NO156493B - MARIN PAINTING comprising a film-forming acrylic polymer and an acrylic polymer for use in the paint - Google Patents

MARIN PAINTING comprising a film-forming acrylic polymer and an acrylic polymer for use in the paint Download PDF

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Publication number
NO156493B
NO156493B NO840005A NO840005A NO156493B NO 156493 B NO156493 B NO 156493B NO 840005 A NO840005 A NO 840005A NO 840005 A NO840005 A NO 840005A NO 156493 B NO156493 B NO 156493B
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Norway
Prior art keywords
units
acrylic polymer
monomer
triorganotin
paint
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NO840005A
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Norwegian (no)
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NO156493C (en
NO840005L (en
Inventor
Marius Sghibartz Christian
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Jotungruppen As
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Application filed by Jotungruppen As filed Critical Jotungruppen As
Priority to NO840005A priority Critical patent/NO156493C/en
Priority to DK610484A priority patent/DK172317B1/en
Priority to GB08432163A priority patent/GB2152947B/en
Priority to NL8403867A priority patent/NL192114C/en
Priority to IT49342/84A priority patent/IT1178318B/en
Priority to DE3446971A priority patent/DE3446971C2/en
Priority to FR8419796A priority patent/FR2557585B1/en
Priority to AU37147/84A priority patent/AU570530B2/en
Priority to ES539165A priority patent/ES8607995A1/en
Priority to SE8406666A priority patent/SE465574B/en
Priority to BR8406783A priority patent/BR8406783A/en
Priority to CA000471098A priority patent/CA1260186A/en
Priority to BE0/214280A priority patent/BE901426A/en
Priority to JP59274997A priority patent/JPS60158211A/en
Priority to PT79776A priority patent/PT79776B/en
Priority to GR82615A priority patent/GR82615B/en
Priority to KR1019840008526A priority patent/KR930008744B1/en
Publication of NO840005L publication Critical patent/NO840005L/en
Publication of NO156493B publication Critical patent/NO156493B/en
Publication of NO156493C publication Critical patent/NO156493C/en
Priority to SG799/90A priority patent/SG79990G/en
Priority to HK948/92A priority patent/HK94892A/en

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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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1668—Vinyl-type polymers
    • 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
    • C08F220/00—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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • 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
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C08F220/00—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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate

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

Description

Denne oppfinnelse angår nye marine malinger og visse nye terpolymerer som er nyttige komponenter deri. This invention relates to new marine paints and certain new terpolymers which are useful components therein.

Det er kjent marine malinger hvor en vesentlig komponent There are known marine paints where an essential component

er en kopolymer som inneholder enheter av alkylakrylater og -metakrylater og enheter av triorganotinnestere av akryl- og metakrylsyre. Alkylakrylat- og -metakrylat-enhetene tilfører hardhet til den film som oppnås når den marine maling påføres på et underlag, og triorganotinnester-enhetene tilfører biocid såvel som selvpolerende virkning. Under bruk avspaltes triorganotinn-enhetene fra polymeren ved hydrolyse og/eller ionebytting, hvorved filmen av den marine maling utøver en ønsket biocid virkning. Samtidig nedbrytes filmen, og dette resulterer i den selvpolerende virkning. is a copolymer containing units of alkyl acrylates and methacrylates and units of triorganotin esters of acrylic and methacrylic acid. The alkyl acrylate and methacrylate units add hardness to the film obtained when the marine paint is applied to a substrate, and the triorganotin ester units add biocide as well as self-polishing action. During use, the triorganotin units are split off from the polymer by hydrolysis and/or ion exchange, whereby the film of the marine paint exerts a desired biocidal effect. At the same time, the film breaks down, and this results in the self-polishing effect.

