JP4132787B2 - Method for producing laminate of polymer foam and fabric and laminate - Google Patents
Method for producing laminate of polymer foam and fabric and laminate Download PDFInfo
- Publication number
- JP4132787B2 JP4132787B2 JP2001349957A JP2001349957A JP4132787B2 JP 4132787 B2 JP4132787 B2 JP 4132787B2 JP 2001349957 A JP2001349957 A JP 2001349957A JP 2001349957 A JP2001349957 A JP 2001349957A JP 4132787 B2 JP4132787 B2 JP 4132787B2
- Authority
- JP
- Japan
- Prior art keywords
- laminate
- polymer foam
- fabric
- xanthate
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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- 239000003795 chemical substances by application Substances 0.000 claims description 3
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- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
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- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は、ウェットスーツ，サポーター，靴用材料等として有用なゴム発泡体と布類の積層体を接着するに当たり良好な接着強度、特に耐有機溶剤性に優れる積層体を作製するための接着方法に関する。また、該方法を用いて作製した積層体に関する。
【０００２】
【従来の技術】
従来、ゴム発泡体と布類を接着する際には溶剤系の接着剤が主に採用されていた。しかし、溶剤系接着剤の場合、トルエン，酢酸エチル，メチルエチルケトン等の有機溶剤が多量に用いられていることから、作業員の安全衛生面、環境面で好ましくなかった。
そのため、接着剤の水性化の要求が年々高まってきており、例えば特開２０００−１０４０２８や特開２００１−８９７２７等、幾つかの提案がなされている。これら従来の接着剤や接着方法では、常態強度や耐水強度は充分であり、一般的な用途には使用可能であった。しかし、ウェットスーツ，サポーター，靴材料等に使用される積層体の場合にはその製造工程上の要求から耐溶剤性が必要であるが、従来知られている水系接着剤では耐溶剤性が実用的には不足しているという問題点が残されていた。
【０００３】
【発明が解決しようとする課題】
本発明は、かかる現状を鑑み、従来使用されてきた溶剤系接着剤による接着方法に匹敵する接着強度、特に耐溶剤性を与える、水系接着剤による接着方法を与えることに関するものである。
【０００４】
【課題を解決するための手段】
本発明者らは、上記目的を達成すべく鋭意検討を重ねた結果、キサントゲン酸塩を０．１〜１０重量部含有してなるポリクロロプレン系ラテックス組成物を主成分とする水系接着剤を用いて被着体を接着することにより常態強度のみならず、耐溶剤性にも優れる積層体が得られることを見出し、本発明を完成するに至った。
【０００５】
すなわち、本発明は、キサントゲン酸塩を０．１〜１０重量部含有してなるポリクロロプレン系ラテックス組成物を主成分とする水系接着剤を用いて高分子発泡体と布類を接着することを特徴とする高分子発泡体と布類との積層体の製造方法である。また、該製造方法によって与えられる高分子発泡体と布類を接着してなる積層体である。
【０００６】
以下、本発明の内容を詳細に説明する。本発明で云うポリクロロプレン系ラテックスとは、ポリクロロプレン系重合体を水媒体中に乳化分散させたものである。ここで云うポリクロロプレン系重合体とは、２−クロロ−１，３−ブタジエン（以下クロロプレンと記す）の単独重合体、またはクロロプレンと、クロロプレンと共重合可能な単量体との共重合体とのことである。ここで云う共重合体とは、ポリクロロプレン存在下にその他の単量体をグラフト重合させた様なグラフト共重合体も含む。
【０００７】
クロロプレンと共重合可能な単量体としては、例えば、２，３−ジクロロ−１，３−ブタジエン、１−クロロ−１，３−ブタジエン、ブタジエン、イソプレン、スチレン、アクリロニトリル、アクリル酸及びそのエステル類、メタクリル酸及びそのエステル類等が挙げられ、必要に応じて２種類以上用いても構わない。
【０００８】
