CN104053690A - Method for producing vinyl polymer and resin composition for water-based antifouling paint containing vinyl polymer - Google Patents
Method for producing vinyl polymer and resin composition for water-based antifouling paint containing vinyl polymer Download PDFInfo
- Publication number
- CN104053690A CN104053690A CN201380005769.6A CN201380005769A CN104053690A CN 104053690 A CN104053690 A CN 104053690A CN 201380005769 A CN201380005769 A CN 201380005769A CN 104053690 A CN104053690 A CN 104053690A
- Authority
- CN
- China
- Prior art keywords
- methyl
- acrylate
- monomer mixture
- acid
- based polymer
- 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.)
- Granted
Links
Classifications
-
- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/04—Polymers provided for in subclasses C08C or C08F
- C08F290/046—Polymers of unsaturated carboxylic acids or derivatives thereof
-
- 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
- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/06—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
Landscapes
- 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)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Provided is a method for producing a vinyl polymer comprising step (1) for polymerization of a monomer mixture (M1) comprising a carboxyl group-containing ethylenic unsaturated monomer (a1) and step (2) for polymerization of a monomer mixture (M2) comprising a divalent metal-containing ethylenic unsaturated monomer (a2), and in the method for producing a vinyl polymer, the monomer mixture (M1) and/or the monomer mixture (M2) comprise a macromonomer (a3) having radical polymerizable groups, and either the monomer mixture (M2) is added to the polymerization reaction solution after step (1) and then step (2) is performed, or the monomer mixture (M1) is added to the polymerization reaction solution after step (2) and then step (1) is performed.
Description
Technical field
The present invention relates to have the water-based antifouling paint resin combination of didirtresistance.In addition, also relate to the manufacture method that is suitable for the vinyl based polymer for obtaining water-based antifouling paint resin combination.
Background technology
Antifouling paint is the coating of coating underwater structures, fishing net, hull bottom etc. for object that adheres to that prevents marine creature and seaweeds.The film being obtained by antifouling paint is brought into play anti-fouling effect by antifouling drug ingredient contained in coating in marine stripping.Known have various antifouling paints, for example, by the film that has used the disintegration-type antifouling paint of rosin series compound to obtain, impregnated in for a long time marine in the situation that, and dissolved element tails off at leisure, dissolved element does not become many.Therefore, the effect of antifouling medicine reduces, and then coated surface concave-convex surface, therefore, prevents that the effect of the biological attachment such as marine creature from significantly reducing.
On the other hand, also known have water-disintegrable from polishing type antifouling paint.By the film obtaining from polishing type antifouling paint, in seawater, film coated surface is carried out Surface Renewal (from polishing) lentamente, and antifouling composition always exposes in film coated surface, therefore, can bring into play long-term anti-fouling effect.; in these coating, contain the various organic solvents such as a large amount of dimethylbenzene, alcohol; consider from VOC (Volatile Organic Compound, volatile organic compounds) problem in recent years, the water-based antifouling paint that replaces them has been carried out to various research.
As from polishing type water-based antifouling paint, for example, in patent documentation 1, record the water-based antifouling paint resin combination that is dispersed with the polymkeric substance that contains divalent metal in water.
In patent documentation 2, record the water-based paint compositions that contains the graft copolymer that comprises the macromonomer that is connected to main chain end.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2010-1395 communique
Patent documentation 2: the flat 10-500721 communique of Japanese Unexamined Patent Application Publication
Summary of the invention
Invent problem to be solved
, the water-based antifouling paint of recording in patent documentation 1 is the material that ethylene unsaturated monomer is polymerized by common free radical polymerisation process with the multipolymer using in resin combination, is random copolymers.Although the film being obtained by the antifouling paint that comprises such random copolymers has from polishability, hardness is low, and water tolerance is also insufficient, expects further improvement.
In addition, about in patent documentation 2 record coating composition, the film being obtained by this coating composition do not have utilize hydrolysis from polishability, do not show didirtresistance.
The object of the present invention is to provide a kind of water-based antifouling paint resin combination, described water-based antifouling paint resin combination is the antifouling paint resin combination that has solved the problems referred to above and suppressed organic solvent content, the film being obtained by this resin combination shows good didirtresistance, water tolerance excellence, has sufficient hardness.In addition, another object of the present invention is to provide a kind of vinyl based polymer and manufacture method thereof, described vinyl based polymer is suitable for for obtaining such water-based antifouling paint resin combination.
For solving the method for problem
Comprise according to the manufacture method of the vinyl based polymer of a mode of the present invention: the operation (1) that makes to comprise monomer mixture (M1) polymerization of the ethylene unsaturated monomer (a1) that contains carboxyl, and make to comprise the operation (2) of monomer mixture (M2) polymerization of the ethylene unsaturated monomer (a2) that contains divalent metal, at least either party in aforementioned monomer mixture (M1) and monomer mixture (M2) comprises the macromonomer (a3) with free-radical polymerised group, add monomer mixture (M2) to the polymerization liquid after operation (1) thus carry out operation (2), or add monomer mixture (M1) to the polymerization liquid after operation (2) thus carry out operation (1).
It is the vinyl based polymer obtaining by above-mentioned manufacture method according to the vinyl based polymer of another way of the present invention.
To make above-mentioned vinyl based polymer be dispersed in the resin combination obtaining in the dispersion medium that comprises water according to the water-based antifouling paint resin combination of another way of the present invention.
The effect of invention
According to the embodiment of the present invention, a kind of antifouling paint resin combination can be provided, described antifouling paint can form demonstration good didirtresistance, water tolerance excellence, have the film of sufficient hardness with resin combination, and has suppressed the content of organic solvent.According to another embodiment of the present invention, can provide the vinyl based polymer and the manufacture method thereof that are suitable for for obtaining this water-based antifouling paint resin combination.
Embodiment
The manufacture method of vinyl based polymer according to the embodiment of the present invention comprises the operation (1) of monomer mixture (M1) polymerization that makes to comprise the ethylene unsaturated monomer (a1) that contains carboxyl and makes to comprise the operation (2) of monomer mixture (M2) polymerization of the ethylene unsaturated monomer (a2) that contains divalent metal.Below, each operation is described.
< operation (1) >
Operation (1) is the operation that makes to comprise monomer mixture (M1) polymerization of the ethylene unsaturated monomer (a1) that contains carboxyl.
[ethylene unsaturated monomer (a1) that contains carboxyl]
As the ethylene unsaturated monomer that contains carboxyl (a1), can enumerate monoprotic acid or the dicarboxylic acid monomer classes such as such as methacrylic acid, vinylformic acid, β-crotonic acid, vinyl benzoic acid, fumaric acid, methylene-succinic acid, toxilic acid, citraconic acid, monomethyl maleate, ethyl maleate, butyl maleate, single-ethylhexyl maleate, monomethyl itaconate, methylene-succinic acid mono ethyl ester, monobutyl itaconate, methylene-succinic acid mono octyl ester, monomethyl fumarate, monomethyl ester, fumaric acid mono—n—butylester, fumaric acid mono octyl ester, citraconic acid mono ethyl ester, tetrahydrophthalic acid monohydroxy ethyl (methyl) acrylate, tetrahydrophthalic acid monohydroxy propyl group (methyl) acrylate, tetrahydrophthalic acid monohydroxy butyl (methyl) acrylate, phthalic acid monohydroxy ethyl (methyl) acrylate, phthalic acid monohydroxy propyl group (methyl) acrylate, mono succinate hydroxyethyl (methyl) acrylate, mono succinate hydroxypropyl (methyl) acrylate, toxilic acid monohydroxy ethyl (methyl) acrylate, the diprotic acid of the representative such as toxilic acid monohydroxy propyl group (methyl) acrylate or monoesters class of anhydride monomers etc.
