymerizable monomers. For example, styrene, vinyl toluene, methyl styrene, paramethyl styrene, chloro styrene, dichloro styrene, vinyl naphthalene, ethyl vinyl ether, methyl vinyl, ketone methyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, acrylonitrile, Methacrylonitrile, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, N-vinylpyrrolidone, 1-vinylimidazole, isobornyl (meth) Acrylate, tetrahydrofurphyryl (meth) acrylate, carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, 1,3-butanedi (meth) Acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate ester neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butylene glycol di (Meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane All di (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta (meth) ) Acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol di (meth) acrylate, methoxydiethylene glycol di (meth) acrylate, methoxytriethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) ) Acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tripropylene glycol Koruji (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate is more than one kind selected from the PO-modified trimethylolpropane tri (meth) acrylate.

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、水酸基含有ア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）アクリル化合物（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アリルエーテル、ジエチレングリコールモノアリルエーテル、トリエチレングリコールモノアリルエーテル、ポリエチレングリコールモノアリルエーテル、プロピレングリコールモノアリルエーテル、ジプロピレングリコールモノアリルエーテル、トリプロピレングリコールモノアリルエーテル、ポリプロピレングリコールモノアリルエーテル、１，２ーブチレングリコールモノアリルエーテル、１，３ーブチレングリコールモノアリルエーテル、ヘキシレングリコールモノアリルエーテル、オクチレングリコールモノアリルエーテル、トリメチロールプロパンジアリルエーテル、グリセリンジアリルエーテル、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アリルエーテル化合物等が挙げられ、水酸基を１個有するアリルエーテル化合物が好ましい。   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 when cured. It can also be used. For example, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, polyethylene glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, tripropylene glycol monoallyl ether, polypropylene glycol monoallyl Ether, 1,2-butylene glycol monoallyl ether, 1,3-butylene glycol monoallyl ether, hexylene glycol monoallyl ether, octylene glycol monoallyl ether, trimethylolpropane diallyl ether, glyceryl diallyl ether, pentaerythritol triallyl Allyl ether compounds of polyhydric alcohols such as ether Is, allyl ether compound having one hydroxyl group are preferred.

本発明において、（メタ）ア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（Ａ）の製造方法の一例を挙げれば、先ずジイソシアネート化合物（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）／（Ａ１）＝２〜１．５モル比で反応させ、イソシアネート基含有化合物（Ａ３）を生成し、次いでそれに１個の水酸基を含有する（メタ）アクリル化合物（Ａ４）を、イソシアネート基に対して水酸基がほぼ当量となるように反応する方法が挙げられる。   In this invention, if an example of the manufacturing method of the polycarbonate frame | skeleton containing urethane resin (A) which has a (meth) acryloyl group is given, first, the diisocyanate compound (A2), Preferably the polycarbonate diol (with a number average molecular weight of 300-3000) ( A1) is reacted with (A2) / (A1) = 2 to 1.5 molar ratio to produce an isocyanate group-containing compound (A3), and then a (meth) acrylic compound containing one hydroxyl group ( A method in which A4) is reacted with respect to an isocyanate group so that the hydroxyl group is approximately equivalent.

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い。   The radical polymerizable resin composition of the present invention contains the polycarbonate skeleton-containing urethane resin (A) and the polymerizable unsaturated monomer (B). Especially, what melt | dissolved 90-10 mass parts of said polycarbonate frame | skeleton containing urethane resins (A) and said polymerizable unsaturated monomer (B) 10-90 mass parts is preferable.

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く、該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、パラベンゾキノン、トルハイドロノン、ｐ−ｔｅｒｔ−ブチルカテコール、２，６−ｔｅｒｔ−ブチル−４−メチルフェ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１０〜１０００ｐｐｍが好ましい。   A polymerization inhibitor is preferably added to the resin composition of the present invention. Examples of the polymerization inhibitor include trihydroquinone, hydroquinone, 1,4-naphthoquinone, parabenzoquinone, toluhydronone, p-tert- Examples include butyl catechol and 2,6-tert-butyl-4-methylphenol. The amount of the polymerization inhibitor used is preferably 10 to 1000 ppm in the resin composition.