ポリクロロプレンの重合方法は、特に限定されるものではないが、乳化重合による方法が一般的であり、かつ簡便である。
本発明を完成させるに当たっては、ポリクロロプレンを水に分散させる必要があるが、乳化重合であれば、得られたポリクロロプレン・ラテックスをそのまま使用することが出来る。
【０００９】
ポリクロロプレン系ラテックスの乳化重合に使用される乳化剤及び／または分散剤は特に限定するものではなく、通常クロロプレンラテックスに使用されている各種アニオン型、ノニオン型、カチオン型が使用できる。アニオン型の乳化剤としては、カルボン酸型，スルホン酸型，硫酸エステル型等があり、例えば、ロジン酸のアルカリ金属塩、炭素数が８〜２０個のアルキルスルホネート、アルキルアリールサルフェート、ナフタリンスルホン酸ナトリウムとホルムアルデヒドとの縮合物等が挙げられる。ノニオン型の具体例としては、ポリビニルアルコールまたはその共重合体（例えば、アクリルアミドとの共重合体）、ポリビニルエーテルまたはその共重合体（例えば、マレイン酸との共重合体）、ポリビニルピロリドンまたはその共重合体（例えば、酢酸ビニルとの共重合体）、あるいは、これら（共）重合体を化学修飾したもの、あるいは、セルロース系誘導体（ヒドロキシエチルセルロース）等を挙げることができる。カチオン型の具体例としては、脂肪族アミン塩、脂肪族４級アンモニウム塩等があり、例えば、オクタデシルトリメチルアンモニウムクロリド、ドデシルトリメチルアンモニウムクロリド、ジラウリルジメチルアンモニウムクロリド等が挙げられる。
【００１０】
本発明におけるポリクロロプレン系ラテックス中の乳化剤及び／または分散剤の添加量は、初期仕込み単量体の合計１００質量部に対して０．５〜２０質量部が好ましい。０．５質量部未満の場合には、乳化力が十分でなく、２０質量部を超えると耐水接着力を低下させてしまう欠点がある。
【００１１】
本発明におけるポリクロロプレン系ラテックスの重合温度は特に限定されるものではないが重合反応を円滑に行うために、重合温度を０〜５０℃とすることが好ましい。
重合の開始剤としては、過硫酸カリウム等の過硫酸塩、第３−ブチルヒドロパーオキサイド等の有機過酸化物などが好適に用いられるが、これらに限定されるものではない。
【００１２】
重合に用いる連鎖移動剤の種類は特に限定されるものではなく、通常クロロプレンの乳化重合に使用されるものが使用できる。例えばｎ−ドデシルメルカプタンやｔｅｒｔ−ドデシルメルカプタン等の長鎖アルキルメルカプタン類、ジイソプロピルキサントゲンジスルフィドやジエチルキサントゲンジスルフィド等のジアルキルキサントゲンジスルフィド類、ヨードホルム等の公知の連鎖移動剤を使用することができる。
【００１３】
ポリクロロプレンの重合停止剤（重合禁止剤）は特に限定するものでなく、例えば、２，６−ターシャリーブチルー４−メチルフェノール、フェノチアジン、ヒドロキシアミン等が使用できる。
【００１４】
ポリクロロプレンの最終重合率は、特に限定するものではなく、任意に調節することができ、未反応のモノマーは脱モノマー操作によって除去されるが、その方法は特に限定するものではない。
本発明のポリクロロプレン系ラテックスは、濃縮あるいは、水等の添加で希釈することで、固形分濃度を必要な濃度に制御することができる。濃縮の方法としては、減圧濃縮などがあるが、特に限定するものではない。
【００１５】
本発明におけるポリクロロプレン系ラテックスの構造は、特に限定されるものではないが、重合温度、重合開始剤、連鎖移動剤、重合停止剤、最終重合率、脱モノマー、濃縮条件等を適切に選定、制御することで、固形分濃度、トルエン可溶部の分子量、トルエン不溶分（ゲル含有量）等を調整することが可能である。
初期接着力と常態接着力のバランスの点からは、ポリクロロプレン系ラテックス中の（共）重合体のゲル含有量を３〜６０重量％に調整することが、好ましい。
【００１７】
本発明に用いられるキサントゲン酸塩とは、下記の一般式で表され、具体的にはブチルキサントゲン酸亜鉛，イソプロピルキサントゲン酸亜鉛等が例示されるが、これらに限定されるものではない。
【化２】
【００１８】
キサントゲン酸塩の添加量は特に限定されるものではないが、０．１〜１０重量部の間で使用されるのが好ましい。０．１部よりも少ない量では、耐有機溶剤性のレベルが充分ではなく、１０重量部を越えて用いた場合にはラテックス組成物の安定性を損なう可能性がある。
【００１９】
キサントゲン酸塩を水系接着剤へ添加する方法は特に限定されるものではないが、粉末状の場合には事前に、キサントゲン酸塩の乳化分散液を調製し、該乳化分散液をポリクロロプレン系ラテックスに添加する方法が、薬品の分散性の点から好ましい。
【００２０】
また、本発明の方法では、ポリイソシアネートを併用し、２液型水系接着剤として使用することによりさらに良好な常態強度，耐水強度，耐溶剤性を実現することが出来る。
この際、ポリイソシアネートは、使用直前に０．１〜１０重量部の範囲で用いることが好ましいが、この条件に特に限定するものではない。
【００２１】
本発明に用いる水系接着剤には、初期接着力，耐水接着力，粘着保持時間等の特性をより実用的にバランスするために、粘着付与樹脂を添加することができる。
