JP2021008574A - 接着剤用共重合体ラテックスおよび接着剤組成物 - Google Patents
接着剤用共重合体ラテックスおよび接着剤組成物 Download PDFInfo
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- JP2021008574A JP2021008574A JP2019123491A JP2019123491A JP2021008574A JP 2021008574 A JP2021008574 A JP 2021008574A JP 2019123491 A JP2019123491 A JP 2019123491A JP 2019123491 A JP2019123491 A JP 2019123491A JP 2021008574 A JP2021008574 A JP 2021008574A
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- copolymer latex
- monomer
- less
- adhesive
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- 238000007865 diluting Methods 0.000 description 1
- REQPQFUJGGOFQL-UHFFFAOYSA-N dimethylcarbamothioyl n,n-dimethylcarbamodithioate Chemical class CN(C)C(=S)SC(=S)N(C)C REQPQFUJGGOFQL-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical class CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 1
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- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
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- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
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- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
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- C09J109/08—Latex
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F2/00—Processes of polymerisation
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- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F212/00—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 aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08F236/06—Butadiene
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- 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
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Abstract
Description
接着剤用共重合体ラテックスは、共重合体ラテックス(A)と共重合体ラテックス(B)とを含有する。接着剤用共重合体ラテックスは、好ましくは、共重合体ラテックス(A)および共重合体ラテックス(B)からなる。
共重合体ラテックス(A)は、単量体組成物(a)の乳化重合物である。単量体組成物(a)は、ブタジエン単量体、ビニルピリジン単量体、およびスチレン単量体を含有する。言い換えると、共重合体ラテックス(A)中のラテックス粒子は、ブタジエン単量体に由来する構造単位と、ビニルピリジン単量体に由来する構造単位と、スチレン単量体に由来する構造単位とを有する。
共重合体ラテックス(B)は、単量体組成物(b)の乳化重合物である。単量体組成物(b)は、ブタジエン単量体と、スチレン単量体とを含有する。言い換えると、共重合体ラテックス(B)中のラテックス粒子は、ブタジエン単量体に由来する構造単位と、スチレン単量体に由来する構造単位とを有する。また、単量体組成物(b)は、必要により、ビニルピリジン単量体と、ブタジエン単量体およびスチレン単量体と共重合可能な他の単量体とを含有してもよい。
接着剤用共重合体ラテックス中において、共重合体ラテックス(A)の固形分と共重合体ラテックス(B)の固形分との総量に対する共重合体ラテックス(A)の固形分の割合は、50質量%以上、好ましくは、60質量%以上、85質量%よりも少なく、好ましくは、80質量%以下である。
(1)共重合体ラテックスの製造
接着剤用共重合体ラテックスを製造するには、まず、共重合体ラテックス(A)と共重合体ラテックス(B)とを製造する。
接着剤用共重合体ラテックスは、共重合体ラテックス(A)と共重合体ラテックス(B)とが上記した割合で混合されることにより、調製される。なお、接着剤用共重合体ラテックスは、共重合体ラテックス(A)と共重合体ラテックス(B)との混合物が水で希釈されることにより、調製されてもよい。
接着剤用共重合体ラテックスは、接着剤組成物に配合される。接着剤組成物は、好ましくは、ゴムとゴム補強繊維とを接着するために用いられる。