本発明の樹脂組成物は、通常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、該樹脂組成物１００質量部に対して、０．１〜１０質量部が好ましく、１〜５質量部がより好ましい。   The resin composition of the present invention is usually cured by adding a curing agent. 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. 0.1-10 mass parts is preferable with respect to 100 mass parts of this resin composition, and, as for the usage-amount of a hardening | curing agent, 1-5 mass parts is more preferable.

前記紫外線硬化剤とは、光増感性物質であり、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；ベンゾフェノン、メチルオルソベンゾイルベンゾエートなどのベンゾフェノン系；ベンジルジメチルケタール、２，２−ジエトキシアセトフェノン、２−ヒドロキシ−２−メチルプロピオフェノン、４−イソプロピル−２−ヒドロキシ−２−メチルプロピオフェノン、１，１−ジクロロアセトフェノンなどのアセトフェノン系；２−クロロチオキサントン、２−メチルチオキサントン、２−イソプロピルチオキサントンなどのチオキサントン系などが挙げられる。   The ultraviolet curing agent is a photosensitizing substance, and specific examples thereof include, for example, benzoin ethers such as benzoin alkyl ethers; benzophenones such as benzophenone and methyl orthobenzoylbenzoate; benzyldimethyl ketal, 2 , 2-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, 1,1-dichloroacetophenone and other acetophenone series; 2-chlorothioxanthone, 2 -Thioxanthone type such as methylthioxanthone and 2-isopropylthioxanthone.

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。   Examples of the electron beam curing agent include halogenated alkylbenzenes and disulfide compounds.

前記光硬化剤としては、例えば、ヒドロキシアルキルフェノン系化合物、アルキルチオキサントン系化合物、スルホニウム塩系化合物が挙げられる。   Examples of the photocuring agent include hydroxyalkylphenone compounds, alkylthioxanthone compounds, and sulfonium salt compounds.

前記熱硬化剤としては、有機過酸化物が挙げられ、具体的には例えば、ジアシルパーオキサイド系、パーオキシエステル系、ハイドロパーオキサイド系、ジアルキルパーオキサイド系、ケトンパーオキサイド系、パーオキシケタール系、アルキルパーエステル系、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。   Examples of the thermosetting agent include organic peroxides. Specific examples include diacyl peroxides, peroxyesters, hydroperoxides, dialkyl peroxides, ketone peroxides, and peroxyketals. Well known ones such as alkyl peresters and percarbonates can be used, and are appropriately selected depending on kneading conditions, curing temperature, and the like.

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、オクテン酸コバルトなどの有機金属塩、アミン系、β−ジケトン類等の公知のものを併用することが出来る。   Moreover, well-known things, such as organic metal salts, such as cobalt naphthenate and cobalt octenoate, amine type, (beta) -diketone, can be used together with the resin composition of this invention as a hardening accelerator.

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、ビニルウレタン樹脂、ビニルエステルウレタン樹脂、ポリイソシアネート、ポリエポキシド、アクリル樹脂類、アルキッド樹脂類、尿素樹脂類、メラニン樹脂類、ポリ酢酸ビニル、酢酸ビニル系共重合体、ポリジエン系エラストマー、飽和ポリエステル類、飽和ポリエーテル類；ニトロセルローズ、セルローズアセテートブチレートなどのセルローズ誘導体；アマニ油、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。   The resin composition of the present invention includes generally known unsaturated polyester resins, vinyl urethane resins, vinyl ester urethane resins, polyisocyanates, polyepoxides, acrylic resins, alkyd resins, urea resins, melanin resins, poly Vinyl acetate, vinyl acetate copolymers, polydiene elastomers, saturated polyesters, saturated polyethers; cellulose derivatives such as nitrocellulose and cellulose acetate butyrate; linseed oil, tung oil, soybean oil, castor oil, epoxidized oil, etc. Other conventional natural and synthetic polymer compounds such as oils and fats can be added as long as the effects of the present invention are not impaired.