水系接着剤に粘着付与樹脂を配合する場合、その種類は特に限定されるものではない。具体的には、ロジン樹脂、重合ロジン樹脂、α−ピネン樹脂、β−ピネン樹脂、テルペンフェノール樹脂、Ｃ5留分系石油樹脂、Ｃ9留分系石油樹脂、Ｃ5／Ｃ9留分系石油樹脂、ＤＣＰＤ系石油樹脂、アルキルフェノール樹脂、キシレン樹脂、クマロン樹脂、クマロンインデン樹脂などが挙げられる。十分な初期接着力を得るためには、軟化点温度が５０〜１６０℃の樹脂が好ましい。
【００２２】
粘着付与樹脂の添加方法は特に限定されるものではないが、プライマー中に樹脂を均一に分散させるために、水性エマルジョンとして添加することが好ましい。
粘着付与樹脂の水性エマルジョンの製法には、トルエン等の有機溶剤に溶解させたものを乳化剤を用いて水中に乳化／分散させた後、有機溶剤を減圧しながら加熱して取り除く方法と、微粒子に粉砕して乳化／分散させる方法などがあるが、より微粒子のエマルジョンが作製できる前者が好ましい。
【００２３】
本発明に用いる水系接着剤には、上述した以外にも、要求性能に合わせて、増粘剤、金属酸化物、充填剤、造膜助剤、紫外線吸収剤、酸化防止剤、可塑剤、加硫剤、加硫促進剤、消泡剤等を任意に添加することができる。
【００２４】
本発明の積層体に用いられる高分子発泡体とは、ゴム，エラストマー，合成樹脂等の材料からなる発泡体でありが、特に限定されるものではない。具体的には、ブタジエンゴム（ＢＲ），クロロプレンゴム（ＣＲ），天然ゴム（ＮＲ），イソプレンゴム（ＩＲ），スチレン−ブタジエンゴム（ＳＢＲ），ブチルゴム（ＩＩＲ），ノルボルネンゴム（ＮＯＲ），ニトリルゴム（ＮＢＲ），水素化ニトリルゴム（ＨＮＢＲ），臭素化ブチルゴム（ＢＩＩＲ），塩素化ブチルゴム（ＣＩＩＲ），アクリロニトリル−イソプレン共重合体（ＮＩＲ），エチレン−プロピレン−ジエンゴム（ＥＰＤＭ）等の加硫ゴム、スチレン−ブタジエン−スチレン・ブロック共重合体（ＳＢＳ），ポリエステル系，ウレタン系，オレフィン系等の熱可塑性エラストマー、塩化ビニル樹脂（ＰＶＣ），エチレン−酢ビ共重合体（ＥＶＡ），１，２−ポリブタジエン（ＲＢ），ポリオレフィン樹脂、スチレン系樹脂，アクリロニトリル−ブタジエン−スチレン共重合体（ＡＢＳ）等の合成樹脂などがある。
積層体をウェットスーツ用に用いる際にはＣＲ，ＮＲ等のゴム発泡体が好適に用いられる。
【００２５】
本発明における布類とは、織物、編物または不織布であるが、伸縮性を有する織物または編物が好ましく、ツーウェイトリコット（縦、横の両方にストレッチ性を有する）の織編物であることがより好ましい。具体的には、ナイロンジャージまたはポリエステルジャージ等が挙げられる。特に、ウェットスーツ用途には、ストレッチ性、通気性を考慮すれば、ナイロンジャージが最も好ましい。
【００２６】
【実施例】
以下、実施例及び比較例により本発明の効果を詳しく説明するが、これらの実施例は本発明を限定するものではない。なお、以下の説明において特に断りのない限り部および％は質量基準で表す。
【００２７】
［実験例１］
内容積３リットルの反応器を用いて、窒素雰囲気中で、水９６重量部にポリビニルアルコール３．５重量部を６０℃で溶解させた。このポリビニルアルコール水溶液を室温近くまで冷却した後、この中にクロロプレン単量体９９重量部、メタクリル酸１重量部、オクチルメルカプタン０．４重量部を加えた。これを４５℃に保持しながら亜硫酸ナトリウムと過硫酸カリウムを開始剤として重合し、ポリクロロプレンラテックスを得た。次に、このポリクロロプレンラテックスに２０重量％ジエタノールアミン水溶液を添加してｐＨを７に調製し、減圧加温により濃縮し、固形分を５５重量％になるように調製した。
【００２８】
［実験例２］
イソプロピルキサントゲン酸亜鉛（大内新興化学工業株式会社製ノクセラーＺＩＸ）を下記の処方でボールミルに仕込み一昼夜撹拌し、乳化分散液を得た。
イソプロピルキサントゲン酸亜鉛 １００[重量部]
１０％アンモニア・カゼイン水溶液 ３０
１０％ダーバンＮｏ．１水溶液 ３０
純水 １４０
【００２９】
［実験例３〜５］
実験例２のイソプロピルキサントゲン酸亜鉛の替わりに下記薬品を用いた以外は実験例２と同様に乳化分散液を調製した。
実験例３：ブチルキサントゲン酸亜鉛（大内新興化学工業株式会社製ノクセラーＺＢＸ）
実験例４：ジエチルジチオカルバミン酸テルル（大内新興化学工業株式会社製ノクセラーＴＴＴＥ）
実験例５：ジメチルジチオカルバミン酸銅（大内新興化学工業株式会社製ノクセラーＴＴＣＵ）
【００３０】
［実施例１］
実験例１で得られたポリクロロプレンラテックスを用い、ポリクロロプレンラテックス１００部に対し、酸化亜鉛エマルジョン（大崎工業株式会社製ＡＺ−ＳＷ）を５部、実験例２で得られた乳化分散液３部、増粘剤としてプライマルＲＭ−８Ｗ（Ｒｏｈｍ＆Ｈａａｓ社製）０．３部を加え、水系接着剤の主剤とした。
この主剤に水分散型ポリイソシアネートであるタケネートＷＤ−７３０（三井武田ケミカル株式会社製）３部を加え、水系接着剤を調製した。
クロロプレンゴム製発泡体（厚さ３ｍｍ）の表面に上記で調製した水系接着剤を８０ｇ／ｍ２（ウェット基準）塗布し、次いでナイロンジャージを重ねた。１３０℃に熱したプレス装置で１分間圧着し、積層体を得た。