For således å oppnå en tilfredsstillende selvpolerende Virkning, må en viss mengde av triorganotinn-enheter være til stede i kopolymeren som anvendes i den marine maling, eftersom den selvpolerende virkning er en følge av avspaltningen av nevnte enheter. På den annen side ønskes det å holde mengden av triorganotinnenheter så lav som mulig, under hensyntagen til den ønskede biocide og selvpolerende virkning, eftersom triorganotinnmonomerer er forholdsvis kostbare og også har en myknende virkning på kopolymeren. In order to thus achieve a satisfactory self-polishing effect, a certain amount of triorganotin units must be present in the copolymer used in the marine paint, since the self-polishing effect is a consequence of the splitting off of said units. On the other hand, it is desired to keep the amount of triorganotin units as low as possible, taking into account the desired biocidal and self-polishing effect, since triorganotin monomers are relatively expensive and also have a softening effect on the copolymer.

Kopolymerer av den ovenfor angitte type er beskrevet bl.a. Copolymers of the above-mentioned type have been described i.a.

i britisk patent 1.457.590. in British patent 1,457,590.

I norsk patentansøkning 81.3553 er det foreslått å erstatte noen av eller alle triorganotinnester-enhetene med metylakrylat-og/eller etylakrylat-enheter. Den marine maling kan inneholde noe ytterligere biocid, særlig hvis kopolymeren ikke inneholder noen triorganotinnester-enheter. Nevnte metylakrylat- og etylakrylat-enheter vil til en viss grad hydrolyseres i vann og vil gi det ferdige belegg en selvpolerende virkning. På grunn av den resulterende kopolymers lave hydrolysehastighet vil imidlertid den selvpolerende virkning ikke være helt tilfredsstillende. In Norwegian patent application 81.3553, it is proposed to replace some or all of the triorganotin ester units with methyl acrylate and/or ethyl acrylate units. The marine paint may contain some additional biocide, particularly if the copolymer does not contain any triorganotin ester units. Said methyl acrylate and ethyl acrylate units will be hydrolysed to a certain extent in water and will give the finished coating a self-polishing effect. However, due to the resulting copolymer's low hydrolysis rate, the self-polishing effect will not be completely satisfactory.

Ifølge foreliggende oppfinnelse tilveiebringes en marin maling, som i tillegg til vanlige malingkomponenter så som pigmenter, farvestoffer, oppløsningsmidler osv., omfatter en filmdannende akrylpolymer inneholdende enheter av monomerer med formelen According to the present invention, a marine paint is provided which, in addition to usual paint components such as pigments, dyes, solvents, etc., comprises a film-forming acrylic polymer containing units of monomers with the formula

hvor R<1> er C^_^-alkyl, og eventuelt også enheter av where R<1> is C^_^-alkyl, and optionally also units of

2. ett eller flere triorganotinnmetakrylater eller 2. one or more triorganotin methacrylates or

-akrylater. - acrylates.

Det karakteristiske ved oppfinnelsen er at kopolymeren også inneholder enheter av monomerer med formelen The characteristic feature of the invention is that the copolymer also contains units of monomers with the formula

hvor R=H eller CH3, R" = CH3 eller C2H5, n = 1 eller 2. where R=H or CH3, R" = CH3 or C2H5, n = 1 or 2.

Enhetene av monomer nr. 3 hydrolyseres lett for å danne frie karboksylgrupper, hvilket resulterer i en polymer som gradvis nedbrytes slik at det oppnås en selvpolerende virkning. The units of monomer No. 3 are readily hydrolyzed to form free carboxyl groups, resulting in a polymer that gradually degrades to achieve a self-polishing effect.

Monomer nr. 1 er til stede for å gjøre filmen tilstrekkelig hard. Monomer #1 is present to make the film sufficiently hard.

Når kopolymeren som anvendes i de marine malinger ifølge foreliggende oppfinnelse, bare består av enheter av monomerene 1 When the copolymer used in the marine paints according to the present invention only consists of units of the monomers 1

og 3, inneholder den vanligvis fra 15 til 80 vekt% av monomer nr. 3 og fra 20 til 85 vekt% av monomer nr. 1. and 3, it generally contains from 15 to 80% by weight of monomer No. 3 and from 20 to 85% by weight of monomer No. 1.