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。
本発明の樹脂組成物には、例えば、炭酸カルシウム、タルク、マイカ、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ができる。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。 Moreover, 5-70 mass% of glass fiber, carbon fiber, organic fiber, metal fiber, etc. can be added to the resin composition of this invention as a reinforcing material.
In the resin composition of the present invention, for example, a putty containing a filler such as calcium carbonate, talc, mica, clay, silica powder, colloidal silica, barium sulfate, aluminum hydroxide, glass powder, glass beads, crushed sand, etc. It can be used as a sealing agent, paint, and 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.

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ニルを有する部位に対して用いられ、ポリ塩化ビニ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、ポリ塩化ビニルに対して用いるプライマーや塗料、各種基材ポリ塩化ビニル樹脂に対する被覆材、フィルムラミネート材、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が、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、軟質塩化ビニル樹脂、硬質塩化ビニル樹脂、或いは金属、繊維、紙、皮革、プラスチックであり、特に塩化ビニル樹脂と該基材とを強固に接着、被覆する用途に使用可能である。 The radically polymerizable resin composition for coating adhesion of the present invention is preferably used for a portion having polyvinyl chloride, and is an adhesive between polyvinyl chlorides or an adhesive to a polyvinyl chloride substrate, the adhesive Base resin, primer and paint used for polyvinyl chloride, coating material for various base polyvinyl chloride resin, film laminate material, putty, paste, adhesive resin using fiber reinforcement, ink vehicle, etc. Although it is suitable for applications requiring adhesion, it is not particularly limited thereto.
In the present invention, the base material is a soft vinyl chloride resin, a hard vinyl chloride resin, or a metal, fiber, paper, leather, or plastic, and is used particularly for the purpose of firmly bonding and covering the vinyl chloride resin and the base material. Is possible.

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った塩化ビニル樹脂、特に軟質塩化ビニル樹脂に対しても、優れた接着性能を示すものである。従って、本発明の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本発明の構造物は、この優れた接着性能を活かしたものであり、塩化ビニ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、塩化ビニ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ニル樹脂をこの順に積層してなるものであるが、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、イソシアネート系、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。   The resin composition of the present invention exhibits excellent adhesion performance even with respect to vinyl chloride resins, particularly soft vinyl chloride resins, which could not exhibit good adhesion performance with conventional adhesives. Therefore, the structure of the present invention in which the vinyl chloride resin layer is provided on the base material through the resin composition of the present invention utilizes this excellent adhesive performance, and the vinyl chloride resin layer is formed on the base material. Is stably immobilized. Thus, the method of adhering the vinyl chloride resin to the base material using the resin composition of the present invention is an excellent method that has not existed before. As an adhesion 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 the vinyl chloride resin in this order, but between the base material and the resin composition of the present invention. In addition, a primer such as a known epoxy-based, urethane-based, isocyanate-based, acrylic-based, or aqueous dispersion may be used.

以下本発明を実施例によって更に詳細に説明するが、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。   EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples. In addition, “part” in the text indicates mass part.

（合成例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
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、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℃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℃迄冷却し、２−ヒドロキシエ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℃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。 (Synthesis example 1) Preparation of polycarbonate skeleton containing urethane resin having methacryloyl group Polycarbonate diol (UH manufactured by Ube Industries, Ltd.) was added to a 1 liter four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. -CARB100, number average molecular weight 1000) was charged in 510 parts, and 222 parts of IPDI was added and reacted at 80 ° C. for 4 hours while suppressing heat generation. Since the NCO equivalent was 732, which was almost the same as the theoretical value, and stabilized, it was 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, Reacted for hours. Since NCO% became 0.3 mass% or less, 0.05 part of hydroquinone was added to obtain a polycarbonate skeleton-containing urethane resin having a methacryloyl group.

