JPH11148031A - Antifouling paint composition - Google Patents
Antifouling paint compositionInfo
- Publication number
- JPH11148031A JPH11148031A JP33084897A JP33084897A JPH11148031A JP H11148031 A JPH11148031 A JP H11148031A JP 33084897 A JP33084897 A JP 33084897A JP 33084897 A JP33084897 A JP 33084897A JP H11148031 A JPH11148031 A JP H11148031A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- acrylate
- antifouling
- antifouling paint
- copolymer
- 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.)
- Pending
Links
- 239000003973 paint Substances 0.000 title claims abstract description 21
- 239000000203 mixture Substances 0.000 title claims abstract description 16
- 230000003373 anti-fouling effect Effects 0.000 title abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 31
- 229920001577 copolymer Polymers 0.000 claims abstract description 18
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 241001474374 Blennius Species 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 41
- -1 2-chloro-1-methylethyl Chemical group 0.000 description 20
- 239000002519 antifouling agent Substances 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
- 239000008096 xylene Substances 0.000 description 7
- 239000008199 coating composition Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 235000015170 shellfish Nutrition 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000000453 2,2,2-trichloroethyl group Chemical group [H]C([H])(*)C(Cl)(Cl)Cl 0.000 description 1
- 125000005999 2-bromoethyl group Chemical group 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000238586 Cirripedia Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 241000545593 Scolytinae Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- BQVVSSAWECGTRN-UHFFFAOYSA-L copper;dithiocyanate Chemical compound [Cu+2].[S-]C#N.[S-]C#N BQVVSSAWECGTRN-UHFFFAOYSA-L 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 230000005183 environmental health Effects 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 231100000225 lethality Toxicity 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
(57)【要約】
【課題】 水中構築物、漁網、船底への海中生物および
海藻類の付着を防止することのできる防汚塗料の開発。
【解決手段】 （ａ）下記一般式（Ｉ）
【化１】
で表わされる重合性単量体、および（ｂ）共重合可能な
不飽和単量体、からなる単量体混合物を重合して得られ
る共重合体を防汚性塗料のビヒクル成分として含有させ
る。(57) [Summary] [PROBLEMS] To develop an antifouling paint capable of preventing adhesion of marine organisms and seaweeds to underwater structures, fishing nets, and ship bottoms. (A) The following general formula (I): A copolymer obtained by polymerizing a monomer mixture consisting of the polymerizable monomer represented by the formula (b) and a copolymerizable unsaturated monomer (b) is contained as a vehicle component of the antifouling paint.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、防汚性塗料組成物
に関し、より詳しくは水中構築物、漁網、船底への海中
生物および海藻類の付着を防止することができる防汚性
塗料組成物に関する。The present invention relates to an antifouling paint composition, and more particularly to an antifouling paint composition capable of preventing the adhesion of marine organisms and seaweeds to underwater structures, fishing nets, and ship bottoms. .
【０００２】[0002]
【従来の技術および発明が解決しようとする課題】従
来、船舶や海洋構造物の浸水部分には、フジツボ、フナ
クイムシ、藻類など海中生物の付着による腐食防止や船
舶の航行速度低下の防止を目的として、有機錫等で代表
される防汚剤成分を含有する防汚塗料が塗装されてい
る。また、養殖用の網においても、海中生物の付着によ
る魚介類の致死防止等の目的で有機錫等の防汚剤成分を
含有する防汚塗料が塗装されている。2. Description of the Related Art Conventionally, inundated portions of ships and marine structures have been used for the purpose of preventing corrosion due to the attachment of marine organisms such as barnacles, bark beetles, and algae, and preventing a decrease in the navigation speed of ships. An antifouling paint containing an antifouling agent component represented by organic tin or the like is coated. Further, anti-fouling paints containing anti-fouling components such as organotin are also applied to aquaculture nets for the purpose of preventing lethality of fish and shellfish due to the attachment of marine organisms.