En foretrukket representant for monomer nr. 3 er 2-metoksyetylakrylat, og en foretrukket representant for monomer nr. 1 A preferred representative of monomer No. 3 is 2-methoxyethyl acrylate, and a preferred representative of monomer No. 1

er metylmetakrylat. is methyl methacrylate.

En marin maling som omfatter en kopolymer som inneholder A marine paint comprising a copolymer containing

enheter av de ovennevnte to monomerer nr. 1 og nr. 3, kan, som påpekt ovenfor, også inneholde biocide komponenter for å oppnå units of the above two monomers no. 1 and no. 3, may, as pointed out above, also contain biocidal components to achieve

den ønskede biocide virkning, så som kobber(I)oksyd, ditio-karbamater og triorganotinnfdrbindélser som er kjent innen teknikken. the desired biocidal effect, such as copper (I) oxide, dithiocarbamates and triorganotin compounds known in the art.

I tillegg til de to typer monomer som er angitt ovenfor, kan kopolymerene som anvendes i de marine malinger ifølge oppfinnelsen, også inneholde enheter av monomer nr. 2, dvs. triorganotinnakrylater og -metakrylater. Eksempler på slike triorganotinnmonomerer er tributyltinnmetakrylat og -akrylat, tripropyltinnmetakrylat og -akrylat og trifenyltinnmetakrylat og -akrylat. Triorganotinn-monomerene kan utgjøre opp til 60 vekt% av kopolymeren (terpolymer). In addition to the two types of monomer indicated above, the copolymers used in the marine paints according to the invention can also contain units of monomer no. 2, i.e. triorganotin acrylates and methacrylates. Examples of such triorganotin monomers are tributyltin methacrylate and acrylate, tripropyltin methacrylate and acrylate and triphenyltin methacrylate and acrylate. The triorganotin monomers can make up up to 60% by weight of the copolymer (terpolymer).

Slike terpolymerer er nye, og et ytterligere trekk ved oppfinnelsen er således akrylterpolymerer som inneholder enheter av de følgende monomerer Such terpolymers are new, and a further feature of the invention is thus acrylic terpolymers containing units of the following monomers

hvor R' = C^_4-alkyl, og where R' = C1-4-alkyl, and

2. triorganotinnmetakrylater eller -akrylater, 2. triorganotin methacrylates or acrylates,

hvor R = H eller CH3, R" er CH3 eller C2H5, n = 1 eller 2. where R = H or CH3, R" is CH3 or C2H5, n = 1 or 2.

Kopolymerene som inneholder monomerene nr. 1 og 3 kan frem-stilles ved vanlig polymerisasjon av egnede monomerer under anvendelse av egnede initiatorer og polymerisasjonsbetingelser. The copolymers containing the monomers no. 1 and 3 can be produced by ordinary polymerization of suitable monomers using suitable initiators and polymerization conditions.

Når det ønskes å fremstille en kopolymer (terpolymer) som også inneholder triorganotinn-metakrylat- eller -akrylatenheter (monomer 2), kan dette gjøres enten ved å polymerisere monomerene nr. 1 og 3 sammen med den ønskede triorganotinnmetakrylat- eller -akrylat-monomer, eller monomerene nr. 1 og 3 kan polymeriseres med met-akryl- eller akrylsyre, og karboksylgruppene på den resulterende polymer forestres derefter med triorganotinngrupper på i og for seg kjent måte. When it is desired to produce a copolymer (terpolymer) which also contains triorganotin methacrylate or acrylate units (monomer 2), this can be done either by polymerizing monomers no. 1 and 3 together with the desired triorganotin methacrylate or acrylate monomer, or the monomers no. 1 and 3 can be polymerized with methacrylic or acrylic acid, and the carboxyl groups on the resulting polymer are then esterified with triorganotin groups in a manner known per se.

