JPH0569873B2 - - Google Patents
Info
- Publication number
- JPH0569873B2 JPH0569873B2 JP60293487A JP29348785A JPH0569873B2 JP H0569873 B2 JPH0569873 B2 JP H0569873B2 JP 60293487 A JP60293487 A JP 60293487A JP 29348785 A JP29348785 A JP 29348785A JP H0569873 B2 JPH0569873 B2 JP H0569873B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- adhesive
- metal
- styrene
- 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 - Lifetime
Links
- 239000000839 emulsion Substances 0.000 claims description 25
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 22
- 239000000853 adhesive Substances 0.000 claims description 22
- 230000001070 adhesive effect Effects 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- -1 polypropylene Polymers 0.000 claims description 19
- 239000004743 Polypropylene Substances 0.000 claims description 16
- 229920001155 polypropylene Polymers 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- 229920003051 synthetic elastomer Polymers 0.000 claims description 15
- 239000005061 synthetic rubber Substances 0.000 claims description 15
- 239000010426 asphalt Substances 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000002270 dispersing agent Substances 0.000 claims description 13
- 239000003208 petroleum Substances 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 150000002736 metal compounds Chemical class 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000004816 latex Substances 0.000 claims description 7
- 229920000126 latex Polymers 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 239000002313 adhesive film Substances 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 235000015170 shellfish Nutrition 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 229920005789 ACRONAL® acrylic binder Polymers 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229920001585 atactic polymer Polymers 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- WABPQHHGFIMREM-NOHWODKXSA-N lead-200 Chemical compound [200Pb] WABPQHHGFIMREM-NOHWODKXSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Description
〔産業上の利用分野〕
本発明は、漁網、ロープ、および船舶など海中
で用いられる物品に金属または金属化合物の粉体
を接着する方法に関する。
〔従来の技術〕
種々の目的で金属粉を海中で用いられる物品に
接着または被覆することが行われている。例え
ば、漁網の高比重化および強度の増大ならびに船
底における貝類の付着防止などである。
従来、金属および金属化合物の粉体を物品に接
着または被覆するには次のような方法が採られて
きた。
(イ) 溶剤系接着剤を用いる方法
ポリウレタン、アクリル系樹脂、ナイロン系樹
脂などを有機溶剤に溶かした接着剤を用いる方法
である。この方法は、金属含有被覆体が水中で膨
潤し接着強度が低下したり、有機溶剤を用いるた