【００３１】
得られた積層体について、下記の試験を行った。
［常態接着力評価試験］
圧着してから５日後に、引張試験機で引張速度２００ｍｍ／ｍｉｎでＴ型剥離強度を測定した。
［耐水性接着力評価試験］
圧着してから５日たった積層体を、室温で２日間純水中に浸漬した。２日後、取り出した積層体表面の水分を軽く拭き取り、直ちに引張試験機で引張速度２００ｍｍ／ｍｉｎでＴ型剥離強度を測定した。
［耐溶剤性接着力評価試験］
圧着してから５日たった積層体を、室温で２秒間トルエン中に浸漬した。取り出した積層体表面のトルエンを軽く拭き取り、直ちに引張試験機で引張速度２００ｍｍ／ｍｉｎでＴ型剥離強度を測定した。試験の結果は、ＣＲ発泡体の材料破壊した割合で示した。
【００３２】
［実施例２〜４］
水系接着剤の主剤に添加する乳化分散液を実験例２で調製したものから変更した以外は実施例１と同様に試験を実施し、実施例２〜４とした。
【００３３】
［比較例１］
ジチオカスバミン酸塩またはキサントゲン酸塩の乳化分散液を加えない以外は実施例１と同様に試験を実施し、比較例１とした。
【００３４】
実施例及び比較例の結果を、表１にして示した。
【表１】
２）ノクセラーＺＩＸ／大内新興化学工業株式会社製
３）ノクセラーＺＢＸ／大内新興化学工業株式会社製
４）ノクセラーＴＴＴＥ／大内新興化学工業株式会社製量
５）ノクセラーＴＴＣＵ／大内新興化学工業株式会社製量
６）プライマルＲＭ−８Ｗ／Ｒｏｈｍ＆Ｈａａｓ製
７）タケネートＷＤ−７３０／三井武田ケミカル株式会社製
８）常態接着強度及び耐水接着強度は剥離状態（何れもＣＲ発泡体の切断）、
耐溶剤性接着強度はＣＲ発泡体表面の材料破壊率で表示
【００３５】
【発明の効果】
表１より明らかな如く、本発明の接着方法、及び該方法によって作製された積層体は、良好な常態，耐水接着強度のみならず、実用上充分な耐有機溶剤性をも兼ね備えるものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a bonding method for producing a laminate having good adhesive strength, particularly excellent organic solvent resistance, for bonding a laminate of a rubber foam and a fabric useful as a wet suit, a supporter, a shoe material, and the like. About. The present invention also relates to a laminate manufactured using the method.
[0002]
[Prior art]
Conventionally, solvent-based adhesives have been mainly employed for bonding rubber foam and fabrics. However, in the case of a solvent-based adhesive, a large amount of an organic solvent such as toluene, ethyl acetate, methyl ethyl ketone, etc. is used, which is not preferable in terms of safety and health of workers and the environment.
For this reason, the demand for water-based adhesives has been increasing year by year, and several proposals have been made, for example, JP 2000-104028 A and JP 2001-89727 A. These conventional adhesives and bonding methods have sufficient normal strength and water resistance, and can be used for general purposes. However, in the case of laminates used for wet suits, supporters, shoe materials, etc., solvent resistance is necessary due to the requirements in the manufacturing process, but solvent resistance is practical with conventional water-based adhesives. The problem of being insufficient was left.
[0003]
[Problems to be solved by the invention]