Eksempel 1 Example 1

Metylmetakrylat (300 g, 3,00 mol) og 2-metoksyetylakrylat Methyl methacrylate (300 g, 3.00 mol) and 2-methoxyethyl acrylate

(200 g, 1,54 mol) ble oppløst i xylen (750 g). Azobisisobutyronitril (4 g, 0,024 mol) ble tilsatt, og oppløsningen ble opp-varmet til 7 5°C med omrøring og under nitrogen. (200 g, 1.54 mol) was dissolved in xylene (750 g). Azobisisobutyronitrile (4 g, 0.024 mol) was added and the solution was warmed to 75°C with stirring and under nitrogen.

Polymerisasjonen ble utført ved den ovenfor angitte tempera-tur i 5 timer og ble overvåket ved forandring i brytningsindeksen. The polymerization was carried out at the temperature indicated above for 5 hours and was monitored by changes in the refractive index.

Temperaturen ble hevet til 100°C i 30 minutter for å øde-legge eventuell gjenværende katalysatoraktivitet. The temperature was raised to 100°C for 30 minutes to destroy any remaining catalyst activity.

Det ble oppnådd en oppløsning av en kopolymer av metylmetakrylat - 2-metoksyetylakrylat (60:40 efter vekt). A solution of a copolymer of methyl methacrylate - 2-methoxyethyl acrylate (60:40 by weight) was obtained.

Eksempel 2 Example 2

Tributyltinnmetakrylat (150 g, 0,40 mol), metylmetakrylat Tributyltin methacrylate (150 g, 0.40 mol), methyl methacrylate

(250 g, 2,50 mol) og 2-metoksyetylakrylat (100 g, 0,77 mol) ble oppløst i xylen (750 g). Azobisisobutyronitril (4 g, 0,02 mol) ble tilsatt, og polymerisasjonen ble foretatt på lignende måte som i eksempel 1. (250 g, 2.50 mol) and 2-methoxyethyl acrylate (100 g, 0.77 mol) were dissolved in xylene (750 g). Azobisisobutyronitrile (4 g, 0.02 mol) was added and the polymerization was carried out in a similar manner to Example 1.

Det ble oppnådd en oppløsning av en terpolymer av tributyltinnmetakrylat - metylmetakrylat - 2-metoksyetylakrylat (30:50:20 A solution of a terpolymer of tributyltin methacrylate - methyl methacrylate - 2-methoxyethyl acrylate (30:50:20

efter vekt). by weight).

Eksempel 3 Example 3

409,2 g av kopolymeroppløsningen fra eksempel 1 ble blandet med kobber(I)oksyd (365,4 g) , sinkoksyd (151,2 g) , Aerosil® 409.2 g of the copolymer solution from example 1 was mixed with copper (I) oxide (365.4 g), zinc oxide (151.2 g), Aerosil®

(kolloidal kiselsyre) (4,0 g), Bentone® (fortykningsmiddel) (colloidal silicic acid) (4.0 g), Bentone® (thickener)

(8,0 g), denaturert etanol (4,8 g) og xylen (57,4 g) og ble malt natten over for å gi en maling med et forhold mellom kobber(I)oksyd og sinkoksyd på 70:30 efter volum. (8.0 g), denatured ethanol (4.8 g) and xylene (57.4 g) and was ground overnight to give a paint with a ratio of cupric oxide to zinc oxide of 70:30 by volume .