The ethylene unsaturated monomer (a1) that contains carboxyl is one or more in them of choice for use suitably.Wherein, from easily and the good viewpoint of the water tolerance of other ethylene unsaturated monomer copolymerization, the film that obtained with resin combination by the antifouling paint that comprises the vinyl based polymer obtaining, preferable methyl vinylformic acid, vinylformic acid.
About the content of the ethylene unsaturated monomer that contains carboxyl (a1), in the whole monomers (total amount of the monomer of the monomer of monomer mixture (M1) and monomer mixture (M2)) that use in the manufacture of vinyl based polymer according to the embodiment of the present invention, preferably contain 1～30 quality %, more preferably 3～15 quality %.If the content of the ethylene unsaturated monomer that contains carboxyl (a1) is more than 1 quality %, antifouling paint is good with the storage stability of resin combination.If the tendency that this content below 30 quality %, exists the water tolerance of the film being obtained by antifouling paint resin combination in seawater to improve.
[demonomerization (a1) monomer in addition in monomer mixture (M1)]
Monomer mixture (M1) can comprise the monomer in addition of ethylene unsaturated monomer (a1) that contains carboxyl, as this monomer, can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, the positive lauryl of (methyl) vinylformic acid, the positive stearyl ester of (methyl) vinylformic acid, (methyl) cyclohexyl acrylate, (methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) isobornyl acrylate etc. has (methyl) acrylate of alkyl, (methyl) acrylate that (methyl) vinylformic acid 2-methoxyl group ethyl ester, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid phenoxy ethyl etc. contain alkoxyl group or phenoxy group, (methyl) acrylate that (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid glyceryl ester etc. contain hydroxyl, the ethene base system monomer that maleic anhydride, itaconic anhydride etc. contain anhydride group, (methyl) glycidyl acrylate, α-ethylacrylate glycidyl ester, (methyl) vinylformic acid 3, the ethene base system monomer that 4-epoxy butyl ester etc. contains epoxy group(ing), (methyl) vinylformic acid dimethylamino ethyl ester, (methyl) vinylformic acid diethylamino ethyl ester etc. contain amino (methyl) acrylic ester ethene base system monomer, the ethene base system monomer that (methyl) acrylamide, the N-tertiary butyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-methoxymethyl (methyl) acrylamide, N-butoxymethyl (methyl) acrylamide, diacetone-acryloamide(DAA), maleinamide, maleimide etc. contain amide group, the heterocycles such as vinyl pyrrolidone, vinyl pyridine, vinylcarbazole are alkaline monomer, the ethene base system monomers such as vinylbenzene, Vinyl toluene, alpha-methyl styrene, vinyl cyanide, methacrylonitrile, vinyl-acetic ester, propionate, the end alkoxy group allylation polyether monomers such as methoxyl group ethylene glycol allyl ethers, methoxy poly (ethylene glycol) allyl ethers, methoxyl group polypropylene glycol allyl ethers, butoxy polyoxyethylene glycol allyl ethers, butoxy polypropylene glycol allyl ethers, methoxy poly (ethylene glycol)-polypropylene glycol allyl ethers, butoxy polyethylene glycol-propylene glycol allyl ethers, ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, 1, 4-butyleneglycol two (methyl) acrylate, 1, 6-hexylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1, 9-nonanediol two (methyl) acrylate, 1, 10-decanediol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, allyl methacrylate(AMA), triallyl cyanurate, diallyl maleate, the polyfunctional monomers such as polypropylene glycol diallyl ether.Monomer mixture (M1) contained, suitably one kind or two or more in them of choice for use of the ethylene unsaturated monomer (a1) that contains carboxyl monomer in addition.
Wherein, " (methyl) acrylate " meaning is " acrylate and/or methacrylic ester "; " (methyl) vinylformic acid " meaning is " vinylformic acid and/or methacrylic acid "; " (methyl) acryl " meaning is " acryl and/or methacryloyl "; " (methyl) vinyl cyanide " meaning is " vinyl cyanide and/or methacrylonitrile ", and " (methyl) acrylamide " meaning is " acrylamide and/or Methacrylamide ".
About monomer mixture (M1) contained, the ethylene unsaturated monomer (a1) that contains carboxyl monomer in addition, wherein, from the viewpoint good with the copolymerizable of other ethene base system monomers, preferably (methyl) acrylate.
< operation (2) >
Operation (2) is the operation that makes to comprise monomer mixture (M2) polymerization of the ethylene unsaturated monomer (a2) that contains divalent metal.
[ethylene unsaturated monomer (a2) that contains divalent metal]
As the ethylene unsaturated monomer that contains divalent metal (a2), can use the ethylene unsaturated monomer that contains divalent metal (a2b) shown in the ethylene unsaturated monomer that contains divalent metal (a2a) or the following general formula (1) with 2 unsaturated groups.
CH
2=C (R
1)-COO-M-R
2formula (1)
(in formula (1), M represents divalent metal, R
1represent hydrogen atom or methyl, R
2represent organic acid residue.)
As the contained divalent metal of the ethylene unsaturated monomer that contains divalent metal (a2), the viewpoint from the long-term performance of the film that obtains from polishability, is preferably at least a kind of metal of the group of selecting free Mg, Ca, Zn and Cu composition.From the transparent viewpoint of the vinyl based polymer that obtains, be preferably at least one metal that is selected from Mg, Ca, Zn, more preferably Zn.Two or more kinds may be used for aforementioned metal.
As the ethylene unsaturated monomer that contains divalent metal (a2a) with 2 unsaturated groups, can enumerate for example Magnesium Acrylate Prepared [(CH
2=CHCOO)
2mg], magnesinm methacrylate [(CH
2=C (CH
3) COO)
2mg], calcium acrylate [(CH
2=CHCOO)
2ca], methacrylic acid calcium [(CH
2=C (CH
3) COO)
2ca], zinc acrylate resin [(CH
2=CHCOO)
2zn], zinc methacrylate [(CH
2=C (CH
3) COO)
2zn], vinylformic acid copper [(CH
2=CHCOO)
2cu], methacrylic acid copper [(CH
2=C (CH
3) COO)
2cu] etc. (methyl) vinylformic acid divalent metal-salt.Aforementioned monomer (a2a) can be as required suitably choice for use two or more.For the color of film that exists the transparency of the vinyl based polymer obtaining to uprise, obtained by the antifouling paint that comprises this vinyl based polymer resin combination becomes beautiful tendency, preferably (methyl) zinc acrylate resin.Wherein, " (methyl) vinylformic acid " meaning is " vinylformic acid " or " methacrylic acid ".
The ethylene unsaturated monomer that contains divalent metal (a2a) with 2 unsaturated groups is that the method for for example, reacting in for example organic solvent or ethylene unsaturated monomer by the ethylene unsaturated monomer (vinylformic acid, methacrylic acid) that makes inorganic metal compound and contain carboxyl obtains.The consistency excellence of the mixture that contains the ethylene unsaturated monomer that contains divalent metal (a2a) composition being obtained by preceding method and organic solvent, other monomers, can make the polymerization that comprises operation (2) easily carry out.Further preferably previous reaction is carried out under the existence of water, preferably the content of water in reactant is made as to the scope of 0.01～30 quality %.