（合成例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
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−ＣＡＲＢ１００、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℃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℃迄冷却し、空気雰囲気下で２−ヒドロキシエチルメタクリレート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℃で５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０．０４９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。 (Synthesis Example 2) Preparation of polycarbonate skeleton-containing urethane resin having methacryloyl group 510 parts of polycarbonate diol (UH-CARB100, Ube Industries, Ltd., UH-CARB100, number average molecular weight 1000) was charged in the same reaction apparatus as in Example 1, and then TDI. 174 parts was added and kept at 80 ° C. for 4 hours while paying attention to heat generation. Since the NCO equivalent was 684 which was almost the same as the theoretical value and stabilized, it was cooled to 40 ° C., 137 parts of 2-hydroxyethyl methacrylate was added in an air atmosphere, 0.037 parts of tin catalyst was added as a reaction promoting catalyst, and 90 ° C. For 5 hours. Since NCO% became 0.3 mass% or less, 0.049 part of hydroquinone was added to obtain a polycarbonate skeleton-containing urethane resin having a methacryloyl group.

（合成例３）ポリエーテル骨格含有ウレタンアクリレート樹脂組成物の調製
ポリオールジオール（三井化学社製アクトコール、数平均分子量７００）を２８３部、ＴＤＩを１４４部仕込み、窒素雰囲気中で反応温度を８０℃に保持し、５時間後理論ＮＣＯ当量５１６を確認した。３０℃迄冷却し、２−ヒドロキシエチルメタアクリレートを１０９部仕込み、窒素雰囲気中において８０℃で４時間反応させ、ＮＣＯ％が０．３質量％以下になったので、ハイドロキノン０．０８部を加え、ポリエーテル骨格含有ウレタンアクリレート樹脂組成物を得た。 (Synthesis Example 3) Preparation of Polyether Skeleton-Containing Urethane Acrylate Resin Composition 283 parts of polyol diol (Mitsui Chemicals Actol, number average molecular weight 700) and 144 parts of TDI were charged, and the reaction temperature was 80 ° C. in a nitrogen atmosphere. The theoretical NCO equivalent 516 was confirmed after 5 hours. Cooled to 30 ° C, charged with 109 parts of 2-hydroxyethyl methacrylate and reacted for 4 hours at 80 ° C in a nitrogen atmosphere. NCO% was 0.3% by mass or less, so 0.08 part of hydroquinone was added. A polyether skeleton-containing urethane acrylate resin composition was obtained.

（合成例４）不飽和ポリエステルの調製
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、プロピレングリコール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℃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℃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℃まで冷却し、不飽和ポリエステルソリッドを得た。 Synthesis Example 4 Preparation of Unsaturated Polyester 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 a nitrogen stream. Below, heating was started. A dehydration condensation reaction is carried out in an ordinary manner at an internal temperature of 200 ° C., the Gardner 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 is 24 KOHmg / When it became g, it cooled to 180 degreeC and 0.09 part of toluhydroquinone was added. Furthermore, it cooled to 150 degreeC and obtained the unsaturated polyester solid.

（実施例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ニルオキシエチルメタクリレート（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、更に促進剤として８％オクテン酸コバルト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、化薬アクゾ社製）を３部添加、混合させ、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。 (Example 1)
100 parts of the urethane resin obtained in Synthesis Example 1 was dissolved by heating in 186 parts of dicyclopentenyloxyethyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.) to obtain a radical polymerizable resin composition, and further 8% cobalt octenoate 0% as an accelerator. .6 parts were added and mixed so as to be uniform, and 3 parts of radical curing agent 328E (trade name, manufactured by Kayaku Akzo Co., Ltd.) was added and mixed, and adhesion evaluation was performed according to the following adhesion evaluation method. The obtained resin was a resin composition with little odor.

（実施例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ニルオキシエチルメタクリレート（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、更に促進剤として８％オクテン酸コバルト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、化薬アクゾ社製）を３部添加、混合させ、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。 (Example 2)
100 parts of the urethane resin obtained in Synthesis Example 2 was dissolved by heating in 186 parts of dicyclopentenyloxyethyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.) to obtain a radical polymerizable resin composition, and further 8% cobalt octenoate as an accelerator. .6 parts were added and mixed so as to be uniform, and 3 parts of radical curing agent 328E (trade name, manufactured by Kayaku Akzo Co., Ltd.) was added and mixed, and adhesion evaluation was performed according to the following adhesion evaluation method. The obtained resin was a resin composition with little odor.