【０００３】この防汚塗料においては、その塗膜に含ま
れる防汚剤成分が海中に溶出することによって防汚効果
を発揮するものであり、毒性の強い有機錫に代表される
防汚剤を含有するため、魚介類に対して悪影響を及ぼす
欠点がある。そのために、毒性が少なく、かつ長期にわ
たり海中で防汚機能を発揮する防汚性塗料組成物の開発
に対する要請はきわめて強くなっている。In this antifouling paint, the antifouling agent component contained in the coating film exerts an antifouling effect by eluting into the sea, and the antifouling agent represented by highly toxic organotin is used. There is a disadvantage that it has an adverse effect on fish and shellfish due to its inclusion. Therefore, the demand for the development of an antifouling paint composition having low toxicity and exhibiting an antifouling function in the sea for a long period of time has become extremely strong.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、魚介
類等に悪影響を及ぼす防汚剤成分を含有しない場合にお
いても、長期にわたって海中で防汚効果を発揮すること
ができる防汚塗料を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide an antifouling paint capable of exhibiting an antifouling effect in the sea for a long time even when it does not contain an antifouling agent component which adversely affects fish and shellfish. To provide.
【０００５】[0005]
【課題を解決するための手段】本発明者等は、上記の目
的達成するために、鋭意検討を進めた結果、特定の共重
合体をビヒクル成分とする防汚性塗料組成物が優れた性
能を示し、上記の目的を達成できることを見い出し本発
明を完成した。すなわち本発明は、（ａ）下記一般式
（Ｉ）Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, the antifouling coating composition containing a specific copolymer as a vehicle component has excellent performance. And found that the above object could be achieved, and completed the present invention. That is, the present invention relates to (a) the following general formula (I)
【０００６】[0006]
【化２】 で表わされる重合性単量体、および（ｂ）共重合可能な
不飽和単量体、からなる単量体混合物を重合して得られ
る共重合体をビヒクルとして含有することを特徴とする
防汚性塗料組成物にある。Embedded image Characterized in that it contains, as a vehicle, a copolymer obtained by polymerizing a monomer mixture consisting of a polymerizable monomer represented by the formula: and (b) a copolymerizable unsaturated monomer. In a water-soluble coating composition.
【０００７】[0007]
【発明の実施の形態】以下、本発明の防汚塗料組成物で
使用するビヒクル用共重合体の単量体成分について説明
する。BEST MODE FOR CARRYING OUT THE INVENTION The monomer components of the copolymer for vehicles used in the antifouling coating composition of the present invention will be described below.
【０００８】一般式（Ｉ）で表わされる重合性単量体
（ａ）は、生物を付着しにくくするために用いる成分で
ある。具体例としては、２−クロロエチル（メタ）アク
リレート、２−クロロ−１−メチルエチル（メタ）アク
リレート、３−クロロプロピル（メタ）アクリレート、
２，３−ジクロロプロピル（メタ）アクリレート、２−
クロロ−１−クロロメチルエチル（メタ）アクリレー
ト、２，２，２−トリクロロエチル（メタ）アクリレー
ト、６−クロロ−ｎ−ヘキシル（メタ）アクリレート、
２−ブロモエチル（メタ）アクリレート、２−ブロモ−
１−メチルエチル（メタ）アクリレート、３−ブロモプ
ロピル（メタ）アクリレート、２，３−ジブロモプロピ
ル（メタ）アクリレート等が挙げられる。これらの単量
体は１種または２種以上を組み合わせて使用することが
できる。The polymerizable monomer (a) represented by the general formula (I) is a component used to make it difficult for organisms to adhere. Specific examples include 2-chloroethyl (meth) acrylate, 2-chloro-1-methylethyl (meth) acrylate, 3-chloropropyl (meth) acrylate,
2,3-dichloropropyl (meth) acrylate, 2-
Chloro-1-chloromethylethyl (meth) acrylate, 2,2,2-trichloroethyl (meth) acrylate, 6-chloro-n-hexyl (meth) acrylate,
2-bromoethyl (meth) acrylate, 2-bromo-
Examples thereof include 1-methylethyl (meth) acrylate, 3-bromopropyl (meth) acrylate, and 2,3-dibromopropyl (meth) acrylate. These monomers can be used alone or in combination of two or more.