In view of the present situation, the present invention relates to providing an adhesion method using a water-based adhesive that provides adhesion strength, particularly solvent resistance, comparable to that of a conventionally used adhesion method using a solvent-based adhesive.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors used an aqueous adhesive mainly composed of a polychloroprene latex composition containing 0.1 to 10 parts by weight of xanthate. Thus, by adhering the adherend, it has been found that a laminate having not only normal strength but also excellent solvent resistance can be obtained, and the present invention has been completed.
[0005]
That is, the present invention uses a water-based adhesive mainly composed of a polychloroprene-based latex composition containing 0.1 to 10 parts by weight of xanthate to bond the polymer foam and the fabric. It is a manufacturing method of the laminated body of the polymer foam and cloth characterized by the above-mentioned. Further, it is a laminate obtained by adhering a polymer foam and a cloth provided by the production method.
[0006]
Hereinafter, the contents of the present invention will be described in detail. The polychloroprene latex referred to in the present invention is obtained by emulsifying and dispersing a polychloroprene polymer in an aqueous medium. The polychloroprene polymer referred to here 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. That is. The term “copolymer” as used herein also includes a graft copolymer obtained by graft polymerization of other monomers in the presence of polychloroprene.
[0007]
Examples of the monomer copolymerizable with chloroprene include 2,3-dichloro-1,3-butadiene, 1-chloro-1,3-butadiene, butadiene, isoprene, styrene, acrylonitrile, acrylic acid and esters thereof. , Methacrylic acid and esters thereof, and the like, and two or more kinds may be used as necessary.
[0008]
The polymerization method of polychloroprene is not particularly limited, but a method by emulsion polymerization is common and simple.
In completing the present invention, it is necessary to disperse polychloroprene in water. However, in the case of emulsion polymerization, the obtained polychloroprene latex can be used as it is.
