WO2018043586A1 - クロロプレンゴムラテックス接着剤組成物 - Google Patents
クロロプレンゴムラテックス接着剤組成物 Download PDFInfo
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- WO2018043586A1 WO2018043586A1 PCT/JP2017/031221 JP2017031221W WO2018043586A1 WO 2018043586 A1 WO2018043586 A1 WO 2018043586A1 JP 2017031221 W JP2017031221 W JP 2017031221W WO 2018043586 A1 WO2018043586 A1 WO 2018043586A1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/14—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen
- C08F236/16—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen containing halogen
- C08F236/18—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen containing halogen containing chlorine
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- C09J111/00—Adhesives based on homopolymers or copolymers of chloroprene
- C09J111/02—Latex
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C09J11/08—Macromolecular additives
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- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
- C09J123/28—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
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- C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
- C09J129/02—Homopolymers or copolymers of unsaturated alcohols
- C09J129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
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- C09J147/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Adhesives based on derivatives of such polymers
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C08L2205/00—Polymer mixtures characterised by other features
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- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Definitions
- Patent Document 1 discloses an adhesive composition in which heat-resistant creep resistance is improved by using chloroprene rubber latex having a specific gel content.
- Patent Document 2 discloses a blended adhesive composition in which adhesive properties are further improved by blending chloroprene rubber latexes having different gel contents and adding a carbodiimide crosslinking agent.
- the chloroprene rubber latex (also referred to as “chloroprene polymer latex”) is a latex (emulsion) obtained by dispersing polychloroprene in water.
- the chloroprene rubber is a homopolymer of 2-chloro-1,3-butadiene (hereinafter referred to as chloroprene) or a copolymer of chloroprene and a monomer copolymerizable with chloroprene.
- Examples of monomers copolymerizable with chloroprene include, for example, 2,3-dichloro-1,3-butadiene, 1-chloro-1,3-butadiene, sulfur, butadiene, isoprene, styrene, methacrylic acid and esters thereof. There are acrylic acid and esters thereof, and two or more kinds may be used as necessary.
- the amount of the ethylenically unsaturated carboxylic acid charged is not particularly limited as long as the effects of the present invention are not impaired, and can be freely set.
- the charged amount of ethylenically unsaturated carboxylic acid is preferably 0.5 to 10% by mass, and more preferably 1 to 4% by mass.
- the amount of the ethylenically unsaturated carboxylic acid in the carboxy-modified chloroprene copolymer latex (A) is determined by measuring a gas chromatograph using a sample with a known binding amount of the ethylenically unsaturated carboxylic acid as a calibration curve. Can do.
- polyvinyl alcohol is essential as an emulsifier used for emulsion polymerization of chloroprene.
- This PVA is a nonionic surfactant and is obtained by saponifying a homopolymer of a vinyl ester monomer or a copolymer of a vinyl ester monomer and a monomer copolymerizable therewith. It is a polymer obtained.
- chloroprene polymer latex (B) chloroprene alone or a monomer copolymerizable with chloroprene and chloroprene is used in the presence of a rosin acid metal salt using a polymerization initiator and a chain transfer agent. What is necessary is just to stop a polymerization by adding a polymerization terminator when emulsion polymerization is carried out and it becomes a predetermined polymerization rate.
- the content of the rosin acid metal salt can be determined from the peak area of the rosin component obtained by cutting the freeze-dried chloroprene rubber latex, placing it in an eggplant-shaped flask attached to a condenser, and measuring the components extracted by ETA by gas chromatography. .
- the content of the chlorinated polyolefin resin emulsion (C) is not particularly limited as long as the effects of the present invention are not impaired, and can be freely set. In the present embodiment, it is preferable to use 1 to 50 parts by mass of the chlorinated polyolefin resin emulsion (C) in terms of solid content, based on 100 parts by mass in terms of solid content of the chloroprene rubber latex, and 5 to 40 in terms of solid content. It is more preferable to use parts by mass. If the chlorinated polyolefin resin emulsion is not added, good adhesion to the polyolefin resin cannot be obtained, and if the addition amount is too large, the heat-resistant creep resistance may be lowered, and the cost increase cannot be avoided.
- chlorinated polyolefin resin emulsion (C) Commercial products that can be used as the chlorinated polyolefin resin emulsion (C) include EW-5303 and EH-801 manufactured by Toyobo Co., Ltd.
- Zinc white is added to improve the adhesive strength and heat-resistant creep property of the adhesive composition.
- a carboxy group is contained in the adhesive composition, cross-linking between the divalent metal ion and the carboxy group occurs, so that the heat resistance creep resistance can be further improved.
- the adhesiveness at the time of using polyolefin as a to-be-adhered body can be improved.
