JP3701706B2 - Antifouling resin composition and method for producing the same - Google Patents
Antifouling resin composition and method for producing the same Download PDFInfo
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- JP3701706B2 JP3701706B2 JP05490395A JP5490395A JP3701706B2 JP 3701706 B2 JP3701706 B2 JP 3701706B2 JP 05490395 A JP05490395 A JP 05490395A JP 5490395 A JP5490395 A JP 5490395A JP 3701706 B2 JP3701706 B2 JP 3701706B2
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- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
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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
- C09D133/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—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
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/064—Copolymers with monomers not covered by C09D133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
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- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、分子内に金属カルボキシレートを有する樹脂を有効成分とする防汚性組成物及びその製造方法に関する。
【０００２】
【従来の技術とその課題】
従来、分子内に金属塩構造を有する樹脂は防汚塗料のバインダーとして研究され、実用化されてきた。最も有名なのが錫のカルボキシレートであるが、このものは毒性が問題となったために、最近は銅や亜鉛のカルボキシレートが用いられている。これらの樹脂の共通点は樹脂中にフリーの水酸基が残存していないことであって、下記一般式（Ｂ）又は（Ｃ）で表わされる。
Ｒｐ−ＣＯＯ−Ｍ−（Ｒ）ｎ （Ｂ）
Ｒｐ−ＣＯＯ−Ｍ−（ＯＣＯＲ）ｎ （Ｃ）
（式中、Ｒｐは基体樹脂を、Ｍは２価の金属原子を、Ｒは炭化水素基を、ｎは１〜３の整数をそれぞれ示す。）
水酸基が存在すると合成時にゲル化してしまうので防汚性樹脂組成物として欠陥を生ずるからである。
化合物（Ｂ）の合成はコスト高になり、また、（Ｃ）の合成は２個以上の水酸基の反応性差が小さいので種々の化合物の混合物になりやすく、精製は非常にコスト高になる。
【０００３】
【課題を解決するための手段】
本発明は、
「１． 一般式
Ｒｐ −ＣＯＯ−Ｍ−ＯＨ （Ａ）
（式中、Ｒｐ は基体樹脂を、Ｍは２価の金属原子をそれぞれ示し、−ＣＯＯ−Ｍ−ＯＨは、Ｒｐの側鎖または末端に存在する。）
で表わされる分子内に金属カルボキシレートを有する樹脂を有効成分とし、基体樹脂が分子内にカルボキシル基を有し酸価が３０〜３００である樹脂に由来する防汚性樹脂組成物。
２． ２価の金属原子が銅、亜鉛、カルシウム、マグネシウム、鉄から選んだ１または２以上である、１項に記載された樹脂組成物。
３． 分子内にカルボキシル基を有し酸価が３０〜３００である樹脂がビニル重合体である、１項または２項に記載された樹脂組成物。
４． 分子内にカルボキシル基を有し酸価が３０〜３００である樹脂に２価の金属の酸化物あるいは水酸化物を、該樹脂に対して０．５〜５重量％の水の存在下で反応させることを特徴とする一般式
Ｒｐ −ＣＯＯ−Ｍ−ＯＨ （Ａ）
（式中、Ｒｐ は基体樹脂を、Ｍは２価の金属原子をそれぞれ示し、基体樹脂が分子内にカルボキシル基を有する樹脂に由来し、−ＣＯＯ−Ｍ−ＯＨ は、Ｒｐの側鎖または末端に存在する。）
で表わされる分子内に金属カルボキシレートを有する樹脂を有効成分とする防汚性樹脂組成物の製造方法。
５． ２価の金属原子が銅、亜鉛、カルシウム、マグネシウム、鉄から選んだ１または２以上である、４項に記載された防汚性樹脂組成物の製造方法。
６． 分子内にカルボキシル基を有し酸価が３０〜３００である樹脂がビニル重合体である、４項または５項に記載された防汚性樹脂組成物の製造方法。」
に関する。
【０００４】
【作用】