（比較例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、更に促進剤として８％オクテン酸コバルト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、下記接着性評価法に従い、接着性評価を行った。 (Comparative Example 1)
200 parts of the urethane resin obtained in Synthesis Example 3 is heated and dissolved in 108 parts of styrene to obtain a radical polymerizable resin composition, and 0.6 parts of 8% cobalt octenoate is further added as an accelerator so as to be uniform. After mixing, 3 parts of radical curing agent Parmec N (trade name, a thermosetting agent manufactured by Nippon Oil & Fats Co., Ltd.) was added and mixed, and adhesion evaluation was performed according to the following adhesion evaluation method.

（比較例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ニルオキシエチルメタクリレート（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、更に促進剤として８％オクテン酸コバルト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、化薬アクゾ社製）を３部添加、混合させ、下記接着性評価法に従い、接着性評価を行った。 (Comparative Example 2)
100 parts of the urethane resin obtained in Synthesis Example 3 was heated and dissolved in 186 parts of dicyclopentenyloxyethyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.) to obtain a radical polymerizable resin composition, and further 8% cobalt octenoate 0% as an accelerator. Then, 6 parts were added and mixed so as to be uniform, and 3 parts of radical curing agent 328E (trade name, manufactured by Kayaku Akzo Co., Ltd.) was added and mixed.

（比較例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、更に促進剤として８％オクテン酸コバルト０．６部を添加して均一になる様混合し、ラジカル硬化剤パーメックＮ（商品名、日本油脂社製）を３部添加、混合させ、下記接着性評価法に従い、接着性評価を行った。 (Comparative Example 3)
200 parts of the urethane resin obtained in Synthesis Example 1 was dissolved in 108 parts of styrene by heating to obtain a radical polymerizable resin composition, and 0.6 parts of 8% cobalt octenoate was further added as an accelerator so as to be uniform. After mixing, 3 parts of radical curing agent Parmec N (trade name, manufactured by Nippon Oil & Fats Co., Ltd.) was added and mixed.

（比較例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、更に促進剤として８％オクテン酸コバルト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、下記接着性評価法に従い、接着性評価を行った。 (Comparative Example 4)
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, and 0.4 parts of 8% cobalt octenoate was further added uniformly as an accelerator. Then, 1.5 parts of radical curing agent Parmec N (trade name, manufactured by NOF Corporation) was added and mixed, and the adhesion was evaluated according to the following adhesion evaluation method.