[0009]
The emulsifier and / or dispersant used for the emulsion polymerization of the polychloroprene latex is not particularly limited, and various anionic, nonionic, and cationic types that are usually used for chloroprene latex can be used. Examples of anionic emulsifiers include carboxylic acid type, sulfonic acid type, and sulfuric acid ester type. For example, alkali metal salts of rosin acid, alkyl sulfonates having 8 to 20 carbon atoms, alkyl aryl sulfates, sodium naphthalene sulfonate And condensates of formaldehyde and the like. Specific examples of the nonionic type include polyvinyl alcohol or a copolymer thereof (for example, a copolymer with acrylamide), polyvinyl ether or a copolymer thereof (for example, a copolymer with maleic acid), polyvinyl pyrrolidone or a copolymer thereof. Examples thereof include polymers (for example, copolymers with vinyl acetate), those obtained by chemically modifying these (co) polymers, and cellulose derivatives (hydroxyethyl cellulose). Specific examples of the cation type include aliphatic amine salts and aliphatic quaternary ammonium salts, such as octadecyltrimethylammonium chloride, dodecyltrimethylammonium chloride, dilauryldimethylammonium chloride and the like.
[0010]
The addition amount of the emulsifier and / or dispersant in the polychloroprene latex in the present invention is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass in total of the initially charged monomers. If the amount is less than 0.5 parts by mass, the emulsifying power is not sufficient, and if it exceeds 20 parts by mass, the water-resistant adhesive strength is reduced.
[0011]
The polymerization temperature of the polychloroprene latex in the present invention is not particularly limited, but the polymerization temperature is preferably 0 to 50 ° C. in order to smoothly perform the polymerization reaction.
As the polymerization initiator, persulfates such as potassium persulfate and organic peroxides such as 3-butyl hydroperoxide are preferably used, but are not limited thereto.
[0012]
The kind of chain transfer agent used for the polymerization is not particularly limited, and those usually used for emulsion polymerization of chloroprene can be used. For example, long chain alkyl mercaptans such as n-dodecyl mercaptan and tert-dodecyl mercaptan, dialkylxanthogen disulfides such as diisopropylxanthogen disulfide and diethylxanthogen disulfide, and known chain transfer agents such as iodoform can be used.
[0013]
The polymerization stopper (polymerization inhibitor) for polychloroprene is not particularly limited, and for example, 2,6-tertiarybutyl-4-methylphenol, phenothiazine, hydroxyamine, and the like can be used.
[0014]
The final polymerization rate of polychloroprene is not particularly limited and can be arbitrarily adjusted. Unreacted monomers are removed by the demonomer operation, but the method is not particularly limited.
The polychloroprene-based latex of the present invention can be controlled to a required concentration by concentration or dilution by addition of water or the like. The concentration method includes, but is not limited to, vacuum concentration.
[0015]
The structure of the polychloroprene latex in the present invention is not particularly limited, but the polymerization temperature, polymerization initiator, chain transfer agent, polymerization terminator, final polymerization rate, demonomer, concentration conditions, etc. are appropriately selected. By controlling, it is possible to adjust the solid content concentration, the molecular weight of the toluene soluble part, the toluene insoluble content (gel content), and the like.
From the viewpoint of the balance between the initial adhesive force and the normal adhesive force, it is preferable to adjust the gel content of the (co) polymer in the polychloroprene latex to 3 to 60% by weight.
[0017]
The xanthate used in the present invention is represented by the following general formula, and specific examples include zinc butylxanthate and zinc isopropylxanthate, but are not limited thereto.
[Chemical 2]
[0018]
The amount of xanthate added is not particularly limited, but it is preferably used between 0.1 and 10 parts by weight. If the amount is less than 0.1 part, the level of organic solvent resistance is not sufficient, and if used in excess of 10 parts by weight, the stability of the latex composition may be impaired.
[0019]
The method for adding xanthate to the water-based adhesive is not particularly limited, but in the case of powder, an xanthate salt emulsified dispersion is prepared in advance, and the emulsified dispersion is added to polychloroprene latex. The method of adding to is preferable from the viewpoint of dispersibility of chemicals.
[0020]
Further, in the method of the present invention, by using a polyisocyanate in combination and using it as a two-component aqueous adhesive, it is possible to realize even better normal strength, water resistance, and solvent resistance.
In this case, the polyisocyanate is preferably used in the range of 0.1 to 10 parts by weight immediately before use, but is not particularly limited to this condition.
