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WO1992016570A1 - Peinture de protection marine - Google Patents

Peinture de protection marine Download PDF

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Publication number
WO1992016570A1
WO1992016570A1 PCT/JP1992/000299 JP9200299W WO9216570A1 WO 1992016570 A1 WO1992016570 A1 WO 1992016570A1 JP 9200299 W JP9200299 W JP 9200299W WO 9216570 A1 WO9216570 A1 WO 9216570A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
antifouling paint
marine antifouling
formula
polymer
Prior art date
Application number
PCT/JP1992/000299
Other languages
English (en)
Japanese (ja)
Inventor
Kiyomi Mori
Takeshi Hamachi
Shigemi Kojima
Keiji Ueda
Hitoshi Tabuchi
Original Assignee
Nitto Kasei Co., Ltd.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nitto Kasei Co., Ltd. filed Critical Nitto Kasei Co., Ltd.
Publication of WO1992016570A1 publication Critical patent/WO1992016570A1/fr

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52Amides or imides
    • C08F20/54Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F20/58Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-acryloylmorpholine
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10Esters
    • C08F20/26Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/28Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16Antifouling paints; Underwater paints
    • C09D5/1656Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662Synthetic film-forming substance
    • C09D5/1668Vinyl-type polymers

Definitions

  • the present invention relates to a marine antifouling paint for preventing marine organisms from adhering to underwater structures such as ships and fish nets, a method for protecting ships and fish nets using the paint, and a polymer used therefor.
  • Marine antifouling paint using an organotin-containing copolymer is gradually hydrolyzed in seawater, and the organotin portion of the copolymer side chain is appropriately eluted from the coating film surface, and can exhibit a long-term antifouling effect It has been widely used.
  • the use of marine antifouling agents using organotin-containing copolymers has recently been restricted due to the problem of marine pollution.
  • an antifouling agent is introduced into the side chain of the polymer instead of the organotin compound, and the antifouling agent is released into seawater to release the antifouling agent.
  • a submarine antifouling agent has been proposed which is found in the patent applications of Japanese Patent Application Laid-Open No. 60-500452 and Japanese Patent Application Laid-Open No. 61-26374, which exhibit high performance.
  • ester moieties in the copolymers disclosed in these patent applications are not sufficiently hydrolyzed under weak alkaline conditions such as natural seawater (pH 8.0 to 8.9), and are therefore practically resistant to antifouling. There was a major drawback in that it was not effective.
  • the present inventors have conducted intensive studies to solve the above-mentioned disadvantages of the prior art, and as a result, the antifouling coating film is appropriately hydrolyzed in natural seawater for a long time.
  • the present inventors have found a marine antifouling paint and a polymer used therein, and have reached the present invention. That is, according to the present invention, a) an antifouling component b) a binder of the formula (I)
  • R is an alkyl group, cycloalkyl group, aryl group or an aralkyl group which may be optionally substituted in the aryl group
  • A is a hydrogen atom or a methyl group
  • a marine antifouling paint comprising: a) a solvent and, if necessary, d) an additive. According to the present invention, further, the formula (I)
  • ⁇ , ⁇ and R have the same meanings as described above, By polymerizing one or more unsaturated monomers represented by the general formula (1) or one or more unsaturated monomers represented by the general formula (() and another ethylenically unsaturated monomer It can be obtained by copolymerizing one or more monomers.
  • Examples of the unsaturated monomer represented by the formula (1 ′) include the following:
  • CH 2 C-C00 (CH 2 ) 2 -0C-C-0C 2 H 5 (A: H, CH 3 )
  • CH 2 C-C00 (CH 2 ) 2-OC-C-OC4H9 (A: H, CH 3 ) A
  • CH 2 C-C00 (CH 2 ) 2-0C-C-0CH 2 (A: H, CH 3 )
  • CE 2 C-C00 (CH 2 ) 3-0C-C-0C 2 H 5 (A: H, CH 3 )
  • I II II II CH 2 CC-CH 2 0C-C-0C 2 H 5 (A: H, CH 3 )
  • the unsaturated monomer of the above formula ( ⁇ ') is represented by the formula (II) It is obtained by reacting an unsaturated monomer having a free hydroxyl group with an acid halide represented by the formula (III) in the presence of a base such as triethylamine, pyridine, sodium hydroxide, or sodium carbonate. .
  • A is a hydrogen atom or a methyl group
  • R 1 represents an alkylene group or a phenylene group, respectively.
  • R represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and X represents a chlorine atom, a bromine atom or an iodine atom.
  • unsaturated monomers having a free hydroxyl group represented by the formula (II) include, for example, aryl alcohol; 5-methallyl alcohol,
  • Examples of the acid halide represented by the formula (III) include ethyl chloroglyoxylate, propyl bromoglyoxylate, butyl chloroglyoxylate, octyl chloroglyoxylate, phenyl chloroglyoxylate, benzyl chloroglyoxylate, Examples include acid chlorides such as cyclohexyl chloroglyoxylate and acid bromides obtained by substituting the bromo atom of the above compound with a bromo atom.
  • the unsaturated monomer of the formula (1 ′) is obtained by converting an unsaturated monomer having a free carboxyl group (for example, acrylic acid or methacrylic acid) and a halide represented by the formula (IV) into triethylamine. It can also be obtained by reacting in the presence of a base such as pyridine, sodium hydroxide and sodium carbonate.
  • a base such as pyridine, sodium hydroxide and sodium carbonate.
  • halide represented by the formula (IV) examples include methyl bromopyruvate, ethyl bromopyruvate, butyl bromopyruvate, octyl bromopyruvate, phenyl bromopyruvate, benzyl bromopyruvate, and cyclobromopyruvate. Brominated compounds such as xyl, and chlorinated compounds obtained by substituting the prom atom of the above compound with a ketone atom are included.
  • the polymer according to the present invention having a repeating unit represented by the formula (I) further comprises one or more unsaturated monomers having a free hydroxyl group represented by the formula (II).