上記樹脂組成物の接着性能について、基材として塩化ビニル樹脂（以下、ＰＶＣと略す）を用い評価を行った。
（接着性評価：実施例１〜２、比較例１〜４）
基材として市販の硬質塩化ビニル樹脂（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２５ｍｍ×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い様に重りを載せて硬化させ、さらに６０℃の乾燥機に１時間入れ、樹脂組成物を完全硬化させた。
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ＰＶＣ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いる場合は、接着性能が劣り、評価判定を不良：×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：○とした。
次に、基材である軟質塩化ビニル樹脂（軟質ＰＶＣ）との接着性能評価法について、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、可塑剤としてジオクチルフタレート５０部を添加し、粉末バリウム／亜鉛系安定剤２部を常温ブレンド後、１７０℃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１ｍｍ厚の軟質ＰＶＣシートを得た。得られた軟質ＰＶCシートを、長さ２００ｍｍ、幅２５ｍｍの短冊状に切断し、上記各樹脂組成物を縦長さ１５０ｍｍ×幅２５ｍｍの面積に均一に塗布し、上か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、樹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℃の乾燥機に１時間入れ、樹脂組成物を完全硬化させた。
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、１０ｍｍ／分）により行い、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：×とし、接着剤層自体が破壊され、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：○として評価した。
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：○、そうでないものを不良：×として評価した。結果を表１及び２に示す。 The adhesive performance of the resin composition was evaluated using a vinyl chloride resin (hereinafter abbreviated as PVC) as a base material.
(Adhesive evaluation: Examples 1-2 and Comparative Examples 1-4)
A commercially available hard vinyl chloride resin (hard PVC, manufactured by Takiron Co., Ltd., 3 mm thickness, gray color) was cut into a vertical length of 100 mm and a width of 25 mm, and the surface was lightly degreased with acetone to remove dust. Thereafter, the above-mentioned various resin compositions were applied to the two test pieces so that the adhesion area was 25 mm × 25 mm, and a weight was placed on the test piece so that the adhesion part did not shift until the resin composition was cured, and further, The resin composition was completely cured by placing 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 rigid PVC base material was destroyed by the test was described as base material destruction. If it has peeled off at the substrate interface, the adhesion performance is inferior, and the evaluation judgment is poor: x. If the adhesive strength is superior to the substrate strength and the substrate breaks, the evaluation judgment is good: ○. .
Next, the adhesive performance evaluation method with the soft vinyl chloride resin (soft PVC) as the base material will be described below.
Soft PVC is made by adding 50 parts of dioctyl phthalate as a plasticizer to 100 parts of vinyl chloride resin powder (ZEST1000Z manufactured by Shin Daiichi PVC Co., Ltd.), blending 2 parts of powdered barium / zinc stabilizer at room temperature, and heating at 170 ° C. It was melted and kneaded uniformly with a mixing roll for 5 minutes to obtain a soft PVC sheet having a thickness of about 1 mm. The obtained flexible PVC sheet was cut into strips having a length of 200 mm and a width of 25 mm, and each of the resin compositions was uniformly applied to an area of a length of 150 mm × width of 25 mm, and the strips were stacked from above. The test piece was sandwiched between two glass plates and the resin composition was hardened while removing bubbles. 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 performed according to JIS-K-6854 by a 180 degree peel test (T-shaped peel test, 10 mm / min), and the peel strength and the state of the adhesive interface after the test were observed. According to the test, when only one side of the adhesive is attached and the interface peels off, it is judged as bad: x, the adhesive layer itself is destroyed, adheres to both sides of the base material, and the adhesive strength is obtained. The case where it is good was evaluated as ◯.
From the above results, a comprehensive judgment of the adhesion to both the hard PVC substrate and the soft PVC substrate is performed, and those that adhere well to both substrates are evaluated as good: ◯, those that do not are evaluated as poor: × did. The results are shown in Tables 1 and 2.

Figure 2008069307
Figure 2008069307

Figure 2008069307
Figure 2008069307

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かった軟質ＰＶＣ基材同士の接着性においても、優れた接着特性を示していることが判った。   From the above table, it can be seen that the resin composition of the present invention exhibits excellent adhesive properties even in the adhesion between hard PVC substrates and between soft PVC substrates that could not be bonded with conventional adhesives. understood.

（実施例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オキシエチルメタクリレート（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、促進剤として８％オクテン酸コバルト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、化薬アクゾ社製）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、イソシア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、その鋼板表面に、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ニル樹脂（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、軟質塩化ビニル樹脂シート／本発明の樹脂組成物／鋼板基材からなる構造物を作成した。
完全硬化後、軟質塩化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が、軟質塩化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化しており、容易に剥がすことができず、軟質塩化ビニル樹脂シートと鋼板基材の一体構造物が得られた。 (Example 3)
100 parts of the urethane resin obtained in Synthesis Example 1 was dissolved by heating in 186 parts of dicyclopentenyloxyethyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.) to obtain a radical polymerizable resin composition, and 8% cobalt octenoate as an accelerator. 6 parts were added and mixed so as to be uniform, and 3 parts of radical curing agent 328E (trade name, manufactured by Kayaku Akzo) was added and mixed. The surface of a cold rolled steel sheet (2 mm thickness, JISG3141 SPCC-SD) used as a base material is degreased with acetone, and a primer PD (trade name, manufactured by Dainippon Ink & Chemicals, Inc.) that is an isocyanate primer is used with a brush. Apply and dry at room temperature for 1 hour, uniformly apply the resin composition with the previously prepared accelerator and curing agent added to the steel sheet surface, and immediately use the sheet-like form used in the above-mentioned adhesive evaluation section A soft vinyl chloride resin (soft PVC) was placed so as not to enter air, and allowed to stand at room temperature for 1 day and cured to prepare a structure composed of a soft vinyl chloride resin sheet / the resin composition of the present invention / steel plate substrate.
After complete curing, an attempt was made to peel off the corners of the soft vinyl chloride resin sheet using a cutter blade, but the soft vinyl chloride resin sheet was integrated with the steel plate base material by the resin composition of the present invention and easily peeled off. Thus, an integral structure of the soft vinyl chloride resin sheet and the steel plate base material was obtained.