- the specific surface area of zinc white used in the present embodiment is not particularly limited, but is preferably 15 to 25 m 2 / g.
- the specific surface area of zinc white is JIS-Z8830 using a specific surface area measuring device (Monosorb: manufactured by QUANTACHROME INSTRUMENTS) using a powder obtained by ultrasonically dispersing zinc white in water and then naturally drying the sample. It is a value measured by the BET method using nitrogen as an adsorbate in conformity.
- zinc white having a specific surface area of 15 m 2 / g or more By using zinc white having a specific surface area of 15 m 2 / g or more, crosslinking of chloroprene rubber latex or chlorinated polyolefin resin emulsion can be promoted, and the adhesive strength of the resulting chloroprene rubber latex adhesive composition can be improved. Can do.
- zinc white having a specific surface area of 25 m 2 / g or less can prevent deterioration of the quality of zinc white because of its low hygroscopicity, and can be suitably used for industrial production.
- Examples of zinc white satisfying the conditions of the number average particle diameter and specific surface area include zinc white dispersion by a wet production method obtained by reacting a reaction liquid composed of an inorganic zinc salt aqueous solution and an alkaline aqueous solution in a stirred reaction tank, for example. can do. In order to facilitate uniform mixing of zinc white, it can be previously dispersed in water before being added to the chloroprene rubber latex.
- a general anionic emulsifier can be used as an emulsifier for dispersing zinc white in water. 1 (trade name, manufactured by RT Verderbilt Company).
- Examples of commercially available products of zinc white that can be used in this embodiment include AZ-SW manufactured by Osaki Kogyo Co., Ltd. and META-Z Inoue Lime Co., Ltd.
- Example demonstrated below shows an example of the typical Example of this invention, and, thereby, the range of this invention is not interpreted narrowly.
- Examples 6 and 7 Other than changing the addition amount of the chlorinated polyolefin resin emulsion (C) under the conditions shown in Table 1, the chloroprene rubber latex adhesive compositions of Examples 6 and 7 were the same as in Example 1 except for the other conditions. Obtained.
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- Health & Medical Sciences (AREA)
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Abstract