Eksempel 4 Example 4

409,2 g av terpolymeroppløsningen fra eksempel 2 ble blandet med kobber(I)oksyd (365,4 g), sinkoksyd (151,2 g), Aerosil® 409.2 g of the terpolymer solution from Example 2 was mixed with copper (I) oxide (365.4 g), zinc oxide (151.2 g), Aerosil®

(4,0 g), Bentone® (8,0 g), denaturert etanol (4,8 g) og xylen (57,4 g) og ble malt natten over for å gi en maling med et forhold mellom kobber(I)oksyd og sinkoksyd på 70:30 efter volum. (4.0 g), Bentone® (8.0 g), denatured ethanol (4.8 g) and xylene (57.4 g) and was ground overnight to give a paint with a ratio of copper(I) oxide and zinc oxide of 70:30 by volume.

Malingene beskrevet i eksemplene 3 og 4 ble undersøkt med hensyn til polering under anvendelse av et rotorapparat med en periferihastighet på 17 knop (ca. 31 km/t) i sjøvann ved en gjennomsnittstemperatur på 23°C. The paints described in Examples 3 and 4 were examined for polishing using a rotor apparatus with a peripheral speed of 17 knots (about 31 km/h) in sea water at an average temperature of 23°C.

En kommesielt vellykket selvpolerende maling inneholdende organotinnpolymer (X) ble anvendt som referanse. Prøvene ble utført over en periode på 90 dager, og malinglagets tykkelse ble bestemt ved elektromagnetisk induksjon. A commercially successful self-polishing paint containing organotin polymer (X) was used as a reference. The tests were carried out over a period of 90 days, and the thickness of the paint layer was determined by electromagnetic induction.

Claims (6)

1. Marin maling som omfatter en filmdannende akrylpolymer inneholdende enheter av monomerer med formelen og eventuelt også enheter av1. Marine paint comprising a film-forming acrylic polymer containing units of monomers of the formula and possibly also units of 2. ett eller flere triorganotinnmetakrylater eller -akrylater, karakterisert ved at akrylpolymeren også inneholder enheter av monomerer med formelen hvor R = H eller CH3, R" = CH3 eller C2Hs, n = 1 eller 2. 2. Marin maling ifølge krav 1, hvor akrylpolymeren inneholder enheter av2. one or more triorganotin methacrylates or acrylates, characterized in that the acrylic polymer also contains units of monomers with the formula where R = H or CH3, R" = CH3 or C2Hs, n = 1 or 2. 2. Marine paint according to claim 1, wherein the acrylic polymer contains units of 1. metylakrylat, og eventuelt1. methyl acrylate, and eventually 2. tributyltinnmetakrylat, karakterisert ved at akrylpolymeren også inneholder enheter av2. tributyltin methacrylate, characterized in that the acrylic polymer also contains units of 3. 2-metoksyetylakrylat. 3. Marin maling ifølge et av kravene 1 og 2, karakterisert ved at akrylpolymeren inneholder 15 til 80 vekt% enheter av monomer 3 og 20 til 85 vekt% enheter av monomer 1, og eventuelt opp til 60 vekt% enheter av monomer 2. 4. Akrylterpolymer, karakterisert ved at den inneholder enheter av de følgende monomerer hvor R' = Ci-4-alkyl, og3. 2-Methoxyethyl acrylate. 3. Marine paint according to one of claims 1 and 2, characterized in that the acrylic polymer contains 15 to 80% by weight units of monomer 3 and 20 to 85% by weight units of monomer 1, and optionally up to 60% by weight units of monomer 2. 4 Acrylic terpolymer, characterized in that it contains units of the following monomers where R' = C 1-4 alkyl, and 2. triorganotinnmetakrylater eller -akrylater, hvor R = H eller CH3, R" er CH3 eller C2Hs, n = 1 eller 2.2. triorganotin methacrylates or acrylates, where R = H or CH3, R" is CH3 or C2Hs, n = 1 or 2. 5. Akrylterpolymer ifølge krav 4, karakterisert ved at den inneholdler enheter av: 1. metylmetakrylat, 2. tributyltinnmetakrylat og 3. 2-metoksyetylakrylat.5. Acrylic terpolymer according to claim 4, characterized in that it contains units of: 1. methyl methacrylate, 2. tributyl tin methacrylate and 3. 2-methoxyethyl acrylate. 6. Akrylterpolymer ifølge et av kravene 4 og 5, karakterisert ved at den inneholder 20 til 85 vekt% enheter av monomer 1, opp til 60 vekt% enheter av monomer 2 og 15 til 80 vekt% enheter av monomer 3.6. Acrylic terpolymer according to one of claims 4 and 5, characterized in that it contains 20 to 85% by weight units of monomer 1, up to 60% by weight units of monomer 2 and 15 to 80% by weight units of monomer 3.
NO840005A 1984-01-02 1984-01-02 MARIN PAINTING INCLUDING A MOVIE-forming ACRYLIC POLYMER AND AN ACRYLIC POLYMER FOR USE IN THE PAINTING. NO156493C (en)