（実施例４）
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オキシエチルメタクリレート（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、更に促進剤として８％オクテン酸コバルト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、化薬アクゾ社製）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、続いて、その表面にイソシア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ニル樹脂（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、軟質塩化ビニル樹脂シート／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。
完全硬化後、軟質塩化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が、本発明の樹脂組成物により、軟質塩化ビニル樹脂シートは、コンクリート板基材と一体化しており、容易に剥がすことができず、軟質塩化ビニ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。 Example 4
100 parts of the urethane resin obtained in Synthesis Example 1 was dissolved by heating in 186 parts of dicyclopentenyloxyethyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.) to obtain a radical polymerizable resin composition, and further 8% cobalt octenoate 0% as an accelerator. .6 parts was added and mixed so as to be uniform, and 3 parts of radical curing agent 328E (trade name, manufactured by Kayaku Akzo) was added and mixed. As a base material, the extreme surface of a 30 cm large, 3 cm thick JIS-compliant concrete board is smoothly cut with a disk sander, and shavings are removed from the concrete board surface with an air gun, followed by an isocyanate primer. Primer PD (trade name, manufactured by Dainippon Ink & Chemicals, Inc.) was applied using a brush and dried at room temperature for 1 hour to prepare a concrete plate. On the concrete plate, the resin composition added with the accelerator and the curing agent prepared above is uniformly applied, and immediately, the sheet-like soft vinyl chloride resin (soft PVC) used in the above-mentioned adhesion evaluation section. Was allowed to stand at room temperature for 1 day and cured to prepare a structure composed of a soft vinyl chloride resin sheet / the resin composition of the present invention / a JIS-compliant concrete board substrate.
After complete curing, an attempt was made to peel off the corners of the soft vinyl chloride resin sheet using a cutter blade, but with the resin composition of the present invention, the soft vinyl chloride resin sheet is integrated with the concrete plate base material and easily Thus, an integrated structure of a soft vinyl chloride resin sheet and a concrete board substrate was obtained.

（比較例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、更に促進剤として８％オクテン酸コバルト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、軟質塩化ビニル樹脂シート／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ニ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ニルシートとの界面で容易に剥がれ、軟質塩化ビニ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。 (Comparative Example 5)
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, and 0.4 parts of 8% cobalt octenoate was further added uniformly as an accelerator. Then, 1.5 parts of radical curing agent Parmec N (trade name, manufactured by NOF Corporation) was added and mixed. Except having used the said resin composition, it carried out similarly to Example 3, and created the molded article which consists of a soft vinyl chloride resin sheet / resin composition / steel plate base material. Then, in the same manner as in Example 3, when the corners of the soft vinyl chloride sheet were peeled off with the cutter blade, the soft vinyl chloride resin sheet and the steel plate base were easily peeled off at the interface between the resin composition and the soft vinyl chloride sheet. A monolithic structure of material was not obtained.

（比較例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、更に促進剤として８％オクテン酸コバルト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４と同様にして、軟質塩化ビニル樹脂シート／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ニ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ニルシートとの界面で容易に剥がれ、軟質塩化ビニ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。 (Comparative Example 6)
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, and 0.4 parts of 8% cobalt octenoate was further added uniformly as an accelerator. Then, 1.5 parts of radical curing agent Parmec N (trade name, manufactured by NOF Corporation) was added and mixed. Except having used the said resin composition, it carried out similarly to Example 4, and created the molded article which consists of a soft vinyl chloride resin sheet / resin composition / concrete board base material. Then, in the same manner as in Example 4, when the corner of the soft vinyl chloride sheet was peeled off with the cutter blade, the soft vinyl chloride resin sheet and the concrete plate were easily peeled off at the interface between the resin composition and the soft vinyl chloride sheet. An integral structure of the substrate was not obtained.