本発明者等は上記の点に鑑み、金属カルボキシレートを有する安価な防汚性樹脂組成物及びその合成方法について鋭意研究した結果、分子内にカルボキシル基を有する樹脂に２価の金属の酸化物あるいは水酸化物を少量の水の存在下で反応させることによって上記一般式（Ａ）の構造を有する樹脂をゲル化させずに合成できることを見いだし、本発明を完成するに至った。更に、使用する金属原子が２価であるためにイオン結合による３次元化がおきても不思議ではないが、驚くべきことにカルボキシル基１モルに対し、０．１〜１モルの範囲で２価の金属の酸化物あるいは水酸化物と反応させてもゲル化するようなことはなかった。本発明者は少量の水の存在がイオン結合による３次元化を防止していると考えている。
【０００５】
水はカルボキシル基１モルに対し０．１モル以下では構造粘性が発現して樹脂が増粘し、１モル以上では過剰の水が分離するため、いずれも良好な結果が得られない。また、カルボキシレートが生成していることは、ＩＲスペクトルによって確認した。
【０００６】
かくして、本発明によれば、一般式
Ｒｐ−ＣＯＯ−Ｍ−ＯＨ （Ａ）
（式中、Ｒｐは基体樹脂を、Ｍは２価の金属原子をそれぞれ示す。）
で表わされる防汚性樹脂組成物及びその合成方法が提供される。
本発明に用いる２価の金属の酸化物あるいは水酸化物としてはどのようなものでも使用可能であるが、コスト、毒性、反応性等の点から銅、亜鉛、カルシウム、マグネシウム、鉄のいずれかの酸化物あるいは水酸化物が好ましい。
【０００７】
本発明に用いる分子内にカルボキシル基を有する樹脂としては、ポリエステル、ポリウレタン、天然樹脂、ビニル重合体等どのようなものでも使用可能であるが、組成変動の自由度からビニル重合体が好ましい。また、該樹脂の分子量が低分子量であれば、１分子あたり１個のカルボキシル基を含有していても構わないが、高分子量になると酸価が３０〜３００範囲内のものが好ましく、カルボキシル基は１分子あたり２個以上必要となる。
【０００８】
本発明の樹脂組成物の合成方法としては、分子内にカルボキシル基を有する樹脂に分子内にカルボキシル基を有する樹脂に対して０．５〜５重量％の水と付加させたい２価の金属の酸化物あるいは水酸化物を添加し、５０〜２００℃の温度で１〜２０時間反応させる。系が水の存在によって濁るようである場合、最小限度の極性溶剤を添加する必要がある。極性溶剤としては、例えば、ｎ−ブタノール、イソプロピルアルコール等のアルコール系溶剤；メチルエチルケトン、メチルイソブチルケトン等のケトン系溶剤；酢酸エチル、酢酸ブチル、酢酸イソブチル等のエステル系溶剤；セロソルブ、ブチルセロソルブ、ジエチレングリコール、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル等のエーテル系溶剤などが挙げられる。最初は粉末状の金属化合物が溶解しないが、反応が進むにしたがって系は透明になる。
【０００９】
【実施例】
以下、本発明を実施例によりさらに具体的に説明する。
【００１０】
実施例１
アクリル酸７．２重量部、メチルメタクリレート５０重量部及びエチルアクリレート４２．８重量部からなる数平均分子量１０，０００の共重合体の５０重量％酢酸ブチル溶液２００ｇに、酸化亜鉛８g 、ブタノール５g および水１g を添加し、１２０℃で１０時間反応させて固形分４９．２重量％の透明な樹脂溶液を得た。ＩＲによると、１６３０cm−１に亜鉛カルボキシレートの吸収が大きく現れていた。
【００１１】
実施例２
アジピン酸／ネオペンチルグリコール／トリメチロールプロパンからなる末端に水酸基を有するポリエステル樹脂１００g に無水コハク酸を付加して数平均分子量３，５００、酸価５６のポリエステル樹脂を得た。この樹脂１１１ｇにセロソルブ１００g 、水酸化カルシウム２g および水２g を添加し、１００℃で１０時間反応させて固形分５０．０重量％の透明な樹脂溶液を得た。ＩＲによると、１５６０cm−１にカルシウムカルボキシレートの吸収が大きく現れていた。
【００１２】
応用例
実施例１および２によって得られた樹脂溶液をアルミ板に乾燥膜厚が１００μになるように夫々塗布して乾燥後、駿河湾の海水中の深さ１ｍに設置した。１夏経過後に引き上げてみると、フジツボ等の付着は全く観察されなかった。
比較として、実施例１および２の金属化合物と反応する前の樹脂を塗布した板は、樹脂が溶解して消失し、そのあとに直径０．５〜３ｍｍのフジツボが多数付着していた。
また、何も塗布していないアルミ板には直径０．５〜３ｍｍのフジツボが多数付着していた。
【００１３】
【発明の効果】
本発明により得られる樹脂は優れた防汚作用があり、防汚塗料に好適に使用できる。[0001]
[Industrial application fields]
The present invention relates to an antifouling composition comprising a resin having a metal carboxylate in the molecule as an active ingredient and a method for producing the same.