【０００９】また、本発明において用いられる共重合可
能な不飽和単量体（ｂ）（以下、共重合単量体（ｂ）と
略記する。）としては、例えばメチル（メタ）アクリレ
ート、エチル（メタ）アクリレート、ｎ−プロピル（メ
タ）アクリレート、ｉ−プロピル（メタ）アクリレー
ト、ｎ−ブチル（メタ）アクリレート、ｉ−ブチル（メ
タ）アクリレート、ｔ−ブチル（メタ）アクリレート、
２−エチルヘキシル（メタ）アクリレート、ラウリル
（メタ）アクリレート、ステアリル（メタ）アクリレー
ト、ベンジル（メタ）アクリレート、フェニル（メタ）
アクリレート、イソボニル（メタ）アクリレート、シク
ロヘキシル（メタ）アクリレート、グリシジル（メタ）
アクリレート等の（メタ）アクリル酸エステル単量体、
２−ヒドロキシエチル（メタ）アクリレート、２−ヒド
ロキシプロピル（メタ）アクリレート、３−ヒドロキシ
プロピル（メタ）アクリレート、２−ヒドロキシブチル
（メタ）アクリレート、４−ヒドロキシブチル（メタ）
アクリレート等の水酸基を含有するビニル単量体、また
２−ヒドロキシエチル（メタ）アクリレートとエチレン
オキサイド、プロピレンオキサイド、γ−ブチロラクト
ンまたはε−カプロラクトン等との付加物、２−ヒドロ
キシエチル（メタ）アクリレート、２−ヒドロキシプロ
ピル（メタ）アクリレート等の二量体、三量体が挙げら
れる。さらにはグリセロール（メタ）アクリレートの如
く水酸基を複数有する単量体、ブチルアミノエチル（メ
タ）アクリレート、（メタ）アクリルアミド等の第一級
および第二級アミノ基含有ビニル単量体、ジメチルアミ
ノエチル（メタ）アクリレート、ジエチルアミノエチル
（メタ）アクリレート、ジメチルアミノプロピル（メ
タ）アクリレート、ジメチルアミノブチル（メタ）アク
リレート、ジブチルアミノエチル（メタ）アクリレー
ト、ジメチルアミノエチル（メタ）アクリルアミド、ジ
メチルアミノプロピル（メタ）アクリルアミド等の第三
級アミノ基含有ビニル単量体、ビニルピロリドン、ビニ
ルピリジン、ビニルカルバゾールの如き複素環族系塩基
性単量体等が挙げられる。さらにその他の共重合単量体
として、スチレン、ビニルトルエン、α−メチルスチレ
ン、（メタ）アクリロニトリル、酢酸ビニル、プロピオ
ン酸ビニル等のビニル系単量体が挙げられる。これらの
単量体は１種または２種以上を組み合わせて使用するこ
とができる。As the copolymerizable unsaturated monomer (b) (hereinafter abbreviated as copolymer monomer (b)) used in the present invention, for example, methyl (meth) acrylate, ethyl ( (Meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate,
2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth)
Acrylate, isobonyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth)
(Meth) acrylate monomers such as acrylates,
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth)
A hydroxyl-containing vinyl monomer such as acrylate, an adduct of 2-hydroxyethyl (meth) acrylate with ethylene oxide, propylene oxide, γ-butyrolactone or ε-caprolactone, 2-hydroxyethyl (meth) acrylate, Examples include dimers and trimers such as 2-hydroxypropyl (meth) acrylate. Further, monomers having a plurality of hydroxyl groups such as glycerol (meth) acrylate, vinyl monomers containing primary and secondary amino groups such as butylaminoethyl (meth) acrylate and (meth) acrylamide, and dimethylaminoethyl ( (Meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide And tertiary amino group-containing vinyl monomers, and heterocyclic basic monomers such as vinyl pyrrolidone, vinyl pyridine and vinyl carbazole. Still other copolymer monomers include vinyl monomers such as styrene, vinyltoluene, α-methylstyrene, (meth) acrylonitrile, vinyl acetate, and vinyl propionate. These monomers can be used alone or in combination of two or more.