め人体に対し種々の障害を誘発する、引火の危険
がある等の問題を抱いていた。
(ロ) エポキシ系その他の熱硬化性接着剤を用いる
方法
エポキシ系接着剤は硬化して硬い被覆物を形成
するため、剛構造体への接着には使用されるが、
高い可撓性が要求される、例えば、漁網、ロープ
等の柔構造体には不適である。
(ハ) 熔着法
金属粉を熔着する方法であつて、小さなパネル
や部品へは適用可能であるが、多くの用途では利
用できない。
〔発明が解決しようとする問題点〕
本発明の目的は、上記のような従来の技術の難
点を解決し、接着性に優れ、適度の可撓性をもつ
接着物を形成するため可撓性を有する物品に適用
でき、海水中で容易に接着強度が低下せず(従つ
て、金属粉が銹び難い)、有機溶剤を用いぬため
人体への障害がなく取扱いが容易であり、且つ安
定性のよいという特性を有する接着剤を用いて金
属または金属化合物を海中で用いられる物品に接
着する方法を提供するにある。
〔問題点を解決するための手段〕
上述の問題点は、接着剤として、固型分が下記
の組成を有する水性エマルジヨン組成物を用いる
ことによつて解決される。
(イ) アタクチツクポリプロピレン 1重量部
(ロ) 合成ゴムまたはそのラテツクス
0.1〜0.7重量部
(ハ) 分散剤 0.03〜0.5重量部
(ニ) 石油樹脂 0.05〜0.7重量部
(ホ) スチレン/アクリル酸アルキルエステル共重
合体 0.03〜0.5重量部
さらに、接着剤として用いる水性エマルジヨン
組成物は上記(イ)ないし(ホ)の5成分に加えて、0.5
〜3.0重量部のアスフアルトを含有することがで
きる。
以下、本発明で用いる水性エマルジヨン組成物
の構成成分について説明する。
本発明において使用する実質的にアタクチツク
なポリプロピレンは平均分子量約3000〜約50000
を有するものである。これは通常、主として成形
材料として有用な結晶性ポリプロピレンの製造時
に副生する。より低い分子量を有するものは、安
全なエマルジヨンは形成するが、得られる接着皮
膜は、接着力機械的強度、耐水性等に劣る。
合成ゴムとしては、スチレン・ブタジエン共重
合体ゴム(SBR)、イソプレンゴム(IR)、ブタ
ジエンゴム(BR)、ネオプレンゴム(NPR)、エ
チレン・プロピレン共重合体ゴム(EPR)、エチ
レン・プロピレン・ジエンターポリマーゴム
(EPT)およびブチルゴム等が挙げられる。これ
らの合成ゴムとしてはブロツク状(固型)のもの
が用いられる。合成ゴムの使用量は高分子量アタ
クチツクポリプロピレン1重量部あたり、0.1〜
0.7重量部、好ましくは0.1〜0.5重量部である。合
成ゴムの量が少いと耐衝撃性に乏しく、反対に合
成ゴムの量が多過ぎると接着力が低下し、接着皮
膜が被接着体から剥離して、フクレを生ずること
がある。
分散剤としては、オレイン酸ソーダ、ステアリ
ン酸ソーダ等のアニオン活性剤、ポリオキシエチ
レンアルキルフエノールエーテルその他のノニオ
ン活性剤、ならびにポリビニルアルコール、カル
ボキシメチルセルロースおよびそのナトリウム
塩、ポリアクリル酸、ポリアクリル酸アミド等の
水溶性または水膨潤性の熱可塑性重合体が挙げら
れる。これらは単独でも2以上を組合せてもよ
い。これらの分散剤の中ではケン化度70〜98%、
特に80〜97%のポリビニルアルコールが好まし
い。
分散剤の配合量は多量であつても安定なエマル
ジヨンは形成するが、得られる接着皮膜の耐水性
が低下する。従つて、得られる接着皮膜の特性お
よび安定なエマルジヨン形成能を考慮して、アタ
クチツクポリプロピレン1重量部に対し0.03〜
0.5重量部、好ましくは、0.05〜0.3重量部を使用
する。
石油樹脂としては、シクロペンタジエンを主原
料とするもの、高級オレフイン系炭化水素を主原
料とするものいずれも使用できるが、常温で固体
のものが好ましい。石油樹脂の配合量は高分子量
アタクチツクポリプロピレン1重量部に対し約
0.05〜約0.7重量部、特に0.1〜0.5重量部が好まし
い。石油樹脂を併用することによつて生成するエ
マルジヨンの粒径はさらに小さくなり、エマルジ
ヨンの安定性は一層向上する。
スチレン/アクリル酸アルキルエステル共重合
体としては、アクリル酸のC1ないしC6アルキル
エステルからの結合した単位を50〜90モル%含有
する共重合体が好ましく、特に、アクリル酸ブチ
ルとスチレンとのモル比が50:50ないし75:25の
共重合体はより好ましい。共重合体の配合量はア
タクチツクポリプロピレン1重量部に対し0.03〜
0.5重量部、好ましくは0.1ないし0.2重量部であ
る。スチレン/アクリル酸アルキルエステル共重
合体は接着剤が海水中で膨潤するのを阻止し、ひ
いては接着強度の低下を小さく抑えるのに有効で
あり、また、船底塗料として用いた場合は塗膜の
耐摩耗性の向上に寄与する。
本発明で用いる水性エマルジヨン組成物は、上
記のアタクチツクポリプロピレン、合成ゴムまた
はそのラテツクス、分散剤、石油樹脂およびスチ
レン/アクリル酸アルキルエステル共重合体の各
成分に加えて、アスフアルトを含有することがで
きる。ここで使用するアスフアルトとは、メジウ
ムまたはマルテンと呼ばれる炭化水素油状成分を
主成分とし、アスフアルト樹脂とよばれる保護質
およびコロイド粒子状ないし超微粒子炭素からな
るビチユーメンを指し、天然アスフアルトであつ
てもまた石油アスフアルトであつてもよい。概し
て、軟化点が約60℃〜約160℃の範囲のものであ
る。アスフアルトの配合量は高分子量アタクチツ