[0002]
[Prior art and its problems]
Conventionally, resins having a metal salt structure in the molecule have been studied and put into practical use as binders for antifouling paints. The most famous is the carboxylate of tin, but since this has become a problem of toxicity, the carboxylate of copper or zinc has been used recently. The common point of these resins is that no free hydroxyl group remains in the resin, which is represented by the following general formula (B) or (C).
R p -COO-M- (R) n (B)
R p -COO-M- (OCOR) n (C)
(In the formula, R p represents a base resin, M represents a divalent metal atom, R represents a hydrocarbon group, and n represents an integer of 1 to 3.)
This is because if a hydroxyl group is present, gelation occurs at the time of synthesis, resulting in defects as an antifouling resin composition.
The synthesis of the compound (B) is expensive, and the synthesis of (C) is easy to be a mixture of various compounds because the difference in reactivity between two or more hydroxyl groups is small, and the purification is very expensive.
[0003]
[Means for Solving the Problems]
The present invention
"1. General formula Rp-COO-M-OH (A)
(Wherein, Rp the base resin, M is a divalent metal atom indicates respectively, -COO-M-OH is present in a side chain or terminal of Rp.)
An antifouling resin composition derived from a resin having a metal carboxylate in the molecule represented by the above formula as an active ingredient and the base resin having a carboxyl group in the molecule and an acid value of 30 to 300.
2. 2. The resin composition according to item 1, wherein the divalent metal atom is one or more selected from copper, zinc, calcium, magnesium, and iron.
3. Resin organic and acid value carboxyl group in the molecule is 30 to 300 is a vinyl polymer, item 1 or the resin composition described in item 2.
4). A resin having a carboxyl group in the molecule and an acid value of 30 to 300 is reacted with a divalent metal oxide or hydroxide in the presence of 0.5 to 5% by weight of water with respect to the resin. General formula Rp-COO-M-OH (A)
(In the formula, Rp represents a base resin, M represents a divalent metal atom, and the base resin is derived from a resin having a carboxyl group in the molecule , -COO-M-OH Is present in the side chain or end of Rp . )
The manufacturing method of the antifouling resin composition which uses as an active ingredient resin which has metal carboxylate in the molecule | numerator represented by these.
5. 5. The method for producing an antifouling resin composition according to item 4, wherein the divalent metal atom is one or more selected from copper, zinc, calcium, magnesium, and iron.
6). Resin organic and acid value carboxyl group in the molecule is 30 to 300 is a vinyl polymer, the production method of the antifouling resin composition according to item 4 or 5 wherein. "
About.
[0004]
[Action]
In view of the above points, the present inventors have diligently studied an inexpensive antifouling resin composition having a metal carboxylate and a synthesis method thereof, and as a result, an oxide of a divalent metal in a resin having a carboxyl group in the molecule. Alternatively, it has been found that a resin having the structure of the general formula (A) can be synthesized without gelation by reacting a hydroxide in the presence of a small amount of water, and the present invention has been completed. Furthermore, since the metal atom to be used is divalent, it is not surprising that three-dimensionalization by ionic bonding occurs, but surprisingly, the divalent content is in the range of 0.1 to 1 mol with respect to 1 mol of the carboxyl group. It did not gel when reacted with metal oxides or hydroxides. The inventor believes that the presence of a small amount of water prevents three-dimensionalization by ionic bonding.