【００１０】本発明においてビヒクルを構成する共重合
体は、上記の一般式（Ｉ）で表わされる重合性単量体
（ａ）と共重合単量体（ｂ）からなる単量体混合物を重
合することにより得られる。重合に際しては、重合性単
量体（ａ）１〜１００重量部に対して、共重合単量体
（ｂ）０〜９９重量部（合計１００重量部）となる割合
で重合することが好ましい。より好ましくは、重合性単
量体（ａ）１０〜７０重量部に対して、共重合単量体
（ｂ）３０〜９０重量部（合計１００重量部）となる割
合である。In the present invention, the copolymer constituting the vehicle is obtained by polymerizing a monomer mixture comprising a polymerizable monomer (a) and a copolymer monomer (b) represented by the above general formula (I). It is obtained by doing. At the time of polymerization, it is preferable to carry out the polymerization at a ratio of 0 to 99 parts by weight (total 100 parts by weight) with respect to 1 to 100 parts by weight of the polymerizable monomer (a). More preferably, the proportion is 30 to 90 parts by weight (total 100 parts by weight) of the copolymerizable monomer (b) with respect to 10 to 70 parts by weight of the polymerizable monomer (a).
【００１１】本発明で用いる共重合体は、公知の方法に
従って製造される。すなわち、上記した単量体を混合
し、この混合物をラジカル重合開始剤の存在下に６０〜
１８０℃の反応温度において５〜１４時間反応を続けて
重合させる。重合方法は、有機溶剤中で行う溶液重合法
のほかに乳化重合法、懸濁重合法等が採用できるが、ト
ルエン、キシレン、メチルイソブチルケトン、酢酸ｎ−
ブチル等の一般の有機溶剤を用いる溶液重合方法を採用
するのが生産性、性能の点で有利である。The copolymer used in the present invention is produced according to a known method. That is, the above-mentioned monomers are mixed, and this mixture is mixed with the radical polymerization initiator in the presence of a radical polymerization initiator.
The reaction is continued at a reaction temperature of 180 ° C. for 5 to 14 hours for polymerization. As the polymerization method, in addition to the solution polymerization method performed in an organic solvent, an emulsion polymerization method, a suspension polymerization method, and the like can be adopted, but toluene, xylene, methyl isobutyl ketone, n-acetic acid n-
It is advantageous in terms of productivity and performance to employ a solution polymerization method using a general organic solvent such as butyl.
【００１２】本発明の防汚性塗料組成物は、上記の共重
合体をビヒクル成分として構成され、必要に応じてこれ
に従来公知の防汚剤が配合される。防汚剤を配合する場
合、防汚性塗料組成物におけるビヒクルとしての共重合
体の割合は、特に限定されるものではない。The antifouling coating composition of the present invention comprises the above copolymer as a vehicle component, and if necessary, a conventionally known antifouling agent is added thereto. When an antifouling agent is added, the proportion of the copolymer as a vehicle in the antifouling coating composition is not particularly limited.
【００１３】防汚剤としては、要求性能に応じて従来使
用されている公知の防汚剤、例えば亜酸化銅、チオシア
ン銅、銅粉末等の銅系防汚剤を始め、鉛、亜鉛、ニッケ
ル等その他の金属化合物、ジフェニルアミン等のアミン
誘導体、ニトリル化合物、ベンゾチアゾール系化合物、
マレイミド系化合物、ピリジン系化合物等が単独あるい
は複数で使用される。Examples of the antifouling agent include known antifouling agents conventionally used according to the required performance, for example, copper-based antifouling agents such as cuprous oxide, copper thiocyanate and copper powder, as well as lead, zinc, nickel and the like. Other metal compounds, such as amine derivatives such as diphenylamine, nitrile compounds, benzothiazole compounds,
A maleimide compound, a pyridine compound, or the like is used alone or in combination.
【００１４】その他、防汚剤ではないが、塗膜表面に潤
滑性を付与し、生物の付着を防止する目的でジメチルポ
リシロキサン、シリコンオイル等のシリコン化合物やフ
ッ化炭素等の含フッ素化合物等も使用することができ
る。さらに本発明の防汚性塗料組成物は、前記した防汚
剤以外にも体質顔料、着色顔料、可塑剤、各種塗料用添
加剤、その他の樹脂等を必要に応じて配合することがで
きる。In addition, although not an antifouling agent, a silicone compound such as dimethylpolysiloxane or silicone oil or a fluorine-containing compound such as fluorocarbon is used for the purpose of imparting lubricity to the coating film surface and preventing the attachment of organisms. Can also be used. Further, the antifouling paint composition of the present invention may further contain, if necessary, extenders, coloring pigments, plasticizers, various paint additives, other resins, and the like, in addition to the above-described antifouling agent.