Priority Applications (19)

Application Number Priority Date Filing Date Title
NO840005A NO156493C (en) 1984-01-02 1984-01-02 MARIN PAINTING INCLUDING A MOVIE-forming ACRYLIC POLYMER AND AN ACRYLIC POLYMER FOR USE IN THE PAINTING.
DK610484A DK172317B1 (en) 1984-01-02 1984-12-19 Marine paints and acrylic polymers for use in marine paints
GB08432163A GB2152947B (en) 1984-01-02 1984-12-20 Marine coating and certain new terpolymers for use therein
NL8403867A NL192114C (en) 1984-01-02 1984-12-20 Method for coating ships and the like with an acrylic polymer-containing coating.
IT49342/84A IT1178318B (en) 1984-01-02 1984-12-21 COMPOSITION FOR MARINE COATINGS AND ACRYLIC TERPOLYMERS TO BE USED IN THEM
DE3446971A DE3446971C2 (en) 1984-01-02 1984-12-21 Use of a film-forming acrylic polymer as a ship's paint
FR8419796A FR2557585B1 (en) 1984-01-02 1984-12-26 UNDERWATER PAINTS AND NEW TRIPOLYMERS INCLUDING THEIR COMPOSITION
AU37147/84A AU570530B2 (en) 1984-01-02 1984-12-27 Acrylic anti-fouling marine coatings
GR82615A GR82615B (en) 1984-01-02 1984-12-28 Marine coating and certain new terpolymers for use therein
ES539165A ES8607995A1 (en) 1984-01-02 1984-12-28 Marine coating and certain new terpolymers for use therein
BR8406783A BR8406783A (en) 1984-01-02 1984-12-28 COATING FOR MARITIME MATERIAL AND ACRYLIC TERPOLYMER
CA000471098A CA1260186A (en) 1984-01-02 1984-12-28 Marine coating and certain new terpolymers for use therein
BE0/214280A BE901426A (en) 1984-01-02 1984-12-28 MARINE PAINT AND NEW TERPOLYMERS FOR USE THEREIN.
JP59274997A JPS60158211A (en) 1984-01-02 1984-12-28 Paint for boat and ship
PT79776A PT79776B (en) 1984-01-02 1984-12-28 Process for preparing marine coating and certain new terpolymers for use therein
SE8406666A SE465574B (en) 1984-01-02 1984-12-28 MARIN FAERG AND ACRYLIC POLYMER BEFORE USING THERE
KR1019840008526A KR930008744B1 (en) 1984-01-02 1984-12-29 Acrylic anti-fouling marine coatings
SG799/90A SG79990G (en) 1984-01-02 1990-09-29 Marine coatings,production and use thereof
HK948/92A HK94892A (en) 1984-01-02 1992-11-26 Marine coatings production and use thereof

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NO840005A NO156493C (en) 1984-01-02 1984-01-02 MARIN PAINTING INCLUDING A MOVIE-forming ACRYLIC POLYMER AND AN ACRYLIC POLYMER FOR USE IN THE PAINTING.