ク重合体1重量部あたり0.5〜3.0重量部、好まし
くは0.7〜2.5重量部である。高分子量アタクチツ
クポリプロピレンに対するアスフアルトの割合が
あまり高くなるとエマルジヨンの安定性が損われ
ると共に、接着性が低下する。
エマルジヨン状組成物を製造するには、まず前
記所定割合の高分子量アタクチツクポリプロピレ
ン、固型合成ゴム、分散剤、少量の水、さらに石
油樹脂からなる配合物を充分に均一混練する。ア
スフアルト含有組成物を調製する場合には、アス
フアルトをこれらの成分とともに混練することが
望ましい。
混練手段としては、大きな剪断力を付与できる
ものであれば、従来公知のいかなる方法でもよ
く、例えばニーダー、バンバリーミキサーが好適
に採用出来る。混練すべき物質の仕込順序には特
に制限はないが、アスフアルト非含有組成物の場
合は、各成分を同時に混練機に投入するか、ある
いは分散剤と水とのペースト状またはパテ状の混
合物をあらかじめ調製し、これをアタクチツクポ
リプロピレン、合成ゴムと混練するのがよい。均
一混練をより効果的に達成するためには、混練を
加温下、好ましくは70℃〜95℃で行うのがよい。
高分子量アタクチツクポリプロピレン、合成ゴ
ム、石油樹脂および分散剤からなる配合物を混練
するに当つて配合すべき水の量は、主として分散
剤の使用量に依存して変るが、通常分散剤1重量
部あたり約0.05〜2重量部、好ましくは約0.1〜
2重量部の範囲で使用する。特に、分散剤として
上述のケン化度を有する部分ケン化ポリビニルア
ルコールを使用し、それとほぼ等重量乃至ほぼ2
倍量の水を用いて混練すると最も良好なエマルジ
ヨンが得られる。
かくして得られた均一混練物質は、次いで、ス
チレン/アクリル酸アルキルエステル重合体デイ
スパージヨンおよび多量の水と均一混合すること
により、直ちに安定なエマルジヨン状となる。な
お、該組成物の低温での安定性をよくするため
に、温度を低下してほぼ常温で混練物質と水を均
一混合するのが望ましい。また、固型合成ゴムで
はなく、そのラテツクスを用いる場合は、スチレ
ン/アクリル酸アルキルエステル共重合体ととも
にこの段階で加えることが望ましい。
上記水性エマルジヨン組成物において、分散媒
である水の量は用途に応じた取扱い易さ、貯蔵・
運搬の便を考慮して任意に決めることができる。
一般に、製品水性エマルジヨン中の全重合体固型
分濃度が20〜70重量%程度とするのが望ましい。
上記水性エマルジヨン組成物によつて接着され
る金属および金属化合物の粉体は格別限定されな
い。金属化合物としては酸化物、水酸化物、硫化
物、金属含有炭酸塩等が挙げられる。
金属または金属化合物の粉体を接着するに際
し、使用する水性エマルジヨン組成の量は使用す
る目的に応じて大巾に変り得る。また、接着方法
は、従来の水性接着剤組成物を適用する方法と同
様でよい。
金属または金属化合物の粉体の接着適用例とし
ては次表のものが挙げられる。
[Industrial Application Field] The present invention relates to a method for adhering metal or metal compound powder to articles used under the sea, such as fishing nets, ropes, and ships. [Prior Art] Metal powder has been adhered or coated onto articles used under the sea for various purposes. Examples include increasing the specific gravity and strength of fishing nets and preventing shellfish from adhering to the bottom of ships. Conventionally, the following methods have been used to adhere or coat metal and metal compound powders onto articles. (a) Method using a solvent-based adhesive This method uses an adhesive prepared by dissolving polyurethane, acrylic resin, nylon resin, etc. in an organic solvent. This method has problems such as the metal-containing coating swells in water, resulting in a decrease in adhesive strength, and the use of organic solvents, which can cause various injuries to the human body and pose a risk of ignition. (b) Method using epoxy or other thermosetting adhesives Epoxy adhesives harden to form a hard coating, so they are used for bonding to rigid structures.