【００１５】本発明の組成物を用いて塗膜を形成するに
は、上述した防汚性塗料組成物を、船舶、各種漁網、港
湾施設、オイルフェンス、橋梁、海底基地等の水中構造
物等の基材表面に直接に、もしくは基材にウオッシュプ
ライマー、塩化ゴム系、エポキシ系等のプライマー、中
塗り塗料等を塗布した塗膜の上に刷毛塗り、吹き付け塗
り、ローラー塗り、沈漬塗り等の手段で塗布する。塗布
量は、一般的には乾燥塗膜として５０〜４００μｍの厚
さの範囲である。塗膜の乾燥は一般的には室温で行われ
るが、加熱乾燥を行っても差し支えない。In order to form a coating film using the composition of the present invention, the above-described antifouling paint composition is applied to underwater structures such as ships, various fishing nets, port facilities, oil fences, bridges and submarine bases. Brush coating, spray coating, roller coating, immersion coating, etc., directly on the surface of the base material, or on a coating film obtained by applying wash primer, chlorinated rubber-based, epoxy-based primer, intermediate coating, etc. Apply by means of The coating amount is generally in the range of 50 to 400 μm in thickness as a dry coating film. The coating film is generally dried at room temperature, but may be dried by heating.
【００１６】[0016]
【実施例】以下、本発明を実施例および比較例によりさ
らに詳しく説明するが、本発明はこれらの例によってな
んら限定されるものではない。なお、例中の部は重量部
を表わす。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. The parts in the examples represent parts by weight.
【００１７】［実施例１〜１２および比較例１〜４］冷
却器、温度計、滴下ロートおよび撹拌機を備えた四つ口
フラスコにキシレン５５部を仕込み、撹拌しながら１０
０℃に昇温した。続いて、滴下ロートから表１に示す単
量体および重合開始剤からなる混合物を４時間で等速滴
下した。滴下終了後にｔ−ブチルパーオクトエート１部
とキシレン１０部を２時間で滴下し、さらに１時間撹拌
した後キシレンを３５部添加して表１に示す特性値を有
するビヒクル用重合体溶液Ａ１〜Ａ６、Ｂ１〜Ｂ２を得
た。ただし、共重合体溶液Ｂ１の製造においては、仕込
み時の有機溶剤量をキシレン５５部からキシレン６０部
とイソプロピルアルコール２０部とからなる混合有機溶
剤に変更し、さらに最後に添加するキシレンの量を３５
部から１０部に変更して行った。[Examples 1 to 12 and Comparative Examples 1 to 4] 55 parts of xylene was charged into a four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer, and stirred while stirring.
The temperature was raised to 0 ° C. Subsequently, a mixture composed of the monomers and the polymerization initiator shown in Table 1 was dropped at a constant rate over 4 hours from the dropping funnel. After completion of the dropwise addition, 1 part of t-butyl peroctoate and 10 parts of xylene were added dropwise over 2 hours. After stirring for 1 hour, 35 parts of xylene was added, and the polymer solutions A1 to vehicle having the characteristic values shown in Table 1 were added. A6 and B1 to B2 were obtained. However, in the production of the copolymer solution B1, the amount of the organic solvent at the time of charging was changed from 55 parts of xylene to a mixed organic solvent composed of 60 parts of xylene and 20 parts of isopropyl alcohol, and the amount of xylene added last was further changed. 35
Was changed from 10 parts to 10 parts.
【００１８】[0018]
【表１】 [Table 1]
【００１９】次いで、このようにして得られた共重合体
溶液Ａ１〜Ａ６を用いて、表２に示す配合割合により本
発明の防汚性塗料（実施例１〜１２）を調製した。ま
た、共重合体溶液Ｂ１〜Ｂ２を用いて、表２に示す配合
割合により比較例１〜４の防汚性塗料を調製した。Next, using the copolymer solutions A1 to A6 thus obtained, antifouling paints of the present invention (Examples 1 to 12) were prepared at the compounding ratios shown in Table 2. Further, using the copolymer solutions B1 and B2, the antifouling paints of Comparative Examples 1 to 4 were prepared at the compounding ratios shown in Table 2.