Description
また、特許文献2では、ゲル含有率の異なるクロロプレンゴムラテックスをブレンドし、かつカルボジイミド架橋剤を添加することで更に接着物性を向上させた配合接着剤組成物が開示されている。
クロロプレン単独重合体又はクロロプレン単量体と他の単量体との共重合体と、ロジン酸金属塩と、を含有するクロロプレン系重合体ラテックス(B)、
及び、塩素化ポリオレフィン樹脂エマルジョン(C)、を含有し、
前記カルボキシ変性クロロプレン系共重合体ラテックス(A)と前記クロロプレン系重合体ラテックス(B)の含有量が固形分換算比で80:20~20:80である、クロロプレンゴムラテックス接着剤組成物を提供する。
本技術に係るクロロプレンゴムラテックス接着剤組成物には、前記カルボキシ変性クロロプレン系共重合体ラテックス(A)及び前記クロロプレン系重合体ラテックス(B)の固形分換算での合計100質量部に対して、前記塩素化ポリオレフィン樹脂エマルジョン(C)を、固形分換算で1~50質量部、含有させることができる。
また、本技術に係るクロロプレンゴムラテックス接着剤組成物には、前記カルボキシ変性クロロプレン系共重合体ラテックス(A)及び前記クロロプレン系重合体ラテックス(B)の固形分換算での合計100質量部に対して、粘着付与樹脂を固形分換算で1~100質量部、及び、亜鉛華を固形分換算で0.5~10質量部、含有させることができる。
本技術に係るクロロプレンゴムラテックス接着剤組成物を用いることができる被着体としては、ポリオレフィンを挙げることができる。
本実施形態に係るクロロプレンゴムラテックス接着剤組成物に用いるカルボキシ変性クロロプレン系共重合体ラテックス(A)は、クロロプレン系重合体が、クロロプレン単量体とエチレン性不飽和カルボン酸との共重合体である。カルボキシ基含有ビニル単量体を共重合させると、接着剤に亜鉛華や酸化マグネシウムといった金属酸化物を配合した時に、2価金属イオンとカルボキシ基の架橋が起こり、耐熱クリープ性や耐溶剤性といった接着性能を向上させることができる。
本実施形態に係るクロロプレンゴムラテックス接着剤組成物に用いるクロロプレン系重合体ラテックス(B)は、クロロプレン単独重合体又はクロロプレン単量体と他の単量体との共重合体と、ロジン酸金属塩と、を含有する。
塩素化ポリオレフィン樹脂エマルジョン(C)とは、ポリオレフィンを塩素化、または酸変性させた樹脂エマルジョンである。塩素化ポリオレフィン樹脂エマルジョン(C)は、クロロプレンゴムラテックス接着剤組成物のポリオレフィン系樹脂に対する付着性を付与するための成分である。
本実施形態に係るクロロプレンゴムラテックス接着剤組成物には、前記カルボキシ変性クロロプレン系共重合体ラテックス(A)、前記クロロプレン系重合体ラテックス(B)、及び前記塩素化ポリオレフィン樹脂エマルジョン(C)に加えて、粘着付与樹脂を用いることができる。
本実施形態に係るクロロプレンゴムラテックス接着剤組成物には、前記カルボキシ変性クロロプレン系共重合体ラテックス(A)、前記クロロプレン系重合体ラテックス(B)、及び前記塩素化ポリオレフィン樹脂エマルジョン(C)に加えて、亜鉛華を用いることができる。
本実施形態に係るクロロプレンゴムラテックス接着剤組成物には、その他、炭酸カルシウムやシリカなどの無機充填材、老化防止剤、加硫促進剤、界面活性剤、防腐剤、消泡剤、分散剤、レベリング剤、凍結安定剤などを適宜配合できる。
[カルボキシ変性クロロプレン系共重合体ラテックス(A)-1の製造]
内容積3リットルの反応器を用い、窒素気流下で、純水100質量部、ポリビニルアルコール(商品名「UHR-20H」、けん化度79mol%、重合度380、ユニチカ株式会社製)4.0質量部を仕込み、溶解後、撹拌しながらクロロプレン系単量体98質量部、メタクリル酸2質量部、及びオクチルメルカプタン0.3質量部を添加した。これを45℃に保持しながら、過硫酸カリウムと亜硫酸ナトリウムを開始剤として用い重合し、カルボキシ変性クロロプレン系共重合体ラテックス(A)-1を得た。
[クロロプレン系重合体ラテックス(B)-1の製造]
内容積3リットルの反応器を用い、窒素気流下で、純水100質量部、ロジン酸のカリウム塩(荒川化学工業株式会社製、商品名「ロンジス」(登録商標))4.0質量部、水酸化カリウム1.0質量部、β-ナフタレンスルフォン酸ナトリウム塩(花王株式会社製、商品名「デモールNL」(登録商標))0.8質量部を仕込み、溶解後、撹拌しながらクロロプレン系単量体90質量部、2,3-ジクロロ1,3-ブタジエン10質量部、ドデシルメルカプタン0.03質量部を添加した。これを40℃に保持しながら、過硫酸カリウムと亜硫酸ナトリウムを開始剤として用い重合し、重合率が90%に達したところでフェノチアジンの乳濁液を加えて重合を停止した。減圧下で未反応単量体を除去し、クロロプレン系重合体ラテックス(B)-1を得た。クロロプレン系重合体ラテックス(B)-1のゲル含有率は90%であった。
[クロロプレン系重合体ラテックス(B)-2の製造]
内容積3リットルの反応器を用い、窒素気流下で、純水100質量部、ロジン酸のカリウム塩(荒川化学工業株式会社製、商品名「ロンジス」(登録商標))4.0質量部、水酸化カリウム1.0質量部、β―ナフタレンスルフォン酸ナトリウム塩(花王株式会社製、商品名「デモールNL」(登録商標))0.8質量部を仕込み、溶解後、撹拌しながらクロロプレン系単量体100質量部、ドデシルメルカプタン0.1質量部を添加した。これを10℃に保持しながら、過硫酸カリウムと亜硫酸ナトリウムを開始剤として用い重合し、重合率が90%に達したところでフェノチアジンの乳濁液を加えて重合を停止した。減圧下で未反応単量体を除去し、クロロプレン系重合体ラテックス(B)-2を得た。クロロプレン系重合体ラテックス(B)-2のゲル含有率は8%であった。