As the R of the ethylene unsaturated monomer that contains divalent metal (a2b) shown in general formula (1)
2organic acid residue, can enumerate by monochloro acetic acid, single gifblaar poison, acetic acid, propionic acid, sad, neodecanoic acid (Versatic acid), Unimac 5680, palmitinic acid, cresotinic acid, α-naphthoicacid, β-naphthoic acid, phenylformic acid, 2,4, the derivative residues of monobasic organic acid such as 5-trichlorophenoxyacetic acid, 2,4 dichloro benzene ethoxyacetic acid, quinoline carboxylic acid, nitrobenzoic acid, nitronaphthoic acid, pyruvic acid.They can suitably be selected as required.Can prevent for a long time crackle, the film that the weather resistance of peeling off is high in order to obtain, preference as the lipid acid of carbonatoms 1～20 (aliphatic monocarboxylic acid) be residue.
Wherein, the R in general formula (1)
2organic acid residue refer to from organic acid carboxyl except remaining part deprotonation, replace this proton and carry out ionic bonding with metal M.
As the ethylene unsaturated monomer that contains divalent metal (a2b) shown in general formula (1), can enumerate for example monochloro magnesium acetate (methyl) acrylate, monochloro lime acetate (methyl) acrylate, monochloro zinc acetate (methyl) acrylate, monochloro venus crystals (methyl) acrylate; Single gifblaar poison magnesium (methyl) acrylate, single gifblaar poison calcium (methyl) acrylate, single gifblaar poison zinc (methyl) acrylate, single gifblaar poison copper (methyl) acrylate; Magnesium acetate (methyl) acrylate, lime acetate (methyl) acrylate, zinc acetate (methyl) acrylate, venus crystals (methyl) acrylate; Propionic acid magnesium (methyl) acrylate, calcium propionate (methyl) acrylate, zinc propionate (methyl) acrylate, propionic acid copper (methyl) acrylate; Sad magnesium (methyl) acrylate, calcium octoate (methyl) acrylate, zinc octoate (methyl) acrylate, cupric octoate (methyl) acrylate; Neodecanoic acid magnesium (methyl) acrylate, neodecanoic acid calcium (methyl) acrylate, zinc neodecanoate (methyl) acrylate, neodecanoic acid copper (methyl) acrylate; Unimac 5680 magnesium (methyl) acrylate, Unimac 5680 calcium (methyl) acrylate, Unimac 5680 zinc (methyl) acrylate, Unimac 5680 copper (methyl) acrylate; Magnesium palmitate (methyl) acrylate, calcium palmitate (methyl) acrylate, zinc palmitate (methyl) acrylate, copper palmitate (methyl) acrylate; Cresotinic acid magnesium (methyl) acrylate, cresotinic acid calcium (methyl) acrylate, cresotinic acid zinc (methyl) acrylate, cresotinic acid copper (methyl) acrylate; α-naphthoicacid magnesium (methyl) acrylate, α-naphthoicacid calcium (methyl) acrylate, α-naphthoicacid zinc (methyl) acrylate, α-naphthoicacid copper (methyl) acrylate; β-naphthoic acid magnesium (methyl) acrylate, β-naphthoic acid calcium (methyl) acrylate, β-naphthoic acid zinc (methyl) acrylate, β-naphthoic acid copper (methyl) acrylate; Magnesium benzoate (methyl) acrylate, calcium benzoate (methyl) acrylate, Zinc dibenzoate (methyl) acrylate, cupric benzoate (methyl) acrylate; 2,4,5-trichlorophenoxyacetic acid magnesium (methyl) acrylate, 2,4,5-trichlorophenoxyacetic acid calcium (methyl) acrylate, 2,4,5-trichlorophenoxyacetic acid zinc (methyl) acrylate, 2,4,5-trichlorophenoxyacetic acid copper (methyl) acrylate; 2,4-dichlorophenoxyacetic acid magnesium (methyl) acrylate, 2,4-dichlorophenoxyacetic acid calcium (methyl) acrylate, 2,4-dichlorophenoxyacetic acid zinc (methyl) acrylate, 2,4 dichloro benzene ethoxyacetic acid copper (methyl) acrylate; Quinoline carboxylic acid's magnesium (methyl) acrylate, quinoline carboxylic acid's calcium (methyl) acrylate, quinoline carboxylic acid's zinc (methyl) acrylate, quinoline carboxylic acid's copper (methyl) acrylate; Nitrobenzoic acid magnesium (methyl) acrylate, nitrobenzoic acid calcium (methyl) acrylate, nitrobenzoic acid zinc (methyl) acrylate, nitrobenzoic acid copper (methyl) acrylate; Nitronaphthoic acid magnesium (methyl) acrylate, nitronaphthoic acid calcium (methyl) acrylate, nitronaphthoic acid zinc (methyl) acrylate, nitronaphthoic acid copper (methyl) acrylate; Pyruvic acid magnesium (methyl) acrylate, CALCIUM PYRUVIC (methyl) acrylate, pyruvic acid zinc (methyl) acrylate, pyruvic acid copper (methyl) acrylate etc.
The ethylene unsaturated monomer (a2) that contains divalent metal can be as required suitable one kind or two or more in them of choice for use.Wherein, if use the monomer that contains zinc, the color of the film that the transparency of the vinyl based polymer obtaining uprises, obtained by the antifouling paint resin combination that comprises the vinyl based polymer obtaining smartens up, so preferably.And then from the viewpoint of the weather resistance of the film that obtains, (M of formula (1) is zinc, R more preferably to use fatty acid zinc (methyl) acrylate
2for fatty acid residue).Wherein, " (methyl) acrylate " meaning is " acrylate " or " methacrylic ester ".
The ethylene unsaturated monomer of the ethylene unsaturated monomer that contains divalent metal (a2b) shown in general formula (1) by making inorganic metal compound, contain carboxyl and corresponding to the organic acid residue R in formula (1)
2non-polymerization organic acid there is the method for reacting in the reactive diluent of polymerizability unsaturated group at thinner or ethylene unsaturated monomers etc. such as organic solvents and obtain.
Wherein, as the ethylene unsaturated monomer that contains divalent metal (a2), from the film that can long term maintenance obtains from polishability, can obtain the viewpoint of good didirtresistance, preferably and by aforementioned monomer (a2a) and aforementioned monomer (a2b).Be more preferably as (methyl) zinc acrylate resin of aforementioned monomer (a2a) with as fatty acid zinc (methyl) acrylate of aforementioned monomer (a2b), (M of formula (1) is zinc, R
2for fatty acid residue) combination.
Also by aforementioned monomer (a2a) and aforementioned monomer (a2b) in the situation that, in monomer mixture (M2) (being in whole monomers of monomer mixture (M1) and monomer mixture (M2)), the mol ratio (a2a/a2b) of aforementioned monomer (a2a) and aforementioned monomer (a2b) is preferably in 10/90～90/10 scope, more preferably in 20/80～80/20 scope, most preferably in 30/70～70/30 scope.If this ratio (a2a/a2b), below 90/10, can obtain the film of resistance to cracking line, adaptation excellence, if more than 10/90, there is the tendency from polishability of the film can long term maintenance obtaining.