It is unsuitable for flexible structures that require high flexibility, such as fishing nets and ropes. (c) Welding method This is a method of welding metal powder, and although it can be applied to small panels and parts, it cannot be used in many applications. [Problems to be Solved by the Invention] The purpose of the present invention is to solve the above-mentioned difficulties of the conventional techniques, and to form a bonded product with excellent adhesiveness and appropriate flexibility. The adhesive strength does not easily decrease in seawater (therefore, the metal powder does not rust easily), and since no organic solvent is used, it is easy to handle without causing any harm to the human body, and is stable. The object of the present invention is to provide a method for bonding metals or metal compounds to articles used under the sea using adhesives having the property of good adhesive properties. [Means for Solving the Problems] The above-mentioned problems can be solved by using, as an adhesive, an aqueous emulsion composition whose solid content has the following composition. (a) Atactic polypropylene 1 part by weight (b) Synthetic rubber or its latex
0.1 to 0.7 parts by weight (c) Dispersant 0.03 to 0.5 parts by weight (d) Petroleum resin 0.05 to 0.7 parts by weight (e) Styrene/acrylic acid alkyl ester copolymer 0.03 to 0.5 parts by weight Furthermore, aqueous emulsion used as an adhesive In addition to the above five components (a) to (e), the composition contains 0.5
It can contain ~3.0 parts by weight of asphalt. The constituent components of the aqueous emulsion composition used in the present invention will be explained below. The substantially atactic polypropylene used in the present invention has an average molecular weight of about 3,000 to about 50,000.
It has the following. It is usually a by-product during the production of crystalline polypropylene, which is primarily useful as a molding material. Those having a lower molecular weight can form a safe emulsion, but the resulting adhesive film is inferior in adhesive strength, mechanical strength, water resistance, etc. Synthetic rubbers include styrene-butadiene copolymer rubber (SBR), isoprene rubber (IR), butadiene rubber (BR), neoprene rubber (NPR), ethylene-propylene copolymer rubber (EPR), and ethylene-propylene-dipropylene rubber. Examples include enteropolymer rubber (EPT) and butyl rubber. As these synthetic rubbers, block-shaped (solid) ones are used. The amount of synthetic rubber used is 0.1 to 1 part by weight of high molecular weight atactic polypropylene.