[0021]
To the water-based adhesive used in the present invention, a tackifying resin can be added in order to more practically balance the properties such as initial adhesive strength, water-resistant adhesive strength, and tack retention time.
When the tackifier resin is blended with the water-based adhesive, the type thereof is not particularly limited. Specifically, rosin resin, polymerized rosin resin, α-pinene resin, β-pinene resin, terpene phenol resin, C 5 fraction petroleum resin, C 9 fraction petroleum resin, C 5 / C 9 fraction Examples include petroleum resins, DCPD petroleum resins, alkylphenol resins, xylene resins, coumarone resins, coumarone indene resins, and the like. In order to obtain a sufficient initial adhesive force, a resin having a softening point temperature of 50 to 160 ° C. is preferable.
[0022]
The method for adding the tackifying resin is not particularly limited, but it is preferably added as an aqueous emulsion in order to uniformly disperse the resin in the primer.
A method for producing an aqueous emulsion of a tackifying resin includes a method in which a solution dissolved in an organic solvent such as toluene is emulsified / dispersed in water using an emulsifier, and then the organic solvent is removed by heating under reduced pressure. There is a method of pulverizing and emulsifying / dispersing, but the former, which can produce a finer particle emulsion, is preferred.
[0023]
In addition to the above, the water-based adhesive used in the present invention includes a thickener, a metal oxide, a filler, a film-forming aid, an ultraviolet absorber, an antioxidant, a plasticizer, an additive, according to the required performance. A sulfurizing agent, a vulcanization accelerator, an antifoaming agent and the like can be optionally added.
[0024]
The polymer foam used in the laminate of the present invention is a foam made of a material such as rubber, elastomer, or synthetic resin, but is not particularly limited. Specifically, butadiene rubber (BR), chloroprene rubber (CR), natural rubber (NR), isoprene rubber (IR), styrene-butadiene rubber (SBR), butyl rubber (IIR), norbornene rubber (NOR), nitrile rubber (NBR), hydrogenated nitrile rubber (HNBR), brominated butyl rubber (BIIR), chlorinated butyl rubber (CIIR), acrylonitrile-isoprene copolymer (NIR), vulcanized rubber such as ethylene-propylene-diene rubber (EPDM), Styrene-butadiene-styrene block copolymer (SBS), polyester-based, urethane-based, olefin-based thermoplastic elastomer, vinyl chloride resin (PVC), ethylene-vinyl acetate copolymer (EVA), 1,2- Polybutadiene (RB), polyolefin resin, styrene resin, Acrylonitrile - butadiene - including synthetic resins such as styrene copolymer (ABS).
When the laminate is used for wet suits, rubber foams such as CR and NR are preferably used.
[0025]
The fabric in the present invention is a woven fabric, a knitted fabric or a non-woven fabric, preferably a stretchable woven fabric or knitted fabric, and more preferably a two-weight ricot (having stretch properties in both length and width). . Specific examples include nylon jersey or polyester jersey. Especially for wet suit applications, nylon jersey is most preferable in consideration of stretchability and breathability.
[0026]
【Example】
Hereinafter, the effects of the present invention will be described in detail with reference to Examples and Comparative Examples, but these Examples do not limit the present invention. In the following description, parts and% are expressed on a mass basis unless otherwise specified.
[0027]
[Experimental Example 1]
Using a reactor having an internal volume of 3 liters, 3.5 parts by weight of polyvinyl alcohol was dissolved at 60 ° C. in 96 parts by weight of water in a nitrogen atmosphere. After cooling this polyvinyl alcohol aqueous solution to near room temperature, 99 parts by weight of chloroprene monomer, 1 part by weight of methacrylic acid, and 0.4 parts by weight of octyl mercaptan were added thereto. While maintaining this at 45 ° C., polymerization was carried out using sodium sulfite and potassium persulfate as initiators to obtain polychloroprene latex. Next, 20% by weight diethanolamine aqueous solution was added to the polychloroprene latex to adjust the pH to 7, and the solution was concentrated by heating under reduced pressure to prepare a solid content of 55% by weight.
[0028]
[Experiment 2]
Zinc isopropyl xanthate (Noxeller ZIX manufactured by Ouchi Shinsei Chemical Co., Ltd.) was charged into a ball mill with the following formulation and stirred for a whole day and night to obtain an emulsified dispersion.