In addition the ethylene unsaturated monomer of the monomer mixture that, contains aforementioned monomer (a2a) and aforementioned monomer (a2b) by making inorganic metal compound, contain carboxyl and corresponding to the organic acid residue R in formula (1)
2non-polymerization organic acid and the acquisitions such as aforementioned method of similarly reacting in the thinners such as organic solvent or ethylene unsaturated monomer isoreactivity thinner.
Now, preferably non-polymerization organic acid content is 0.01～3 times mole with respect to inorganic metal compound.More preferably 0.01～0.95 times mole, more preferably 0.1～0.7 times mole.If non-polymerization organic acid content is more than 0.01 times mole, in the manufacturing process of the monomer mixture that comprises aforementioned monomer (a2a) and aforementioned monomer (a2b), separating out of solid is suppressed, meanwhile, the film obtaining become better from polishability, resistance to cracking line.If below 3 times moles, there is the tendency that can longer-term maintains the didirtresistance of the film obtaining.
The content of the ethylene unsaturated monomer (a2) that contains divalent metal, preferably in the manufacture of vinyl based polymer according to the embodiment of the present invention in monomer (total amount of the monomer of the amount of monomer of monomer mixture (M1) and monomer mixture (M2)) used, in the scope of 1～40 quality %, more preferably in the scope of 7～25 quality %.If the content of the ethylene unsaturated monomer that contains divalent metal (a2) is more than 1 quality %, the film obtaining become good from polishability for a long time.If this content is below 40 quality %, the tendency that exists the balance of the adaptation of the antifouling paint storage stability of resin combination, film, water tolerance in seawater and hardness and resistance to cracking to improve.
As monomer mixture (M2) contained, the ethylene unsaturated monomer (a2) that contains divalent metal monomer in addition, can use monomer contained with monomer mixture (M1), that monomer (a1) monomer is in addition same, from the viewpoint of copolymerizable, preferably (methyl) acrylate.Viewpoint from antifouling paint with the storage stability of resin combination, the ethylene unsaturated monomer that does not contain carboxyl in preferred monomers mixture (M2).
[macromonomer (a3)]
In manufacture method according to the embodiment of the present invention, at least either party in aforementioned monomer mixture (M1) and aforementioned monomer mixture (M2) comprises the macromonomer (a3) with free-radical polymerised group.By the monomer mixture polymerization that makes to comprise macromonomer (a3), can not make the resistance to cracking of the film obtaining worsen, can improve hardness of film, further can also improve water tolerance.
The number-average molecular weight (Mn) of the polystyrene conversion of passing through gel permeation chromatography of macromonomer (a3) is preferably in 200～16000 scope, more preferably in 300～15000 scope, scope below 10000 is suitable, further preferably in 400～8000 scope, in 500～6000 scope.If the Mn of macromonomer (a3) is more than 200, further, if more than 300, the tendency that the hardness of the film that existence obtains, the water tolerance in seawater and adaptation improve.If below 16000, further, if below 15000, there is the tendency of the storage stability raising of antifouling paint resin combination in the Mn of macromonomer (a3).
In the manufacture of vinyl based polymer according to the embodiment of the present invention in whole monomers (total amount of the monomer of the monomer of monomer mixture (M1) and monomer mixture (M2)) used, the content of macromonomer (a3) is preferably in the scope of 1～35 quality %, more preferably in the scope of 5～25 quality %.If the content of macromonomer (a3) is more than 1 quality %,, below 35 quality %, there is the tendency of storage stability raising in the tendency that the hardness of the film that existence obtains, the water tolerance in seawater and adaptation improve if.
As macromonomer (a3), can use to there is the main chain shown in following formula, there is the monomer of terminal double link as free-radical polymerised group:
-(C(X)(COOR)-CH
2)
n-H
(in formula, X is hydrogen atom or methyl, and R is hydrogen atom, silyl, replacement or unsubstituted alkyl, replacement or unsubstituted cycloalkyl or replacement or unsubstituted aryl, the integer that n is 1～150)
N is preferably 3～150.The carbonatoms of the alkyl of R is preferably 1～12.The silyl of R is preferably the trialkylsilkl such as tributyl silyl, triisopropyl silyl.Here, replacing the meaning is to have the substituting groups such as epoxy group(ing), hydroxyl, cyano group, amino, carboxyl, and substituted cycloalkyl and substituted aryl can also have alkyl as substituting group except these substituting groups, and the carbonatoms of this alkyl is preferably 1～6.
As macromonomer (a3), can use the macromonomer at the end of the vinyl based polymer from ethene base system monomer shown in following formula (A) with (methyl) acryl.
[changing 1]
In formula (A), X, Y are hydrogen atom or methyl independently of one another, R
nbe hydrogen atom, silyl, replacement or unsubstituted alkyl, replacement or unsubstituted cycloalkyl or replacement or unsubstituted aryl independently of one another, R ' is the group with the alkylidene group of carbonatoms 1～12, the integer that n is 1～150.N is preferably 3～150.R
nthe carbonatoms of alkyl be preferably 1～12.R
nsilyl be preferably the trialkylsilkl such as tributyl silyl, triisopropyl silyl.Here, replacing the meaning is to have the substituting groups such as epoxy group(ing), hydroxyl, cyano group, amino, carboxyl, and substituted cycloalkyl and substituted aryl can also have alkyl as substituting group except these substituting groups, and the carbonatoms of this alkyl is preferably 1～6.
As the macromonomer shown in formula (A), for example can be by make ethylene unsaturated monomer polymerization under the existence of chain-transfer agent with carboxyl, synthetic end has the prepolymer of carboxyl, then, make the carboxyl of this prepolymer and glycidyl methacrylate generation addition reaction and obtain, but being not particularly limited.
As macromonomer (a3), can use the end shown in following formula (B) to there is α, the macromonomer of β-ethene unsaturated group.
[changing 2]
In formula (B), Z is hydrogen atom or methyl, and R is hydrogen atom, silyl, replacement or unsubstituted alkyl, replacement or unsubstituted cycloalkyl or replacement or unsubstituted aryl independently of one another, the integer that n is 1～150.N is preferably more than 2, more preferably more than 3, is preferably in addition below 149.The carbonatoms of the alkyl of R is preferably 1～12.The silyl of R is preferably the trialkylsilkl such as tributyl silyl, triisopropyl silyl.Here, replacing the meaning is to have the substituting groups such as epoxy group(ing), hydroxyl, cyano group, amino, carboxyl, and substituted cycloalkyl and substituted aryl can also have alkyl as substituting group except these substituting groups, and the carbonatoms of this alkyl is preferably 1～6.
As the macromonomer shown in formula (B), for example, can obtain by making ethylene unsaturated monomer carry out radical polymerization at 150～350 DEG C.
In addition, the macromonomer shown in formula (B) for example can make ethylene unsaturated monomer obtain by CCTP method (the chain transfer polymerization method of the catalyzer) polymerization that uses cobalt complex.
As cobalt complex, for example, can use the cobalt complex shown in following formula.For example, can use the cobalt complex of recording in No. 3587530 communique of Japanese Patent, Japanese Patent Publication 6-23209 communique, Japanese Patent Publication 7-35411 communique, USP45269945 communique, USP4694054 communique, USP4837326 communique, USP4886861 communique, USP5324879 communique, WO95/17435 communique, the flat 9-510499 communique of Japanese Unexamined Patent Application Publication etc.