[0005]
If water is 0.1 mol or less with respect to 1 mol of carboxyl groups, structural viscosity develops and the resin is thickened. If it is 1 mol or more, excess water is separated, so that none of the good results can be obtained. The formation of carboxylate was confirmed by IR spectrum.
[0006]
Thus, according to the present invention, the general formula R p —COO—M—OH (A)
(In the formula, R p represents a base resin, and M represents a divalent metal atom.)
An antifouling resin composition represented by formula (1) and a synthesis method thereof are provided.
Any divalent metal oxide or hydroxide can be used in the present invention, but any one of copper, zinc, calcium, magnesium, and iron can be used from the viewpoint of cost, toxicity, reactivity, and the like. The oxide or hydroxide is preferred.
[0007]
As the resin having a carboxyl group in the molecule for use in the present invention, any resin such as polyester, polyurethane, natural resin, vinyl polymer, etc. can be used, but a vinyl polymer is preferred from the viewpoint of freedom of composition variation. In addition, if the molecular weight of the resin is low, it may contain one carboxyl group per molecule, but when it has a high molecular weight, an acid value within the range of 30 to 300 is preferable. 2 or more per molecule is required.
[0008]
As a method for synthesizing the resin composition of the present invention, a divalent metal to be added to a resin having a carboxyl group in the molecule with 0.5 to 5% by weight of water based on the resin having a carboxyl group in the molecule is used . Oxide or hydroxide is added and reacted at a temperature of 50 to 200 ° C. for 1 to 20 hours. If the system appears to be cloudy due to the presence of water, a minimal amount of polar solvent needs to be added. Examples of the polar solvent include alcohol solvents such as n-butanol and isopropyl alcohol; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate, butyl acetate and isobutyl acetate; cellosolve, butyl cellosolve, diethylene glycol, And ether solvents such as diethylene glycol monoethyl ether and diethylene glycol monobutyl ether. Initially, the powdered metal compound does not dissolve, but the system becomes transparent as the reaction proceeds.
[0009]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples.
[0010]
Example 1
To 200 g of a 50 wt% butyl acetate solution of a copolymer having a number average molecular weight of 10,000 consisting of 7.2 parts by weight of acrylic acid, 50 parts by weight of methyl methacrylate and 42.8 parts by weight of ethyl acrylate, 8 g of zinc oxide, 5 g of butanol and 1 g of water was added and reacted at 120 ° C. for 10 hours to obtain a transparent resin solution having a solid content of 49.2% by weight. According to IR, the absorption of zinc carboxylate appeared greatly at 1630 cm −1 .
[0011]
Example 2
A polyester resin having a number average molecular weight of 3,500 and an acid value of 56 was obtained by adding succinic anhydride to 100 g of a polyester resin having a terminal hydroxyl group consisting of adipic acid / neopentyl glycol / trimethylolpropane. To 111 g of this resin, 100 g of cellosolve, 2 g of calcium hydroxide and 2 g of water were added and reacted at 100 ° C. for 10 hours to obtain a transparent resin solution having a solid content of 50.0% by weight. According to IR, the absorption of calcium carboxylate appeared greatly at 1560 cm −1 .
[0012]
Application Examples The resin solutions obtained in Examples 1 and 2 were each applied to an aluminum plate so that the dry film thickness was 100 μm, dried, and then installed at a depth of 1 m in the seawater of Suruga Bay. When pulled up after the summer, no barnacles were observed.
As a comparison, the plate coated with the resin before reacting with the metal compounds of Examples 1 and 2 was dissolved and disappeared, and many barnacles having a diameter of 0.5 to 3 mm were attached thereafter.
In addition, a large number of barnacles having a diameter of 0.5 to 3 mm adhered to the aluminum plate to which nothing was applied.
[0013]
【The invention's effect】
The resin obtained by the present invention has an excellent antifouling action and can be suitably used for an antifouling paint.