カルボキシ変性クロロプレン系共重合体ラテックス(A)としてカルボキシ変性クロロプレン系共重合体ラテックス(A)-1を固形分換算で50質量部、クロロプレン系重合体ラテックス(B)としてクロロプレン系重合体ラテックス(B)-1を固形分換算で50質量部、塩素化ポリオレフィン樹脂エマルジョン(C)としてEW-5303(東洋紡社製)を固形分換算で15質量部、粘着付与樹脂としてタマノルE-100(荒川化学工業製)を固形分換算で50質量部、亜鉛華としてAZ-SW(大崎工業株式会社製)を固形分換算で1質量部添加し、実施例1のクロロプレンゴムラテックス接着剤組成物を得た。
表1に示す条件で、クロロプレン系重合体ラテックス(B)としてクロロプレン系重合体ラテックス(B)-1の代わりにクロロプレン系重合体ラテックス(B)-2を添加した以外の、その他の条件は実施例1と同様の条件にて、実施例2のクロロプレンゴムラテックス接着剤組成物を得た。
表1に示す条件で、塩素化ポリオレフィン樹脂エマルジョン(C)としてEW-5303の代わりにEH-801(東洋紡社製)を添加した以外の、その他の条件は実施例1と同様の条件にて実施例3のクロロプレンゴムラテックス接着剤組成物を得た。
表1に示す条件でカルボキシ変性クロロプレン系共重合体ラテックス(A)-1とクロロプレン系重合体ラテックス(B)-1の添加量を変更した以外の、その他の条件は実施例1と同様の条件にて実施例4及び5のクロロプレンゴムラテックス接着剤組成物を得た。
表1に示す条件で塩素化ポリオレフィン樹脂エマルジョン(C)の添加量を変更した以外の、その他の条件は実施例1と同様の条件にて実施例6及び7のクロロプレンゴムラテックス接着剤組成物を得た。
表1に示す条件で粘着付与樹脂の添加量を変更した以外の、その他の条件は実施例1と同様の条件にて実施例8及び9のクロロプレンゴムラテックス接着剤組成物を得た。
表1に示す条件で亜鉛華の添加量を変更した以外の、その他の条件は実施例1と同様の条件にて実施例10のクロロプレンゴムラテックス接着剤組成物を得た。
表2に示す条件でそれぞれ接着剤組成物の調整を行ない、その他の条件は実施例1と同様の条件にてクロロプレンゴムラテックス接着剤組成物を得た。
帆布(25×70mm)に300g(固形分)/m2の各接着剤組成物(実施例1~10、比較例1~12)を、ポリプロプレン板(25×70mm)に150g(固形分)/m2の各接着剤組成物をそれぞれ刷毛で塗布し、80℃雰囲気下9分間乾燥した。その後、室温で1分間放置後に塗布面を張り合わせハンドローラーで圧着し、接着体を得た。
(1)初期接着強度
ローラー圧着10分間後、引張り試験機を用い、引張り速度200mm/minで180°剥離強度を測定した。
接着体を23℃雰囲気下で5日間養生後、引張り試験機を用い、引張り速度200mm/minで180°剥離強度を測定した。
接着体を23℃雰囲気下で5日間養生後、80℃雰囲気下で180°方向に100g/25mmの荷重をかけ、24時間後の剥離長さを測定した。
結果を下記の表1及び2に示す。
Claims (4)
- クロロプレン単量体とエチレン性不飽和カルボン酸の共重合体と、ポリビニルアルコールと、を含有するカルボキシ変性クロロプレン系共重合体ラテックス(A)、
クロロプレン単独重合体又はクロロプレン単量体と他の単量体との共重合体と、ロジン酸金属塩と、を含有するクロロプレン系重合体ラテックス(B)、
及び、塩素化ポリオレフィン樹脂エマルジョン(C)、を含有し、
前記カルボキシ変性クロロプレン系共重合体ラテックス(A)と前記クロロプレン系重合体ラテックス(B)の含有量が固形分換算比で80:20~20:80である、クロロプレンゴムラテックス接着剤組成物。 - 前記カルボキシ変性クロロプレン系共重合体ラテックス(A)及び前記クロロプレン系重合体ラテックス(B)の固形分換算での合計100質量部に対して、
前記塩素化ポリオレフィン樹脂エマルジョン(C)を固形分換算で1~50質量部、含有する、請求項1に記載のクロロプレンゴムラテックス接着剤組成物。 - 前記カルボキシ変性クロロプレン系共重合体ラテックス(A)及び前記クロロプレン系重合体ラテックス(B)の固形分換算での合計100質量部に対して、
粘着付与樹脂を固形分換算で1~100質量部、
及び、亜鉛華を固形分換算で0.5~10質量部、含有する、請求項1又は2に記載のクロロプレンゴムラテックス接着剤組成物。 - 少なくとも一方の被着体がポリオレフィンである、請求項1~3のいずれか一項に記載のクロロプレンゴムラテックス接着剤組成物。
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WO2022025118A1 (ja) * | 2020-07-31 | 2022-02-03 | 昭和電工株式会社 | クロロプレンゴムラテックス接着剤組成物とその製造方法、接着層、および積層体 |
WO2023068302A1 (ja) * | 2021-10-21 | 2023-04-27 | 株式会社レゾナック | 接着剤組成物 |
WO2023238748A1 (ja) * | 2022-06-07 | 2023-12-14 | デンカ株式会社 | ポリクロロプレンラテックス接着剤 |
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