[changing 3]
(in formula, R
1～R
4be alkyl, cycloalkyl or aryl independently of one another, X is F atom, Cl atom, Br atom, OH base, alkoxyl group, aryloxy, alkyl or aryl independently of one another.〕
Particularly, can enumerate two (boron difluoro dimethyl two oxyimino group hexanaphthenes) cobalts (II), two (boron difluoro dimethyl glyoxime root closes) cobalt (II), two (boron difluorodiphenyl base glyoxime root closes) cobalt (II), cobalt (II) complex compound of adjacent imino-oxyimino compound, cobalt (II) complex compound of four azepine tetraalkyl ring 14 carbon tetraenes, N, N '-bis-(salicylidene) second diamino cobalt (II) complex compound, cobalt (II) complex compound of dialkyl group diaza dioxo dialkyl group 12 carbon diene, the cobalt complexs such as cobalt (II) porphyrin complex.
Cobalt complex is one or more in them of choice for use suitably.Wherein, preferably can stable existence in polymerization, in ethylene unsaturated monomer high two (boron difluorodiphenyl base glyoxime root closes) cobalt (the II) (R of solvability
1～R
4: phenyl, X:F atom).
The content of cobalt complex is preferably 20 to 350ppm with respect to the ethylene unsaturated monomer 100g using in order to obtain macromonomer (a3).If the content of cobalt complex is lower than 20ppm, the reduction of molecular weight easily becomes insufficient, if exceed 350ppm, the macromonomer (a3) obtaining becomes easily painted.
The ethylene unsaturated monomer using during as manufacture macromonomer (a3), can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, the positive lauryl of (methyl) vinylformic acid, the positive stearyl ester of (methyl) vinylformic acid, (methyl) cyclohexyl acrylate, (methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) isobornyl acrylate, 2-methoxy ethyl (methyl) acrylate, 2-ethoxyethyl group (methyl) acrylate, (methyl) acrylate such as phenoxy group ethyl (methyl) acrylate, (methyl) acrylate that 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, 4-hydroxybutyl (methyl) acrylate, glycerine (methyl) acrylate etc. contain hydroxyl, (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl hexahydrophthalic acid, 2-(methyl) acryloxy propyl group hexahydrophthalic acid, 2-(methyl) acryloxy ethyl phthalic acid, 2-(methyl) acryloxy propyl group phthalic acid, 2-(methyl) acryloxy ethyl toxilic acid, 2-(methyl) acryloxy propyl group toxilic acid, 2-(methyl) acryloxy ethyl succsinic acid, 2-(methyl) acryloxy propyl group succsinic acid, β-crotonic acid, fumaric acid, toxilic acid, methylene-succinic acid, monomethyl maleate, the ethene base system monomer that monomethyl itaconate etc. contain carboxyl, the ethene base system monomer that maleic anhydride, itaconic anhydride etc. contain anhydride group, (methyl) glycidyl acrylate, α-ethylacrylate glycidyl ester, (methyl) vinylformic acid 3, the ethene base system monomer that 4-epoxy butyl ester etc. contains epoxy group(ing), dimethyl aminoethyl (methyl) acrylate, diethylamino ethyl (methyl) acrylate etc. contain amino (methyl) acrylic ester ethene base system monomer, the ethene base system monomer that (methyl) acrylamide, the N-tertiary butyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-methoxymethyl (methyl) acrylamide, N-butoxymethyl (methyl) acrylamide, diacetone-acryloamide(DAA), maleinamide, maleimide etc. contain amide group, the heterocycles such as vinyl pyrrolidone, vinyl pyridine, vinylcarbazole are the ethene base system monomers such as alkaline monomer, vinylbenzene, Vinyl toluene, alpha-methyl styrene, vinyl cyanide, methacrylonitrile, vinyl-acetic ester, propionate, the end alkoxy group allylation polyether monomers such as methoxyl group ethylene glycol allyl ethers, methoxy poly (ethylene glycol) allyl ethers, methoxyl group polypropylene glycol allyl ethers, butoxy polyoxyethylene glycol allyl ethers, butoxy polypropylene glycol allyl ethers, methoxy poly (ethylene glycol)-polypropylene glycol allyl ethers, butoxy polyethylene glycol-propylene glycol allyl ethers, ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, 1, 4-butyleneglycol two (methyl) acrylate, 1, 6-hexylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1, 9-nonanediol two (methyl) acrylate, 1, 10-decanediol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, allyl methacrylate(AMA), triallyl cyanurate, diallyl maleate, the polyfunctional monomers such as polypropylene glycol diallyl ether.Suitably choice for use is one kind or two or more for they.
Wherein, " (methyl) acrylate " meaning is " acrylate and/or methacrylic ester "; " (methyl) vinylformic acid " meaning is " vinylformic acid and/or methacrylic acid "; " (methyl) acryl " meaning is " acryl and/or methacryloyl ", and " (methyl) acrylamide " meaning is " acrylamide and/or Methacrylamide ".
As the manufacture method of macromonomer (a3), for example, can apply the known polymerization processs such as suspension polymerization, mass polymerization, solution polymerization process, emulsion polymerization.Wherein, preferably after polymerization by filtering, washing, dehydration, the dry suspension polymerization that can easily obtain the macromonomer (a3) as solid particles.
[manufacture of vinyl based polymer]
The vinyl based polymer of embodiments of the present invention is by making the operation (1) of monomer mixture (M1) polymerization and the operation (2) of monomer mixture (M2) polymerization being obtained.Now, at least either party in monomer mixture (M1) and monomer mixture (M2) comprises macromonomer (a3).In the polymerization liquid obtaining by an operation in operation (1) and operation (2), add by the monomer mixture of another operation polymerization, carry out polymerization.By carrying out such polymerization technique, the vinyl based polymer obtaining becomes segmented copolymer.The water tolerance of the film obtaining like this, and hardness improve.
The polymerization of operation (1) and operation (2) can be used known polymerization starter to be undertaken by known method.The viewpoint of the molecular weight of the vinyl based polymer obtaining from control, preferred solution polymerization.
The polymerization starter using in polymerization as operation (1) and operation (2), can enumerate the organo-peroxides, 2 such as such as tert-butyl hydroperoxide-2-ethylhexanoate, two-tert-butyl peroxide, lauroyl peroxide, benzoyl peroxide, the peroxidation acid tert-butyl ester, 2 '-azobis isobutyronitrile (AIBN), 2,2 '-azo two (2-methylbutyronitriles) azo based compound such as (AMBN).Polymerization starter can be used alone or two or more kinds may be used.The content of polymerization starter is not particularly limited, and can suitably set.
The polymerization temperature of operation (1) and operation (2) is preferably 60～180 DEG C.About the total of the polymerization time of operation (1) and operation (2), preferred reaction 5～14 hours.
In the polymerization of operation (1) and operation (2), can use as required known chain-transfer agent.As chain-transfer agent, can enumerate the thioglycolic acid such as the thio-alcohols such as such as n-dodecyl mercaptan, thioglycolic acid monooctyl ester ester class, α-methylstyrenedimer, terpinolene etc.They can be used alone or two or more kinds may be used.