It is 0.7 part by weight, preferably 0.1 to 0.5 part by weight. If the amount of synthetic rubber is too small, the impact resistance will be poor, while if the amount of synthetic rubber is too large, the adhesive force will decrease and the adhesive film may peel off from the object to be adhered, causing blisters. Dispersants include anionic activators such as sodium oleate and sodium stearate, nonionic activators such as polyoxyethylene alkyl phenol ether, polyvinyl alcohol, carboxymethyl cellulose and its sodium salt, polyacrylic acid, polyacrylic acid amide, etc. water-soluble or water-swellable thermoplastic polymers. These may be used alone or in combination of two or more. Among these dispersants, saponification degree is 70-98%,
Particularly preferred is 80-97% polyvinyl alcohol. Although a stable emulsion can be formed even if a large amount of dispersant is added, the water resistance of the resulting adhesive film is reduced. Therefore, in consideration of the properties of the resulting adhesive film and the ability to form a stable emulsion, 0.03~1 parts by weight of atactic polypropylene is
0.5 part by weight is used, preferably 0.05 to 0.3 part by weight. As the petroleum resin, either one whose main raw material is cyclopentadiene or one whose main raw material is a higher olefinic hydrocarbon can be used, but one that is solid at room temperature is preferable. The amount of petroleum resin blended is approximately 1 part by weight of high molecular weight atactic polypropylene.
0.05 to about 0.7 parts by weight are preferred, especially 0.1 to 0.5 parts by weight. By using a petroleum resin in combination, the particle size of the emulsion produced becomes even smaller, and the stability of the emulsion is further improved. As the styrene/acrylic acid alkyl ester copolymer, a copolymer containing 50 to 90 mol% of bonded units from C 1 to C 6 alkyl ester of acrylic acid is preferred, and in particular, a copolymer containing butyl acrylate and styrene is preferred. Copolymers with a molar ratio of 50:50 to 75:25 are more preferred. The amount of copolymer blended is 0.03 to 1 part by weight of atactic polypropylene.
0.5 parts by weight, preferably 0.1 to 0.2 parts by weight. Styrene/acrylic acid alkyl ester copolymer is effective in preventing adhesives from swelling in seawater, thereby minimizing the decrease in adhesive strength, and when used as a ship bottom paint, it is effective in preventing the adhesive from swelling in seawater. Contributes to improved wear resistance. The aqueous emulsion composition used in the present invention may contain asphalt in addition to the above-mentioned components of atactic polypropylene, synthetic rubber or its latex, dispersant, petroleum resin, and styrene/acrylic acid alkyl ester copolymer. can. Asphalt as used here refers to a bitumen whose main component is a hydrocarbon oil component called medium or maltene, a protective material called asphalt resin, and colloidal particulate or ultrafine carbon particles, and even if it is natural asphalt, It may also be petroleum asphalt. Generally, the softening point will be in the range of about 60°C to about 160°C. The blending amount of asphalt is 0.5 to 3.0 parts by weight, preferably 0.7 to 2.5 parts by weight per 1 part by weight of the high molecular weight atactic polymer. If the ratio of asphalt to high molecular weight atactic polypropylene becomes too high, the stability of the emulsion will be impaired and the adhesion will be reduced. To produce an emulsion-like composition, first, a mixture consisting of high molecular weight atactic polypropylene, solid synthetic rubber, a dispersant, a small amount of water, and a petroleum resin in the predetermined proportions is thoroughly and uniformly kneaded. When preparing asphalt-containing compositions, it is desirable to knead asphalt with these ingredients. As the kneading means, any conventionally known method may be used as long as it can apply a large shearing force, and for example, a kneader or a Banbury mixer can be suitably employed. There is no particular restriction on the order in which the substances to be kneaded are added, but in the case of asphalt-free compositions, each component may be added to the kneader at the same time, or a paste or putty-like mixture of a dispersant and water may be added. It is preferable to prepare it in advance and knead it with atactic polypropylene and synthetic rubber. In order to achieve uniform kneading more effectively, kneading is preferably carried out at a temperature of 70°C to 95°C. The amount of water to be added when kneading a compound consisting of high molecular weight atactic polypropylene, synthetic rubber, petroleum resin, and dispersant varies depending mainly on the amount of dispersant used, but usually 1 weight of dispersant About 0.05 to 2 parts by weight, preferably about 0.1 to 2 parts by weight
Use within a range of 2 parts by weight. In particular, partially saponified polyvinyl alcohol having the above-mentioned degree of saponification is used as a dispersant, and the weight is approximately equal to approximately 2
The best emulsion is obtained by kneading with twice the amount of water. The homogeneously kneaded material thus obtained is then uniformly mixed with a styrene/acrylic acid alkyl ester polymer dispersion and a large amount of water to immediately form a stable emulsion. In order to improve the stability of the composition at low temperatures, it is desirable to lower the temperature and uniformly mix the kneaded material and water at approximately room temperature. Furthermore, when using the latex instead of solid synthetic rubber, it is desirable to add it at this stage together with the styrene/acrylic acid alkyl ester copolymer. In the above aqueous emulsion composition, the amount of water as a dispersion medium is determined depending on the use, ease of handling, storage and
It can be arbitrarily determined in consideration of transportation convenience.