上記した接着剤用共重合体ラテックスは、共重合体ラテックス(A)と、共重合体ラテックス(B)とを含有する。共重合体ラテックス(A)は、ブタジエン単量体35質量%以上75質量%以下と、ビニルピリジン単量体10質量%以上30質量%以下と、スチレン単量体10質量%以上55質量%以下とを含有する単量体組成物(a)の乳化重合物である。共重合体ラテックス(B)は、ブタジエン単量体3質量%以上30質量%以下を含有する単量体組成物(b)の乳化重合物である。そして、共重合体ラテックス(A)の固形分と共重合体ラテックス(B)の固形分との総量に対する共重合体ラテックス(B)の固形分の割合が、15質量%よりも多く、50質量%以下であり、共重合体ラテックス(B)の個数基準の平均粒子径が、150nm以上である。
(1)合成例1〜3および比較合成例1〜4
攪拌機付きオートクレーブに、水130質量部を仕込み、ナフタレンスルホン酸ナトリウムのホルマリン縮合物(乳化剤)1質量部、水酸化ナトリウム(電解質)0.5質量部およびロジン酸カリウム(乳化剤)4質量部を溶解させた。
攪拌機付きオートクレーブに、水135質量部を仕込み、ナフタレンスルホン酸ナトリウムのホルマリン縮合物1質量部、水酸化ナトリウム0.5質量部およびロジン酸カリウム5.0質量部を溶解させた。
攪拌機付きオートクレーブに、表2に示す量の水を仕込み、表2に示す量の乳化剤(具体的には、合成例8と比較合成例7とは、ロジン酸ナトリウム、その他は、ドデシルベンゼンスルホン酸ナトリウム)、電解質、重合開始剤(具体的には、過硫酸カリウム)を加えて、攪拌した。
共重合体ラテックス(A)、共重合体ラテックス(B)、ワックスエマルジョン系消泡剤、炭酸カルシウムおよびポリオキシアルキレン基を有する界面活性剤を表3、表4に示した配合割合で配合して混合し、各実施例および各比較例の接着剤用共重合体ラテックスを得た。
水260質量部に10%水酸化ナトリウム4質量部を添加して攪拌した後、レゾルシン7.9質量部、および、37%ホルマリン8.6質量部を加えて攪拌混合し、30℃にて6時間熟成し、レゾルシン−ホルマリン樹脂を合成した。レゾルシン−ホルマリン樹脂の固形分(蒸発残分)は、4.1質量%であった。
(1)泡立ち試験
接着剤組成物200g(200ml)を、メスシリンダー(1000ml)に投入し、接着剤組成物に空気700mlを吹き込み、発泡させた。
接着剤組成物の機械的安定性を、マロン式機械安定度試験により評価した。
試験用シングルコードディッピングマシンを用いて、接着剤組成物に、前処理されたポリエステル・タイヤコード(1500D/2)を浸漬し、120℃で120秒間乾燥した後、240℃で60秒間、焼き付けた。
天然ゴム 70質量部
SBRゴム 30質量部
FEFカーボン 40質量部
プロセスオイル 4質量部
アンチゲンRD(住友化学(株)社製) 2質量部
ステアリン酸 1.5質量部
亜鉛華 5質量部
ジベンゾチアジルジスルフィド 0.9質量部
硫黄 2.7質量部
なお、アンチゲンRDは、2,2,4−トリメチル−1,2−ジヒドロキノリン重合物である。
Claims (9)
- ブタジエン単量体35質量%以上75質量%以下と、ビニルピリジン単量体10質量%以上30質量%以下と、スチレン単量体10質量%以上55質量%以下とを含有する単量体組成物(a)の乳化重合物である共重合体ラテックス(A)と、
前記ブタジエン単量体3質量%以上30質量%以下を含有する単量体組成物(b)の乳化重合物である共重合体ラテックス(B)と
を含有し、
前記共重合体ラテックス(A)の固形分と前記共重合体ラテックス(B)の固形分との総量に対する前記共重合体ラテックス(B)の固形分の割合が、15質量%よりも多く、50質量%以下であり、
前記共重合体ラテックス(B)中のラテックス粒子の個数基準の平均粒子径が、150nm以上であることを特徴とする、接着剤用共重合体ラテックス。 - 前記単量体組成物(b)が、前記スチレン単量体50質量%以上85質量%以下を、さらに含有することを特徴とする、請求項1に記載の接着剤用共重合体ラテックス。
- 炭酸カルシウムをさらに含有することを特徴とする、請求項1または2に記載の接着剤用共重合体ラテックス。
- ワックスエマルジョン系消泡剤および鉱物油系消泡剤の少なくともいずれか一方をさらに含有することを特徴とする、請求項1〜3のいずれか一項に記載の接着剤用共重合体ラテックス。
- ポリオキシアルキレン基を有する界面活性剤をさらに含有することを特徴とする、請求項1〜4のいずれか一項に記載の接着剤用共重合体ラテックス。
- ブタジエン単量体35質量%以上75質量%以下と、ビニルピリジン単量体10質量%以上30質量%以下と、スチレン単量体10質量%以上55質量%以下とを含有する単量体組成物(a)の乳化重合物である共重合体ラテックス(A)と、
前記ブタジエン単量体3質量%以上30質量%以下を含有する単量体組成物(b)の乳化重合物である共重合体ラテックス(B)と、
レゾルシン−ホルマリン樹脂と
を含有し、
前記共重合体ラテックス(A)の固形分と前記共重合体ラテックス(B)の固形分との総量に対する前記共重合体ラテックス(B)の固形分の割合が、15質量%よりも多く、50質量%以下であり、
前記共重合体ラテックス(B)中のラテックス粒子の個数基準の平均粒子径が、150nm以上であることを特徴とする、接着剤組成物。 - 炭酸カルシウムをさらに含有することを特徴とする、請求項6に記載の接着剤組成物。
- ワックスエマルジョン系消泡剤および鉱物油系消泡剤の少なくともいずれか一方をさらに含有することを特徴とする、請求項6または7に記載の接着剤組成物。
- ポリオキシアルキレン基を有する界面活性剤をさらに含有することを特徴とする、請求項6〜8のいずれか一項に記載の接着剤組成物。
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JPS6096675A (ja) * | 1983-10-31 | 1985-05-30 | Sumitomo Naugatuck Co Ltd | ゴム補強用接着剤組成物 |
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WO1997013818A1 (fr) * | 1995-10-13 | 1997-04-17 | Bridgestone Corporation | Pneumatique et composition adhesive |
JP2009074182A (ja) * | 2007-09-18 | 2009-04-09 | Bridgestone Corp | 有機繊維コード用接着剤組成物の製造方法、その製造方法により得られた有機繊維コード用接着剤組成物、タイヤ用補強材及びそれを用いたタイヤ |
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