The solvent using in polymerization as operation (1) and operation (2) is not particularly limited, and as object lesson, can enumerate the unary alcohols such as methyl alcohol, ethanol, Virahol; The polyalcohols such as ethylene glycol, 1,2-PD; The ketones such as acetone, methyl ethyl ketone, methyl ethyl diketone; The ethers such as methyl ethyl ether, diox; The glycol ethers such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list n-propyl ether, glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, dipropylene glycol list propyl ether; The ethyl glycol acetate classes such as ethylene glycol acetate, glycol diacetate, ethylene glycol monomethyl ether acetate; The fatty family hydro carbons such as Skellysolve A, normal hexane; The fragrant family hydro carbons such as toluene, dimethylbenzene, solvent naphtha; Aforementioned allylation polyether monomer.These solvents can use separately a kind, or also two or more kinds may be used.Wherein, use manufacture stability and the dispersion stability of resin combination good in order to make to comprise the water-based antifouling paint of the vinyl based polymer obtaining, preferably contain alcohol based compound.
Be not particularly limited as monomer mixture (M1) and the ratio of the use level of monomer mixture (M2), preferred mass ratio (M1/M2) is in 15/85～85/15 scope, more preferably in 20/80～80/20 scope.If within the scope of this, the tendency that exists the storage stability of the antifouling paint resin combination that comprises the vinyl based polymer obtaining to improve.
In manufacture method according to the embodiment of the present invention, can add monomer mixture (M2) and carry out operation (2) to the polymerization liquid after operation (1), also can add monomer mixture (M1) and carry out operation (1) to the polymerization liquid after operation (2).Become well from the dispersion stabilization of the vinyl based polymer that obtains, preferably carrying out after operation (1), carrying out operation (2).
The molecular weight of the vinyl based polymer obtaining in addition, can suitably be determined according to desired characteristic.For example, the weight-average molecular weight of the polystyrene conversion by gel permeation chromatography (Mw) can be set in to 1,000～50,000 scope.
[water-based antifouling paint resin combination]
The vinyl based polymer obtaining by the polymerization process that comprises operation (1) and operation (2) is dispersed in to water or comprise water and dispersion medium that the mixture of organic solvent forms in, thereby can obtain water-based antifouling paint resin combination according to the embodiment of the present invention.From the viewpoint of film-forming properties, didirtresistance, preferably at the water-based antifouling paint obtaining with containing vinyl based polymer with the scope of 20～60 quality % in composition.After polymerization finishes, before dispersion step, the desolventizing operation that can remove by usual method polymerization organic solvent used.
By being dispersed in aforementioned dispersion medium after part or all neutralization of the carboxyl in the vinyl based polymer obtaining, be preferred from the viewpoint of the smooth transfer to water.
Aforementioned neutralization can be undertaken by add basic cpd in vinyl based polymer.Be not particularly limited as the basic cpd using, for example, the alkyl amines such as preferred ammoniacal liquor (aqueous solution), Trimethylamine 99, triethylamine, diisopropylethylamine, butylamine; The alcaminess such as dimethylethanolamine (DMEA), dimethylisopro panolamine, methyldiethanolamine, diethylethanolamine, trolamine, butanolamine; Morpholine, isophorone diamine etc.Basic cpd can use a kind, and also two or more kinds may be used.
The mode that these basic cpds preferably become 40～150% mol ratio with the molar weight of the carboxyl contained with respect to vinyl based polymer coordinates, and more preferably 60～120%.By neutralizing with basic cpd, antifouling paint can be made as with the pH of resin combination preferred 6.0～11.0, more preferably 6.5～9.0.
As aforementioned dispersion medium, can make water or comprise water and the mixture of organic solvent.As this organic solvent, can use the organic solvent using in the polymerization of vinyl based polymer.As this organic solvent, from dispersed viewpoint, the alcohol based compounds such as preferred alcohols, glycol ethers.Wherein, as alcohol, the carbonatoms 1～6 that boiling point is lower, the monohydroxy-alcohol of preferred carbonatoms 2～4 can be suitably used, as glycol ethers, the glycol ethers of carbonatoms 3～11, preferred carbonatoms 3～8 can be suitably used.
Content as aforementioned water-based antifouling paint with aforementioned organic solvent in resin combination, is preferably below 20 quality %, more preferably below 10 quality %.
Water-based antifouling paint according to the embodiment of the present invention can coordinate stain control agent as required with resin combination.As this stain control agent, the suitable choice for use of performance as requested, for example, be headed by stain control agent with copper such as Red copper oxide, cupric thiocyanide, copper powder, can enumerate other the sulfonamide derivatives such as metallic compound, diphenylamine, nitrile compound, benzothiazole based compound, maleimide amine compound, pyridine based compound etc. such as lead, zinc, nickel.They can use separately a kind or be used in combination two or more.More specifically, can enumerate ethylidene dithiocarbamate manganese, ziram, 2-methyl sulfo--4-tertiary butyl amino-6-cyclopropylamino-s-triazine, 2,4,5,6-daconil M, N, N-dimethyl dichlorophenyl urea, zineb, cuprous thiocyanate, the chloro-2-of 4,5-bis-n-octyl-3 (2H) isothiazolones, N-(fluorine dichloromethyl sulfo-) phthalic imidine, N, N '-dimethyl-N '-phenyl-(N-fluorine dichloromethyl sulfo-) sulphamide, 2-mercaptopyridine-1-oxide compound zinc salt, tetramethyl thiuram disulfide, Cu-10%Ni solid solution alloy, 2,4,6-trichlorophenyl maleimide 2,3,5,6-tetrachloro-4-(methylsulfonyl) pyridine, the iodo-2-propynyl butyl of 3-carboxylamine, diiodomethyl is to three sulfones, two Methyl disulfide are for formamyl zinc ethylenebis dithiocarbamate, phenyl (bipyridyl) bismuth dichloride, 2-(4-thiazolyl)-benzoglyoxaline, pyridine-triphenylborane etc.
Water-based antifouling paint is according to the embodiment of the present invention with in resin combination, for film coated surface being given to oilness, prevent from the object of biological attachment from can coordinating the fluorochemicalss such as the silicon compound such as dimethyl polysiloxane, silicone oil, fluorocarbons etc.
And then water-based antifouling paint according to the embodiment of the present invention can contain various pigment, defoamer, pigment dispersing agent, flow agent, antisag agent, matting agent, UV light absorber, antioxidant, thermotolerance rising agent, slipping agent, sanitas, softening agent, other latex resins, water soluble resin, viscosity control agent etc. with resin combination.
Use the film of water-based antifouling paint resin combination according to the embodiment of the present invention on boats and ships, various fishing net, bay base coating film, to be coated with.As this base coating film, can use the formation such as priming paint, floating coat paint of wash primer, chlorinated rubber system, epoxy system etc.The film being obtained by resin combination according to the embodiment of the present invention can the base coating film on substrate surface or base material on method painting fabric aqueous antifouling paint resin combinations such as brushing, spraying, roller coat, the coatings of heavy stain.Generally speaking glue spread can be set as counting with dry coating the amount of the thickness of 10～400 μ m.The dry of film can at room temperature carry out conventionally, also can carry out as required heat drying.
Embodiment
Below, by embodiment and comparative example, the present invention is described in further detail.Wherein, the part in embodiment represents mass parts.The water-based antifouling paint of the present embodiment modulation is undertaken by method shown below with the evaluation of resin combination.