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NO840005L NO840005L (en) 1985-07-03
NO156493B true NO156493B (en) 1987-06-22
NO156493C NO156493C (en) 1987-09-30

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JP (1) JPS60158211A (en)
KR (1) KR930008744B1 (en)
AU (1) AU570530B2 (en)
BE (1) BE901426A (en)
BR (1) BR8406783A (en)
CA (1) CA1260186A (en)
DE (1) DE3446971C2 (en)
DK (1) DK172317B1 (en)
ES (1) ES8607995A1 (en)
FR (1) FR2557585B1 (en)
GB (1) GB2152947B (en)
GR (1) GR82615B (en)
HK (1) HK94892A (en)
IT (1) IT1178318B (en)
NL (1) NL192114C (en)
NO (1) NO156493C (en)
PT (1) PT79776B (en)
SE (1) SE465574B (en)
SG (1) SG79990G (en)

Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4121811A1 (en) * 1991-07-02 1993-01-07 Roehm Gmbh METHOD FOR PRODUCING POLYALKYL METHACRYLATE MACROMONOMERS AND THE USE THEREOF FOR PRODUCING COMB POLYMERS
DK137491D0 (en) * 1991-07-19 1991-07-19 Hempel Skibsfarve Fab S J PAINT COMPOSITION
JP3196361B2 (en) * 1991-12-25 2001-08-06 日立化成工業株式会社 Resin composition for paint and antifouling paint for underwater structures
US5288828A (en) * 1993-03-08 1994-02-22 The Sherwin-Williams Company Dispersant polymers
FR2729965B1 (en) * 1995-01-26 2000-05-19 France Etat SELF-POLISHING ANTI-FOULING PAINTS
ES2138788T3 (en) * 1996-11-07 2000-01-16 Witco Gmbh PROCEDURE FOR THE PREPARATION OF POLYMERIC BINDING AGENTS AND THEIR USE FOR ANTI-SOILING PAINT SYSTEMS.
EP0841353A1 (en) * 1996-11-07 1998-05-13 Witco GmbH Process for the preparation of polymeric binders and their application as antifouling paint
EP1308484A1 (en) 2001-10-30 2003-05-07 Sigma Coatings B.V. Use of silylesters of rosin in self-polishing antifouling paints
EP1475415A1 (en) 2003-05-07 2004-11-10 SigmaKalon Services B.V. Silyl esters, their use in binder systems and paint compositions and a process of production thereof
FR2930778A1 (en) 2008-04-30 2009-11-06 Bluestar Silicones France Soc ARTICLE HAVING ANTIFOULING PROPERTIES AND INTENDED FOR USE IN AQUATIC APPLICATIONS, IN PARTICULAR MARINE
US9744527B2 (en) 2008-05-29 2017-08-29 Bluestar Silicones France Sas Article having antifouling properties for aquatic and particularly sea use
EP2297254B1 (en) 2008-05-29 2014-08-20 Bluestar Silicones France Article having antifouling properties for aquatic and particularly sea use
EP2348077B1 (en) 2010-01-26 2013-04-03 Jotun A/S Antifouling composition
JP2013534543A (en) 2010-06-04 2013-09-05 ヨツン エーエス Antifouling composition
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
KR20150104114A (en) 2012-12-19 2015-09-14 요툰 에이/에스 Silyl ester copolymer
WO2014096572A1 (en) 2012-12-20 2014-06-26 Bluestar Silicones France Sas Article with antifouling properties, intended for aquatic uses and, in particular, for marine uses
FR2999980A1 (en) 2012-12-20 2014-06-27 Bluestar Silicones France ARTICLE HAVING ANTIFOULING PROPERTIES AND INTENDED FOR USE IN AQUATIC APPLICATIONS, IN PARTICULAR MARINE
FR3014107A1 (en) 2013-12-03 2015-06-05 Bluestar Silicones France ARTICLE HAVING ANTIFOULING PROPERTIES AND INTENDED FOR USE IN AQUATIC APPLICATIONS, IN PARTICULAR MARINE
EP2902452A1 (en) 2014-01-31 2015-08-05 Jotun A/S Antifouling composition
EP2902453A1 (en) 2014-01-31 2015-08-05 Jotun A/S Antifouling Composition
EP3078715B1 (en) 2015-04-09 2018-06-06 Jotun A/S Antifouling composition
CN108070055B (en) 2016-11-11 2022-10-04 佐敦公司 Antifouling composition
EP3538614A1 (en) 2016-11-11 2019-09-18 Jotun A/S Antifouling composition
JP7178167B2 (en) 2016-11-11 2022-11-25 ヨトゥン アーエス antifouling composition
GB201718891D0 (en) * 2017-11-15 2017-12-27 Jotun As Antifouling composition
CN112771090A (en) * 2018-09-26 2021-05-07 三菱化学株式会社 Copolymer for inhibiting protein adhesion, method for producing copolymer, resin modifier, molding material, composition containing copolymer, coating film, and article