Generally, it is desirable that the total polymer solids concentration in the product aqueous emulsion be about 20 to 70% by weight. The metal and metal compound powders to be adhered by the aqueous emulsion composition are not particularly limited. Examples of the metal compound include oxides, hydroxides, sulfides, metal-containing carbonates, and the like. In bonding powders of metals or metal compounds, the amount of aqueous emulsion composition used can vary widely depending on the purpose for which it is used. Further, the adhesion method may be the same as the method of applying a conventional aqueous adhesive composition. Examples of adhesion applications of metal or metal compound powder include those in the table below.
本発明で使用する上記の水性エマルジヨン組成
物は、(イ)接着性に優れ、(ロ)適度の可撓性をもつ接
着物を形成するため漁網、ロープ、その他の可撓
性が要求される分野に利用でき、(ハ)接着物は海中
での接着強度の低下が小さく、(ニ)金属粉が銹び難
く、(ホ)有機溶剤を溶媒としていないため人体への
障害がなく、引火のおそれもなく、取扱いが容易
であり、(ヘ)エマルジヨンの温度変化および長期保
存による変化がなく、安定性がよく、また水によ
る希釈の巾が大きい特長をもつている。
〔実施例〕
以下、実施例について本発明を具体的に説明す
る。
実施例1 (漁網用金属粉接着剤)
アタクチツクポリプロピレン(平均分子量約
20000) 1000g
石油樹脂(トーホーハイレジン #60) 200g
ポリビニルアルコール(ゴーセノール GH)
200g
水 400g
上記各成分を加圧されたルーダーニーダー中で
内部温度90℃にて20分間混練し、次いで、約120
℃の熔融アスフアルトを徐々に添加し(アスフア
ルト添加量2000g)、添加終了後、約10分間攪拌
した。
次に、多量の水を加え、約50℃まで冷却してか
らSBRラテツクス(日本合成ゴム)を400g及び
スチレン/アクリル酸ブチルエステル共重合体
(アクロナール)を400g加え、更に水を追加して
固形分40%(重量)の水性エマルジヨンを作つ
た。
得られたエマルジヨンを使つて金属粉と次の配
合でよく混練し、
エマルジヨン 1000g
鉛 粉 2000g
銅 粉 200g
のポリエステル製マルチフイラメントの漁網を浸
漬し、取出して、乾燥した。
金属粉接着漁網の性状は次のとおりであつた。
The above aqueous emulsion composition used in the present invention (a) has excellent adhesion and (b) forms an adhesive with appropriate flexibility, which is required for fishing nets, ropes, etc. (c) The adhesive has a small decrease in adhesive strength underwater, (d) metal powder is hard to rust, and (v) it does not use an organic solvent as a solvent, so there is no harm to the human body and it is non-flammable. It is easy to handle without fear, (f) emulsion does not change due to temperature changes or long-term storage, has good stability, and has a wide range of dilution with water. [Example] The present invention will be specifically described below with reference to Examples. Example 1 (Metal powder adhesive for fishing nets) Atactic polypropylene (average molecular weight approx.