(molecular weight of macromonomer (a3))
Measure with gel permeation chromatography (GPC) (TOSOH Co., Ltd's system, trade(brand)name: HLC-8220).Pillar commodity in use name: TSKgel α-M (TOSOH Co., Ltd's system, 7.8mm × 30cm), trade(brand)name: TSKguardcolumn α (TOSOH Co., Ltd's system, 6.0mm × 4cm).Working curve uses polystyrene standard (TOSOH Co., Ltd's system, trade(brand)name: F288, F128, F80, F40, F20, F2, A1000) and styrene monomer to make.DMF (DMF) solution that modulation makes sample (polymkeric substance) dissolve to become the mode of 0.4 quality %, uses the DMF solution 100 μ l that modulate, and measures at 40 DEG C.Convert by polystyrene standard, calculate number-average molecular weight (Mn).
(storage stability evaluation)
Water-based antifouling paint is preserved 1 month at normal temperatures with resin combination P1～P17, confirmed sedimentary having or not by range estimation.Evaluate and undertaken by following benchmark:
Zero: resinous principle does not precipitate, separates, there is no coagulative formation,
△: there is a small amount of throw out, but can disperse through stirring,
×: resinous principle precipitates, separates, solidifies, even if stir also redispersion not.
(Martens hardness)
On glass substrate, be coated with respectively fabric aqueous antifouling paint resin combination P1～P17 with 4mil applicator, at room temperature dry 2 weeks, produce test board, for the film of these test boards, utilize super micro-hardness tester (the Fisher Instruments of Co., Ltd. sample processed, trade(brand)name: HM2000) to measure Martens hardness.Wherein, Martens hardness is preferably 2.0～15.0N/mm
2scope, more preferably 2.5～10.0N/mm
2scope.
(water tolerance test)
On glass substrate, be coated with respectively fabric aqueous antifouling paint resin combination P1～P17 with 4mil applicator, at room temperature dry 1 week, produce test board.The test board obtaining is flooded after 1 month in sterilising filtration seawater, these test boards are dried to 1 week under the room temperature of 20 DEG C of temperature.Measure the albefaction degree of the film coated surface of dried test board with mist degree instrument (color technical institute system, trade(brand)name: HM-150 in village).Evaluate and undertaken by following benchmark:
Zero: haze value is less than 10,
Zero △: haze value is more than 10 below 20,
△: haze value is more than 20 and lower than 50,
×: haze value is more than 50.
(separability test)
The test board of similarly making with aforementioned water tolerance test is flooded after 1 month in sterilising filtration seawater, by these test boards under the room temperature of 20 DEG C of temperature dry 1 week, carry out stripping test.About stripping test, on film, paste CELLOTAPE (registered trademark) and peel rapidly, evaluate by the area ratio of peeling off.Evaluate and undertaken by following benchmark:
Zero: do not observe and peel off,
Zero △: more than 80% unstripped,
△: 50～80% peel off,
×: peel off comprehensively.
(the consumption degree test of film)
Coordinate each 60 parts of water-based antifouling paint resin combination P1～P17,30 parts, zinc oxide (ZnO), titanium oxide (TiO
2) 1 part of 20 part, tensio-active agent (Asahi Denka Co., Ltd.'s system, trade(brand)name: ADEKA COLW193), stir, obtain title complex.The mode applicator that respectively title complex obtaining is become to 120 μ m with dry film thickness on the hard vinyl chloride plate of 50mm × 50mm × 2mm (thickness) is coated with, and produces test board.These test boards are arranged on the rotating cylinder of being located in seawater, make its rotation with circumferential speed 7.7m/s (15knot).After 1 month, take out test board, measure thickness.Obtain the consumption degree (μ m/M) of the film after 1 month by following formula:
Consumption degree (μ m/M)=120 μ m-(thickness after 1 month) the μ m of the film after 1 month.
[manufacture of macromonomer (a3-1)]
(manufacture of dispersion agent 1)
Possessing in the poly-unit of stirrer, cooling tube, thermometer, add 900 parts of deionized waters, 60 parts of methacrylic acid 2-sulfo group sodium ethyls, 10 parts, methacrylic acid potassium and 12 parts of methyl methacrylates (MMA) and stir, to carrying out nitrogen replacement in poly-unit, be warming up to 50 DEG C on one side on one side.Add therein 0.08 part 2, two (the 2-methyl-prop amidine) dihydrochlorides of 2 '-azo, as polymerization starter, are further warming up to 60 DEG C.After intensification, use dropping liquid pump that MMA is dripped to 75 minutes continuously with the speed of 0.24 part/minute.Reaction soln is kept, after 6 hours, being cooled to room temperature at 60 DEG C, obtain the dispersion agent 1 as the solids component 10 quality % of transparent aqueous solution.
(manufacture of chain-transfer agent 1)
In the synthesizer that possesses whipping appts, under nitrogen atmosphere, the diethyl ether 80ml that add cobaltous acetate (II) tetrahydrate 1.00g and phenylbenzene glyoxime 1.93g, has carried out in advance deoxidation by nitrogen gas foaming, at room temperature stirs 30 minutes.Then, add boron trifluoride diethyl ether complex compound 10ml, further stir 6 hours.Filtering mixt, washs solid with diethyl ether, and vacuum-drying 15 hours, obtains the chain-transfer agent 1 of 2.12g as sorrel solid.
(modulation of macromonomer)
Possessing in the poly-unit of stirrer, cooling tube, thermometer, add 0.25 part of 145 parts of deionized waters, 0.1 part, sodium sulfate and dispersion agent 1 (solids component 10 quality %) and stir, make the uniform aqueous solution.Then, add 100 parts of MMA, 0.002 part of chain-transfer agent 1 and 0.2 part 1,1,3,3-tetramethyl butyl peroxidation 2-ethylhexanoate (Japan Oil Co's system, trade(brand)name: PEROCTA O), obtains aqueous suspension.
Then,, to carrying out nitrogen replacement in poly-unit, be warming up to 80 DEG C and react 1 hour.In order further to improve percent polymerization, be warming up to 90 DEG C and keep 1 hour.Afterwards, make reaction solution be cooled to 40 DEG C, obtain the aqueous suspension of macromonomer.Nylon filter-cloth filtering by this aqueous suspension with mesh 45 μ m, by filtrate with deionized water wash and dewater, be dried 16 hours at 40 DEG C, obtain being equivalent to the macromonomer (a3-1) of the macromonomer shown in formula (B).Mn=7000, the Mw/Mn=2.0 of this macromonomer (a3-1).Table 1 represents the input amount of material and the Mn of the macromonomer obtaining.
[macromonomer (a3-2)～manufacture] (a3-6)
Be made as input amount shown in table 1, in addition, similarly operate with the aforementioned modulation of macromonomer (a3-1), manufacture and be equivalent to the macromonomer (a3-2) of the macromonomer shown in formula (B)～(a3-6).Table 1 represents the input amount of each raw material and the Mn of the macromonomer obtaining.
[table 1]
Writing a Chinese character in simplified form in table is as follows:
N-BMA: n-BMA,
N-BA: n-butyl acrylate,
PEROCTA O (trade(brand)name): 1,1,3,3-tetramethyl butyl peroxidation 2-ethylhexanoate (Japan Oil Co's system).