Claims (6)
Ｒｐ −ＣＯＯ−Ｍ−ＯＨ （Ａ）
（式中、Ｒｐ は基体樹脂を、Ｍは２価の金属原子をそれぞれ示し、−ＣＯＯ−Ｍ−ＯＨは、Ｒｐの側鎖または末端に存在する。）
で表わされる分子内に金属カルボキシレートを有する樹脂を有効成分とし、基体樹脂が分子内にカルボキシル基を有し酸価が３０〜３００である樹脂に由来する防汚性樹脂組成物。General formula Rp-COO-M-OH (A)
(Wherein, Rp the base resin, M is a divalent metal atom indicates respectively, -COO-M-OH is present in a side chain or terminal of Rp.)
An antifouling resin composition derived from a resin having a metal carboxylate in the molecule represented by the above formula as an active ingredient and the base resin having a carboxyl group in the molecule and an acid value of 30 to 300.
Ｒｐ −ＣＯＯ−Ｍ−ＯＨ （Ａ）
（式中、Ｒｐ は基体樹脂を、Ｍは２価の金属原子をそれぞれ示し、基体樹脂が分子内にカルボキシル基を有する樹脂に由来し、−ＣＯＯ−Ｍ−ＯＨ は、Ｒｐの側鎖または末端に存在する。）
で表わされる分子内に金属カルボキシレートを有する樹脂を有効成分とする防汚性樹脂組成物の製造方法。A resin having a carboxyl group in the molecule and an acid value of 30 to 300 is reacted with a divalent metal oxide or hydroxide in the presence of 0.5 to 5% by weight of water with respect to the resin. General formula Rp-COO-M-OH (A)
(In the formula, Rp represents a base resin, M represents a divalent metal atom, and the base resin is derived from a resin having a carboxyl group in the molecule , -COO-M-OH Is present in the side chain or end of Rp . )
The manufacturing method of the antifouling resin composition which uses as an active ingredient resin which has metal carboxylate in the molecule | numerator represented by these.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05490395A JP3701706B2 (en) | 1995-02-08 | 1995-02-08 | Antifouling resin composition and method for producing the same |
| TW085101123A TW346502B (en) | 1995-02-08 | 1996-01-30 | Anti-fouling resin composition and preparation thereof |
| KR1019960002696A KR100349066B1 (en) | 1995-02-08 | 1996-02-05 | Antifouling resin composition and its manufacturing method |
| GB9605268A GB2311070B (en) | 1995-02-08 | 1996-03-13 | Stainproof resin composition and production method therefor |
| DE19611002A DE19611002A1 (en) | 1995-02-08 | 1996-03-20 | Antifouling resin compsn. for antifouling paints |
| SG1996006594A SG74553A1 (en) | 1995-02-08 | 1996-03-21 | Stainproof resin composition and production method therefor |
| US09/333,024 US6303701B1 (en) | 1995-02-08 | 1999-06-15 | Stainproof resin composition and production method therefor |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05490395A JP3701706B2 (en) | 1995-02-08 | 1995-02-08 | Antifouling resin composition and method for producing the same |
| GB9605268A GB2311070B (en) | 1995-02-08 | 1996-03-13 | Stainproof resin composition and production method therefor |
| DE19611002A DE19611002A1 (en) | 1995-02-08 | 1996-03-20 | Antifouling resin compsn. for antifouling paints |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08209005A JPH08209005A (en) | 1996-08-13 |
| JP3701706B2 true JP3701706B2 (en) | 2005-10-05 |
Family
ID=27216050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05490395A Expired - Lifetime JP3701706B2 (en) | 1995-02-08 | 1995-02-08 | Antifouling resin composition and method for producing the same |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP3701706B2 (en) |
| DE (1) | DE19611002A1 (en) |
| GB (1) | GB2311070B (en) |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10219148A (en) * | 1997-02-12 | 1998-08-18 | Kansai Paint Co Ltd | Antifouling resin composition and its production |
| JP2000063708A (en) | 1998-08-25 | 2000-02-29 | Kansai Paint Co Ltd | Antifouling coating composition |