  • the resulting copolymer is mixed with an acid halide represented by the formula (III), triethylamine, pyridine It can also be obtained by reacting in the presence of a base such as sodium hydroxide, sodium carbonate and the like.
  • a base such as sodium hydroxide, sodium carbonate and the like.
  • the other ethylenically unsaturated monomer is not limited as long as it is a copolymerizable monomer.
  • acrylate (methacrylic acid) esters such as methyl methacrylate, ethyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, vinylidene chloride, acrylonitrile, acrylamide, vinyl acetate, and vinyl pyrrolidone.
  • the antifouling component contained in the marine antifouling paint of the present invention is not limited as long as it has a killing or repelling effect on marine fouling organisms.
  • Compounds such as zinc oxide, rodane, and powder; organic compounds such as tetrachloroisophthalonitrile; 3,4-cycle-mouth phenylisothiocynate; zinc dithiolbamate; 2-mercaptopyridine N —Zinc compounds such as zinc oxide, thiuram compounds, maleimide compounds, etc., which can be used alone or as a mixture.
  • the amount of the antifouling component in the marine antifouling paint of the present invention is not particularly limited, but is preferably from 10 to 200% by weight of the polymer having the repeating unit represented by the formula (I).
  • the marine antifouling paint of the present invention further comprises a polymer having a repeating unit of the formula (I) and, if necessary, a rosin, a rubber chloride, an acryl resin, a vinyl chloride-vinyl acid copolymer (VYHH). Natural or synthetic resins such as the above can also be used in combination.
  • the marine antifouling paint of the present invention can contain further additives as necessary.
  • additives include pigments, dyes, and plasticizers.
  • the marine antifouling paint of the present invention contains a solvent for the above polymer, but such a solvent is not particularly limited.
  • a solvent is not particularly limited.
  • methyl ethyl ketone, methyl isobutyl ketone, xylene, propylene glycol Monomethyl ether acetate and the like can be mentioned.
  • the obtained yellow copolymer solution (copolymer solution A) had a viscosity of 630 cps, a heating residue of 38.9%, and a molecular weight of 140,000.
  • the resulting dark brown copolymer solution (Copolymer Solution H) had a viscosity of 1200 cps, a heating residue of 48.2%, and a molecular weight of 81,000.
  • Example 10 In a 50 Om 1 four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, 64 g of the benzyloxalyloxhexyl methacrylate obtained in Production Example 5, 16 g of methyl acrylate, and propylene 120 g of glycol monomethyl ether acetate and 2 g of azobisisobutyronitrile (AIBN) are added, and polymerized under a nitrogen atmosphere at 85 to 90 ° C for 4.5 hours to obtain a pale yellow copolymer. A solution (copolymer solution J) was obtained. The obtained copolymer solution J had a viscosity of 226 cps, a heating residue of 39.5%, and a molecular weight of 57,000.
  • AIBN azobisisobutyronitrile
  • copolymer solution N a pale yellow copolymer solution (copolymer solution N).
  • the obtained copolymer solution N had a viscosity of 262 cps, a heating residue of 39.9%, and a molecular weight of 6,000.
  • Comparative Example 1 The same procedure as in Example 1 was repeated, except that 90 g of funasyl acrylate was used in place of 90 g of 2-ethoxyoxalyloxyshetyl acrylate in Example 1. Polymerized for hours.
  • the obtained funasyl ester-containing copolymer solution (comparative copolymer solution 1) had a viscosity of 850 cps, a heating residue of 49.2%, and a molecular weight of 43,000.
  • benzyl ester-containing copolymer solution (comparative copolymer solution 2) had a viscosity of 980 cps, a heating residue of 49.1%, and a molecular weight of 38,000.
  • a rotating drum with a diameter of 31.8 mm and a height of 450 mm was attached to the center of the water tank, and this could be rotated by a motor.
  • a heating device and a cooling device were installed to keep the seawater temperature constant, and a pH automatic controller was installed to keep the seawater pH constant.
  • Each of the copolymer solutions and marine antifouling paints obtained in Examples 1-34 and Comparative Examples 1-2 was coated on a 1 mm thick hard vinyl chloride plate so as to have a dry film thickness of about 100 microns. After drying, it was dried at 50 ° C. for 24 hours. The test plate coated with the marine antifouling paint is brought into contact with seawater on the rotating drum of the above rotating device.
  • Example 18 34 and Comparative Example 34 were applied to both sides of a hard vinyl chloride plate so as to have a dry film thickness of 200 microns.
  • the test plate was immersed 1.5 m below the sea surface in Oga Bay, Mie Prefecture, and the test plate was stained for 18 months with attached organisms. Table 4 shows the results.
  • Tolerable to use as a culture net due to the adhesion of living things.
  • the polymer having a non-ketoester group of the present invention has excellent adhesion to base materials such as ship bottoms and fish nets, and the coating film is tough. As is clear from Table 3, it is moderately hydrolyzed in natural seawater.
  • the marine antifouling coating composition of the present invention obtained by adding an antifouling component to the polymer can maintain the antifouling effect for a long period of time, and does not have to worry about marine pollution as seen in conventional antifouling coating compositions.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un polymère présentant des unités à répétition et représenté par la formule générale (I), une peinture de protection marine comprenant un composant 'antifouling' et un solvant et contenant une résine comprenant le polymère en tant que liant, et procédé de protection des bateaux ou des filets de pêche par application de ladite peinture. Dans la formule (I), A représente hydrogène ou méthyle, B représente -C(=O)OR'O-, -OR'O-, -C(=O)OCH2-, -C(=O)NHCH2O-, -C(=O)R'O-, -OC(=O)R'O-, -O- ou -R'O-, où R' représente alkylène ou phénylène, et R représente alkyle, cycloalkyle, aryle ou aralkyle pouvant être éventuellement substitué au niveau du groupe aryle.
PCT/JP1992/000299 1991-03-15 1992-03-12 Peinture de protection marine WO1992016570A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP7698791 1991-03-15
JP3/76987 1991-03-15