（実施例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ニルオキシエチルメタクリレート（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、促進剤として８％オクテン酸コバルト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、化薬アクゾ社製）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ニ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塗布にし、常温で硬化後、６０℃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ニル樹脂シート状被覆構造物を作成した。
硬化後、本発明の樹脂組成物被膜を、カッターの刃を用い、端部から塩化ビニ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いることを確認した。 (Example 5)
100 parts of the urethane resin obtained in Synthesis Example 1 was dissolved by heating in 186 parts of dicyclopentenyloxyethyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.) to obtain a radical polymerizable resin composition, and 8% cobalt octenoate as an accelerator. 6 parts were added and mixed so as to be uniform, and 3 parts of radical curing agent 328E (trade name, manufactured by Kayaku Akzo) was added and mixed. Using the 0.25 mm applicator on the hard and soft vinyl chloride resin base materials used in the adhesive evaluation of Examples 1 and 2, the resin composition of the present invention was uniformly applied, cured at room temperature, 60 A hard or soft vinyl chloride resin sheet-like covering structure coated with the resin composition of the present invention was completely cured at 1 ° C. for 1 hour.
After curing, the resin composition film of the present invention was removed from the vinyl chloride resin base material from the end using a cutter blade, but it was sufficiently adhered to the base material, not peeled off, and the vinyl chloride resin and Confirmed that they were united.

（比較例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、更に促進剤として８％オクテン酸コバルト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、端部から塩化ビニ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、塩化ビニル樹脂との一体被膜は得られなかった。 (Comparative Example 7)
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, and 0.4 parts of 8% cobalt octenoate was further added uniformly as an accelerator. Then, 1.5 parts of radical curing agent Parmec N (trade name, manufactured by NOF Corporation) was added and mixed. In the same manner as in Example 5 except that the resin composition was used, when the resin composition film was peeled off from the vinyl chloride resin substrate from the end using a cutter blade, the adhesion to the substrate was improved. Was insufficient, the film was easily peeled off and an integral film with vinyl chloride resin could not be obtained.

以上のように、本発明により、硬質塩化ビニル樹脂、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ニ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ニ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。   As described above, according to the present invention, there is provided a radically polymerizable resin composition for coating adhesion that exhibits excellent adhesion performance to hard vinyl chloride resins and soft vinyl chloride resins that could not be bonded well with conventional adhesives. Can be provided and useful. And since the resin composition of this invention can be apply | coated to a base material and a vinyl chloride resin can be coat-bonded, it is suitable for manufacture of a vinyl chloride steel plate, a vinyl chloride decorative board, a vinyl chloride laminated body, etc.

本発明は、特に各種塩化ビニル樹脂の基材への接着、各種塩化ビニル樹脂の被覆に利用可能である。   The present invention is particularly applicable to adhesion of various vinyl chloride resins to a substrate and coating of various vinyl chloride resins.

Claims (6)

ポリカーボネートジオール（Ａ１）とジイソシアネート化合物（Ａ２）とを反応させてイソシアネート基含有化合物（Ａ３）を得、次いで前記（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（Ａ）と、
ジシクロペンテニ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。 The polycarbonate diol (A1) and the diisocyanate compound (A2) are reacted to obtain the isocyanate group-containing compound (A3), and then the (A3) and the (meth) acrylic compound (A4) containing one hydroxyl group are reacted. A polycarbonate skeleton-containing urethane resin (A) having a (meth) acryloyl group obtained by
A radically polymerizable unsaturated monomer (B) having a dicyclopentenyl group;
A radically polymerizable resin composition for coating adhesion, comprising: 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。   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 3,000. 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。   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. 請求項１〜３のいずれか一項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。   A structure obtained by providing a vinyl chloride resin layer on a substrate through the radically polymerizable resin composition for coating adhesion according to any one of claims 1 to 3. 請求項１〜３のいずれか一項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ニル樹脂の基材への接着方法。   A method for adhering a vinyl chloride resin to a substrate, comprising using the radically polymerizable resin composition for coating adhesion according to any one of claims 1 to 3. 請求項１〜３のいずれか一項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。


A coating material comprising the radically polymerizable resin composition for coating adhesion according to any one of claims 1 to 3 as a main component.


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