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB988171A (en) * 1960-04-14 1965-04-07 Vinyl Products Ltd Improvements in or relating to thermosetting resin compositions
GB1292953A (en) * 1968-10-22 1972-10-18 Hydron Ltd Coating compositions based on acrylate and/or methacrylate copolymers
DE1952721A1 (en) * 1968-10-22 1970-09-10 Hydron Ltd Coating agent for use on humans or animals
GB1457590A (en) * 1974-04-03 1976-12-08 Int Paint Co Marine paint
JPS55164261A (en) * 1979-06-08 1980-12-20 Chugoku Toryo Kk Antifouling coating material
EP0051930B1 (en) * 1980-10-30 1985-04-24 INTERNATIONAL PAINT public limited company Marine paint
JPS5776012A (en) * 1980-10-31 1982-05-12 Mitsubishi Rayon Co Ltd Preparation of high polymeric acrylic resin containing triorganotin
JPS58118868A (en) * 1982-01-07 1983-07-15 Nippon Paint Co Ltd Resin composition for antifouling paint
JPS58180565A (en) * 1982-04-16 1983-10-22 Nippon Oil & Fats Co Ltd Antifouling coating

Also Published As

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DE3446971C2 (en) 1995-09-28
KR850004976A (en) 1985-08-19
GR82615B (en) 1985-05-02
ES539165A0 (en) 1986-01-01
GB8432163D0 (en) 1985-01-30
JPS60158211A (en) 1985-08-19
ES8607995A1 (en) 1986-01-01
HK94892A (en) 1992-12-04
NL192114C (en) 1997-02-04
SE8406666D0 (en) 1984-12-28
SG79990G (en) 1990-11-23
BR8406783A (en) 1985-10-22
IT8449342A0 (en) 1984-12-21
NO156493C (en) 1987-09-30
NO840005L (en) 1985-07-03
NL8403867A (en) 1985-08-01
GB2152947B (en) 1987-09-30
SE465574B (en) 1991-09-30
PT79776B (en) 1987-01-05
PT79776A (en) 1985-01-01
KR930008744B1 (en) 1993-09-13
SE8406666L (en) 1985-07-03
FR2557585A1 (en) 1985-07-05
GB2152947A (en) 1985-08-14
AU570530B2 (en) 1988-03-17
DK172317B1 (en) 1998-03-16
DK610484D0 (en) 1984-12-19
BE901426A (en) 1985-06-28
DE3446971A1 (en) 1985-07-11
IT1178318B (en) 1987-09-09
CA1260186A (en) 1989-09-26
FR2557585B1 (en) 1993-10-08
AU3714784A (en) 1985-07-11
NL192114B (en) 1996-10-01
DK610484A (en) 1985-07-03

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