Zinc isopropyl xanthate 100 [parts by weight]
10% ammonia / casein aqueous solution 30
10% Durban No. 1 aqueous solution 30
Pure water 140
[0029]
[Experimental Examples 3 to 5]
An emulsified dispersion was prepared in the same manner as in Experimental Example 2 except that the following chemicals were used in place of the zinc isopropylxanthate in Experimental Example 2.
Experimental example 3: Zinc butylxanthate (Noxeller ZBX manufactured by Ouchi Shinsei Chemical Co., Ltd.)
Experimental Example 4: Tellurium diethyldithiocarbamate (Noxeller TTTE manufactured by Ouchi Shinsei Chemical Co., Ltd.)
Experimental example 5: Copper dimethyldithiocarbamate (Nouchira TTCU manufactured by Ouchi Shinsei Chemical Co., Ltd.)
[0030]
[Example 1]
Using polychloroprene latex obtained in Experimental Example 1, 5 parts of zinc oxide emulsion (AZ-SW manufactured by Osaki Kogyo Co., Ltd.) and 3 parts of the emulsified dispersion obtained in Experimental Example 2 with respect to 100 parts of polychloroprene latex As a thickener, 0.3 part of Primal RM-8W (Rohm & Haas) was added to make the main component of the aqueous adhesive.
To this main component, 3 parts of Takenate WD-730 (Mitsui Takeda Chemical Co., Ltd.), which is a water-dispersed polyisocyanate, was added to prepare an aqueous adhesive.
80 g / m 2 (wet basis) of the aqueous adhesive prepared above was applied to the surface of a chloroprene rubber foam (thickness 3 mm), and then a nylon jersey was overlaid. The laminate was obtained by pressure bonding for 1 minute with a press apparatus heated to 130 ° C.
[0031]
The following tests were performed on the obtained laminate.
[Normal adhesive strength evaluation test]
Five days after the pressure bonding, the T-type peel strength was measured with a tensile tester at a tensile speed of 200 mm / min.
[Waterproof adhesive strength evaluation test]
The laminate after 5 days from the pressure bonding was immersed in pure water at room temperature for 2 days. Two days later, the moisture on the surface of the taken-out laminate was gently wiped, and the T-type peel strength was immediately measured with a tensile tester at a tensile rate of 200 mm / min.
[Solvent-resistant adhesive strength evaluation test]
The laminate after 5 days from the pressure bonding was immersed in toluene at room temperature for 2 seconds. The toluene on the surface of the laminated body taken out was lightly wiped, and the T-type peel strength was immediately measured with a tensile tester at a tensile speed of 200 mm / min. The result of the test is shown as a ratio of material destruction of the CR foam.
[0032]
[Examples 2 to 4]
A test was carried out in the same manner as in Example 1 except that the emulsified dispersion added to the main component of the aqueous adhesive was changed from that prepared in Experimental Example 2, and Examples 2 to 4 were obtained.
[0033]
[Comparative Example 1]
A test was carried out in the same manner as in Example 1 except that an emulsified dispersion of dithiocasbamate or xanthate was not added.
[0034]
The results of Examples and Comparative Examples are shown in Table 1.
[Table 1]
The solvent-resistant adhesive strength is indicated by the material destruction rate of the CR foam surface.
【The invention's effect】
As is apparent from Table 1, the bonding method of the present invention and the laminate produced by the method have not only good normal state and water-resistant adhesive strength but also practically sufficient organic solvent resistance.
Claims (5)
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| JP2001349957A JP4132787B2 (en) | 2001-11-15 | 2001-11-15 | Method for producing laminate of polymer foam and fabric and laminate |
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| JP4132787B2 true JP4132787B2 (en) | 2008-08-13 |
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| EP3851484B1 (en) * | 2018-09-14 | 2025-11-26 | Zeon Corporation | Xanthogen compound dispersion, conjugated-diene-based polymer latex composition, and film molded body |
| CN110437770A (en) * | 2019-07-08 | 2019-11-12 | 高密市华诚橡胶制品有限公司 | A kind of special-purpose aqueous heat cure adhesive of vulcanized rubber and preparation method thereof |
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