Publications (1)

Publication Number Publication Date
WO1992016570A1 true WO1992016570A1 (fr) 1992-10-01

Family

ID=13621134

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1992/000299 WO1992016570A1 (fr) 1991-03-15 1992-03-12 Peinture de protection marine

Country Status (1)

Country Link
WO (1) WO1992016570A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996041842A1 (fr) * 1995-06-13 1996-12-27 Jotun A/S Polymeres pour des peintures maritimes et un procede pour leur preparation
WO2014148241A1 (fr) * 2013-03-22 2014-09-25 Jsr株式会社 Composition de résine sensible au rayonnement, procédé de formation de motif de réserve, polymère et procédé permettant de produire un composé
JP2015141356A (ja) * 2014-01-29 2015-08-03 Jsr株式会社 感放射線性樹脂組成物、レジストパターン形成方法、重合体及び化合物
CN105175277A (zh) * 2015-05-18 2015-12-23 中山大学肿瘤防治中心 一种3-磷酸甘油醛脱氢酶的抑制剂及其制备方法和应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02288844A (ja) * 1989-01-12 1990-11-28 Nippon Paint Co Ltd 重合性化合物およびそれから得られる重合体

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02288844A (ja) * 1989-01-12 1990-11-28 Nippon Paint Co Ltd 重合性化合物およびそれから得られる重合体

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996041842A1 (fr) * 1995-06-13 1996-12-27 Jotun A/S Polymeres pour des peintures maritimes et un procede pour leur preparation
WO2014148241A1 (fr) * 2013-03-22 2014-09-25 Jsr株式会社 Composition de résine sensible au rayonnement, procédé de formation de motif de réserve, polymère et procédé permettant de produire un composé
US20150323866A1 (en) * 2013-03-22 2015-11-12 Jsr Corporation Radiation-sensitive resin composition, resist pattern-forming method, polymer, and method for producing compound
JPWO2014148241A1 (ja) * 2013-03-22 2017-02-16 Jsr株式会社 感放射線性樹脂組成物、レジストパターン形成方法、重合体及び化合物の製造方法
US9703195B2 (en) 2013-03-22 2017-07-11 Jsr Corporation Radiation-sensitive resin composition, resist pattern-forming method, polymer, and method for producing compound
JP2015141356A (ja) * 2014-01-29 2015-08-03 Jsr株式会社 感放射線性樹脂組成物、レジストパターン形成方法、重合体及び化合物
CN105175277A (zh) * 2015-05-18 2015-12-23 中山大学肿瘤防治中心 一种3-磷酸甘油醛脱氢酶的抑制剂及其制备方法和应用
CN105175277B (zh) * 2015-05-18 2018-04-03 中山大学肿瘤防治中心 一种3‑磷酸甘油醛脱氢酶的抑制剂及其制备方法和应用

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