| NZ512945A (en) | 1999-01-20 | 2003-08-29 | Akzo Nobel Nv | Antifouling paint |
| JP2001098030A (en) | 1999-09-28 | 2001-04-10 | Kansai Paint Co Ltd | Preparation process for metal-containing resin and composition comprising the same |
| ATE344829T1 (en) * | 2000-04-24 | 2006-11-15 | Basf Coatings Japan Ltd | ANTIFOULING COATING MATERIAL, ANTIFOULING COATING FILM, DIPPED STRUCTURE AND ANTIFOULING METHOD |
| US6727304B2 (en) * | 2000-06-28 | 2004-04-27 | Mitsubishi Rayon Co., Ltd. | Metal-containing monomer dissolved mixture, metal-containing resin and antifouling paint composition |
| DE60112943T2 (en) | 2000-07-06 | 2006-06-14 | Akzo Nobel Coatings Int Bv | DEPOSITION PREVENTIVE PAINTING COMPOSITION |
| JP4829428B2 (en) * | 2001-06-14 | 2011-12-07 | 三菱レイヨン株式会社 | Method for producing aqueous metal-containing resin composition and coating resin |
| ATE345361T1 (en) | 2003-07-07 | 2006-12-15 | Akzo Nobel Coatings Int Bv | SILYL ESTER COPOLYMER COMPOSITIONS |
| PT1695956E (en) | 2003-11-27 | 2012-08-27 | Chugoku Marine Paints | Cyclic carboxylic acid compound and use thereof |
| EP2520620B1 (en) | 2009-12-28 | 2015-09-16 | Mitsubishi Rayon Co., Ltd. | Method for producing resin dispersion for antifouling coating |
| EP2348077B1 (en) | 2010-01-26 | 2013-04-03 | Jotun A/S | Antifouling composition |
| KR20130131277A (en) | 2010-06-04 | 2013-12-03 | 요툰 에이/에스 | Antifouling coating |
| KR101267282B1 (en) * | 2011-01-12 | 2013-07-01 | 비엔스틸라(주) | Antifouling coating composition with excellent antifouling property by the various molecular weight distribution control |
| EP2708594A1 (en) | 2012-09-18 | 2014-03-19 | Jotun A/S | Cleaning process |
| EP2725073B1 (en) | 2012-10-23 | 2016-08-03 | Jotun A/S | Antifouling coating composition |
| EP2912120B1 (en) | 2012-10-23 | 2017-12-20 | Jotun A/S | Antifouling coating composition |
| WO2014096102A1 (en) | 2012-12-19 | 2014-06-26 | Jotun A/S | Silyl ester copolymer |
| EP2902453A1 (en) | 2014-01-31 | 2015-08-05 | Jotun A/S | Antifouling Composition |
| EP2902452A1 (en) | 2014-01-31 | 2015-08-05 | Jotun A/S | Antifouling composition |
| CN106047173B (en) | 2015-04-09 | 2020-12-11 | 佐敦集团 | Antifouling composition |
| CN109983083B (en) | 2016-11-11 | 2021-08-17 | 佐敦有限公司 | Antifouling composition |
| WO2018086670A1 (en) | 2016-11-11 | 2018-05-17 | Hempel A/S | An antifouling coating composition comprising novel carbon-based hydrolysable polymers |
| JP7161845B2 (en) | 2016-11-11 | 2022-10-27 | ヨトゥン アーエス | antifouling composition |
| JP7178167B2 (en) | 2016-11-11 | 2022-11-25 | ヨトゥン アーエス | antifouling composition |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4870197A (en) * | 1986-12-12 | 1989-09-26 | Exxon Chemical Patents Inc. | Method for preparing salts of polyolefinic substituted dicarboxylic acids |
| US5319018A (en) * | 1991-04-23 | 1994-06-07 | Rohm And Haas Company | Transition metal crosslinking of acid-containing polymers |
-
1995
- 1995-02-08 JP JP05490395A patent/JP3701706B2/en not_active Expired - Lifetime
-
1996
- 1996-03-13 GB GB9605268A patent/GB2311070B/en not_active Expired - Fee Related
- 1996-03-20 DE DE19611002A patent/DE19611002A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| GB2311070A (en) | 1997-09-17 |
| JPH08209005A (en) | 1996-08-13 |
| GB2311070B (en) | 1999-06-23 |
| DE19611002A1 (en) | 1997-09-25 |
| GB9605268D0 (en) | 1996-05-15 |
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