【００２０】[0020]
【表２】 [Table 2]
【００２１】次いで、上記各防汚塗料を用いて、下記の
要領で塗膜の防汚性試験を行った。Next, using each of the above antifouling paints, a coating film was subjected to an antifouling test in the following manner.
【００２２】［防汚性試験］各防汚性塗料を、あらかじ
め防錆塗料を塗布してあるサンドプラスト鋼板に、乾燥
膜厚が２４０μｍになるように塗布して試験板を作製
し、広島県の広島湾内で２４ヵ月間浸漬し、６ヵ月毎に
付着性物の付着面積（％）を調べた。その結果を表３に
示した。[Anti-fouling test] Each anti-fouling paint was applied to a sand-blasted steel sheet to which a rust-preventive paint had been previously applied so that the dry film thickness was 240 μm, and a test plate was prepared. Was immersed in Hiroshima Bay for 24 months, and the adhesion area (%) of the adhered substance was examined every 6 months. Table 3 shows the results.
【００２３】[0023]
【表３】 [Table 3]
【００２４】表２〜３に示す結果からも明らかなよう
に、共重合体溶液Ｂ１〜Ｂ２を用いた防汚性塗料組成物
（比較例１〜４）では十分な防汚性能が得られなかっ
た。これに対し共重合体溶液Ａ１〜Ａ６を用いた本発明
の防汚性塗料組成物（実施例１〜１２）は、長期にわた
って優れた防汚性能を示した。As is clear from the results shown in Tables 2 and 3, the antifouling paint compositions using the copolymer solutions B1 and B2 (Comparative Examples 1 to 4) did not provide sufficient antifouling performance. Was. On the other hand, the antifouling coating compositions of the present invention using the copolymer solutions A1 to A6 (Examples 1 to 12) exhibited excellent antifouling performance over a long period of time.
【００２５】[0025]
【発明の効果】本発明の防汚性塗料組成物は、ハロゲン
原子を含有する共重合体をビヒクル成分として用いてい
るため、防汚剤を含有しない場合でも長期間にわたって
優れた防汚効果を発揮することができ、環境衛生上極め
て有益なものである。The antifouling paint composition of the present invention uses a copolymer containing a halogen atom as a vehicle component, so that even if it does not contain an antifouling agent, it has an excellent antifouling effect over a long period of time. It can be demonstrated and is extremely beneficial for environmental health.
Claims (1)
不飽和単量体、からなる単量体混合物を重合して得られ
る共重合体をビヒクルとして含有することを特徴とする
防汚性塗料組成物。(A) The following general formula (I): Characterized in that it contains, as a vehicle, a copolymer obtained by polymerizing a monomer mixture consisting of a polymerizable monomer represented by the formula: and (b) a copolymerizable unsaturated monomer. Paint composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33084897A JPH11148031A (en) | 1997-11-17 | 1997-11-17 | Antifouling paint composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33084897A JPH11148031A (en) | 1997-11-17 | 1997-11-17 | Antifouling paint composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11148031A true JPH11148031A (en) | 1999-06-02 |
Family
ID=18237217
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33084897A Pending JPH11148031A (en) | 1997-11-17 | 1997-11-17 | Antifouling paint composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11148031A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102796452A (en) * | 2012-09-06 | 2012-11-28 | 苏州吉人漆业有限公司 | Antifouling self-cleaning nano functional paint and preparation method thereof |
-
1997
- 1997-11-17 JP JP33084897A patent/JPH11148031A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102796452A (en) * | 2012-09-06 | 2012-11-28 | 苏州吉人漆业有限公司 | Antifouling self-cleaning nano functional paint and preparation method thereof |
| CN102796452B (en) * | 2012-09-06 | 2014-11-26 | 苏州吉人漆业有限公司 | Antifouling self-cleaning nano functional paint and preparation method thereof |
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