20000) 1000g Petroleum resin (Toho High Resin #60) 200g Polyvinyl alcohol (Gohsenol GH)
200g water 400g The above ingredients were kneaded in a pressurized Ruder kneader at an internal temperature of 90°C for 20 minutes, and then kneaded at approximately 120°C.
C. molten asphalt was gradually added (amount of asphalt added: 2000 g), and after the addition was completed, the mixture was stirred for about 10 minutes. Next, add a large amount of water and cool to approximately 50℃, then add 400g of SBR latex (Japan Synthetic Rubber) and 400g of styrene/butyl acrylic ester copolymer (Acronal), and then add water to solidify. A 40% (by weight) aqueous emulsion was made. The obtained emulsion was thoroughly kneaded with metal powder in the following composition, and a polyester multifilament fishing net containing 1000 g of emulsion, 2000 g of lead powder, and 200 g of copper powder was immersed, taken out, and dried. The properties of the fishing net bonded with metal powder were as follows.
【表】
この金属粉接着漁網を海中(水深5m)に6ケ
月浸漬した結果、重量の減少はほとんどなく、網
地の膨潤、ばらけ、破損は全く見られず、結節の
ずれも認められなかつた。
貝、藻の付着も極端に少かつた。
実施例2 (土木用ロープ用金属粉接着剤)
アタクチツクポリプロピレン(平均分子量約
20000) 1000g
石油樹脂(トーホーハイレジン #60) 200g
ポリビニルアルコール(ゴーセノール GH)
200g
水 400g
顔料(酸化鉛) 50g
上記各成分を加圧されたルーダーニーダー中で
内部温度90℃にて30分間混練し、次に、多量の水
を加えて、約50℃まで冷却してから、SBRラテ
ツクス(日本合成ゴム)を400g及びスチレン・
アクリル酸ブチル共重合体(アクロナール)を
400g加え、更に水を追加して固形分40%(重量)
の淡黄色エマルジヨンを作つた。
得られたエマルジヨン 1000g
銅 粉 300g
をよく混練し、ナイロン製ロープ(直径12m/
m)をこれに浸漬し、取出して乾燥した。
このロープを海水中に6ケ月間浸漬したが、強
度の低下は全く見られず、貝、藻の付着もなかつ
た。[Table] As a result of immersing this metal powder-adhesive fishing net in the sea (at a depth of 5 m) for 6 months, there was almost no weight loss, no swelling, unraveling, or damage to the net fabric, and no shifting of knots. Ta. There was also extremely little adhesion of shellfish and algae. Example 2 (Metal powder adhesive for civil engineering ropes) Atactic polypropylene (average molecular weight approx.
20000) 1000g Petroleum resin (Toho High Resin #60) 200g Polyvinyl alcohol (Gohsenol GH)
200g Water 400g Pigment (lead oxide) 50g Knead the above ingredients in a pressurized Ruder kneader at an internal temperature of 90℃ for 30 minutes, then add a large amount of water and cool to approximately 50℃. , 400g of SBR latex (Japanese synthetic rubber) and styrene.
Butyl acrylate copolymer (acronal)
Add 400g and add water to make solid content 40% (weight)
A pale yellow emulsion was made. 1000g of the obtained emulsion and 300g of copper powder were thoroughly kneaded, and a nylon rope (diameter 12m/
m) was immersed in this, taken out and dried. This rope was immersed in seawater for 6 months, but no decrease in strength was observed, and no shellfish or algae were attached to it.
Claims (1)
エマルジヨン組成物を用い金属または金属化合物
の粉体を海中で用いられる物品に接着することを
特徴とする接着方法。 (イ) アタクチツクポリプロピレン 1重量部 (ロ) 合成ゴムまたはそのラテツクス
0.1〜0.7重量部 (ハ) 分散剤 0.03〜0.5重量部 (ニ) 石油樹脂 0.05〜0.7重量部 (ホ) スチレン/アクリル酸アルキルエステル共重
合体 0.03〜0.5重量部 2 接着剤として固形分が下記組成を有する水性
エマルジヨン組成物を用い金属または金属化合物
の粉体を海中で用いられる物品に接着することを
特徴とする接着方法。 (イ) アタクチツクポリプロピレン 1重量部 (ロ) 合成ゴムまたはそのラテツクス
0.1〜0.7重量部 (ハ) 分散剤 0.03〜0.5重量部 (ニ) 石油樹脂 0.05〜0.7重量部 (ホ) スチレン/アクリル酸アルキルエステル共重
合体 0.03〜0.5重量部 (ヘ) アスフアルト 0.5〜3.0重量部[Scope of Claims] 1. An adhesion method characterized in that a metal or metal compound powder is adhered to an article to be used under the sea using an aqueous emulsion composition having the following solid content as an adhesive. (a) Atactic polypropylene 1 part by weight (b) Synthetic rubber or its latex
0.1 to 0.7 parts by weight (c) Dispersant 0.03 to 0.5 parts by weight (d) Petroleum resin 0.05 to 0.7 parts by weight (e) Styrene/acrylic acid alkyl ester copolymer 0.03 to 0.5 parts by weight 2 As an adhesive, the solid content is as follows: 1. An adhesion method comprising adhering a metal or metal compound powder to an article to be used under the sea using an aqueous emulsion composition having the above composition. (a) Atactic polypropylene 1 part by weight (b) Synthetic rubber or its latex
0.1 to 0.7 parts by weight (c) Dispersant 0.03 to 0.5 parts by weight (d) Petroleum resin 0.05 to 0.7 parts by weight (e) Styrene/acrylic acid alkyl ester copolymer 0.03 to 0.5 parts by weight (f) Asphalt 0.5 to 3.0 parts by weight Department
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP29348785A JPS62270641A (en) | 1985-12-28 | 1985-12-28 | Aqueous emulsion composition for bonding powder of metal or metallic compound |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP29348785A JPS62270641A (en) | 1985-12-28 | 1985-12-28 | Aqueous emulsion composition for bonding powder of metal or metallic compound |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS62270641A JPS62270641A (en) | 1987-11-25 |
JPH0569873B2 true JPH0569873B2 (en) | 1993-10-01 |
Family
ID=17795373
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP29348785A Granted JPS62270641A (en) | 1985-12-28 | 1985-12-28 | Aqueous emulsion composition for bonding powder of metal or metallic compound |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS62270641A (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5433149B2 (en) * | 2007-12-20 | 2014-03-05 | 株式会社大林組 | Coating finishing method for base material and cement base material |
JP5386245B2 (en) * | 2009-06-18 | 2014-01-15 | 株式会社大林組 | Primer and construction method |
CN103756417A (en) * | 2013-12-27 | 2014-04-30 | 安徽省美域节能环保技术应用有限公司 | Wear-resistant coating for external wall and preparation method thereof |
CN105820402A (en) * | 2016-05-31 | 2016-08-03 | 苏州普京真空技术有限公司 | Heat-conductive flame-retardant insulating material |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4937416A (en) * | 1972-08-10 | 1974-04-08 | ||
JPS532652A (en) * | 1976-06-22 | 1978-01-11 | Loepfe Ag Geb | Observation apparatus for yarn movement of fibre machine |
-
1985
- 1985-12-28 JP JP29348785A patent/JPS62270641A/en active Granted
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4937416A (en) * | 1972-08-10 | 1974-04-08 | ||
JPS532652A (en) * | 1976-06-22 | 1978-01-11 | Loepfe Ag Geb | Observation apparatus for yarn movement of fibre machine |
Also Published As
Publication number | Publication date |
---|---|
JPS62270641A (en) | 1987-11-25 |
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