[modulation of the monomer mixture (m2-1) that comprises the ethylene unsaturated monomer (a2-1) that contains divalent metal]
Possessing in the reaction vessel of stirrer, temperature adjuster, dropper, add 41 parts, MMA70 part and zinc oxide (ZnO), stir while be warming up to 75 DEG C.With within 3 hours, dripping wherein the mixture that comprises 5 parts of 34 parts of methacrylic acids (MAA), 29 parts, vinylformic acid (AA), sad 29 parts, water.After dropping finishes, reaction soln becomes transparent from oyster white state.Further stir after 2 hours, add MMA39.7 part, obtain the monomer mixture (m2-1) of the ethylene unsaturated monomer (a2-1) that transparent comprising contain divalent metal.Table 2 represents the concentration of the ethylene unsaturated monomer that contains metal (a2-1) contained in the input amount, monomer mixture (m2-1) of each raw material.Its concentration is set as 50 quality % by adjustment by amount of moisture.
[comprising respectively the ethylene unsaturated monomer (a2-2) that contains divalent metal, the monomer mixture (m2-2) of (a2-3), the modulation of (m2-3)]
Be made as the input amount shown in table 2, in addition, similarly operate with the aforementioned modulation of monomer mixture (m2-1), obtain and comprise respectively the ethylene unsaturated monomer (a2-2), the mixture (m2-2) of (a2-3), (m2-3) that contain divalent metal.Wherein, in the modulation of monomer mixture (m2-2), use n-BA to replace MMA, in the modulation of monomer mixture (m2-3), use PGM to replace MMA.Table 2 represents the ethylene unsaturated monomer that contains metal (a2-2) contained in the input amount, monomer mixture (m2-2), (m2-3) of each raw material, the concentration of (a2-3).Their concentration is set as 50 quality % by adjustment by amount of moisture.N-BA in table represents n-butyl acrylate, and PGM represents dipropylene glycol monomethyl ether.
[table 2]
* PGM: dipropylene glycol monomethyl ether.
(embodiment 1)
Possessing in the reaction vessel of stirrer, temperature adjuster, dropper, drop into organic solvent (trade(brand)name: SOLVESSO100, exxonmobil chemical company's system) 15 parts, stir while be warming up to 130 DEG C.Then, the polymerization that comprises operation 1 and operation 2 as described below.
< operation 1 >
Then, the monomer mixture (M1) that comprises following raw material with dropping in 2 hours, further carries out copolyreaction in 0.5 hour.
The composition of monomer mixture (M1):
Macromonomer (a3-1): 15 parts,
N-BA:20 part,
MAA:7 part,
Tert-butyl hydroperoxide 2-ethylhexanoate (PERBUTYL O, Japan Oil Co's system): 3 parts.
< operation 2 >
Then, the monomer mixture (M2) that comprises following raw material with dropping in 3 hours, further carries out copolyreaction in 0.5 hour.
The composition of monomer mixture (M2):
M2-1:20 part (wherein, 10 parts of the ethene unsaturated ethylene base system monomer solids components that contains divalent metal),
MMA:7.8 part,
N-BA:23 part,
2-methoxy ethyl methacrylic ester (2-MTMA): 7.2 parts,
Chain-transfer agent (trade(brand)name: NOFMER MSD, Japan Oil Co's system): 1.5 parts,
Tert-butyl hydroperoxide 2-ethylhexanoate (trade(brand)name: PERBUTYL O, Japan Oil Co's system): 5 parts.
Then, further add 0.5 part of PERBUTYL O (trade(brand)name), further continue to carry out 1 hour polyreaction, obtain vinyl based polymer A1.
100 parts of vinyl based polymer A1 that obtain are stirred while be heated to 80 DEG C, add 5.7 parts of dimethylethanolamines (DMEA), mix until evenly, then, slowly add 90 parts of deionized waters, obtain the water-based antifouling paint resin combination P1 that vinyl based polymer A1 is dispersed in water.
The evaluation result of the water-based antifouling paint resin combination P1 obtaining is shown in to table 3.
(embodiment 2～15, comparative example 1,2)
Be made as the input amount shown in table 3, in addition, operation similarly to Example 1, obtains vinyl based polymer A2～A17 and water-based antifouling paint resin combination P2～P17.Evaluation result is shown in to table 3.
In monomer mixture (M1), (M2), all do not use and have in the comparative example 1 of macromonomer (a3) of free-radical polymerised group, the vinyl based polymer obtaining is random copolymers, hardness, the water tolerance of the film that therefore, comprises this vinyl based polymer are insufficient.And in embodiment 1～15, obtain water tolerance excellence, there is the film of sufficient hardness.
Do not use in the comparative example 2 of the ethylene unsaturated monomer (a2) that contains divalent metal, the consumption degree of film is insufficient, does not obtain sufficient antifouling property.And in embodiment 1～15, obtain the film that antifouling property is good.
[table 3]
* the numerical value of epimere in the m2 of operation 2, a2 hurdle: the amount of the mixture (m2) that comprises the ethylene unsaturated monomer that contains divalent metal
The numerical value of hypomere in the m2 of operation 2, a2 hurdle: the content of the contained ethylene unsaturated monomer that contains divalent metal (a2) in mixture m2.
Claims (10)
1. the manufacture method of a vinyl based polymer, it comprises: make to comprise the ethylene unsaturated monomer (a1) that contains carboxyl monomer mixture (M1) polymerization operation (1) and make to comprise the operation (2) of monomer mixture (M2) polymerization of the ethylene unsaturated monomer (a2) that contains divalent metal
At least either party in described monomer mixture (M1) and monomer mixture (M2) comprises the macromonomer (a3) with free-radical polymerised group,
Add monomer mixture (M2) to the polymerization liquid after operation (1) thus carry out operation (2), or add monomer mixture (M1) to the polymerization liquid after operation (2) thus carry out operation (1).
2. the manufacture method of vinyl based polymer according to claim 1, the polystyrene conversion number-average molecular weight Mn that passes through gel permeation chromatography of described macromonomer (a3) is 300～15000.
3. the manufacture method of vinyl based polymer according to claim 1 and 2,
Described macromonomer (a3) has the main chain shown in following formula, and has terminal double link as described free-radical polymerised group,
-(C(X)(COOR)-CH
2)
n-H
In formula, X is hydrogen atom or methyl, and R is hydrogen atom, silyl, replacement or unsubstituted alkyl, replacement or unsubstituted cycloalkyl or replacement or unsubstituted aryl, the integer that n is 1～150.
4. the manufacture method of vinyl based polymer according to claim 1 and 2, described macromonomer (a3) by following formula (A) represent,
In formula (A), X, Y are hydrogen atom or methyl independently of one another, R
nbe hydrogen atom, silyl, replacement or unsubstituted alkyl, replacement or unsubstituted cycloalkyl or replacement or unsubstituted aryl independently of one another, R ' is the group with the alkylidene group of carbonatoms 1～12, the integer that n is 1～150.
5. the manufacture method of vinyl based polymer according to claim 1 and 2, described macromonomer (a3) by following formula (B) represent,
In formula (B), Z is hydrogen atom or methyl, and R is hydrogen atom, silyl, replacement or unsubstituted alkyl, replacement or unsubstituted cycloalkyl or replacement or unsubstituted aryl independently of one another, the integer that n is 1～150.
6. according to the manufacture method of the vinyl based polymer described in any one in claim 1 to 5, in whole monomers of monomer mixture (M1) and monomer mixture (M2), in the scope of 1～35 quality %, coordinate described macromonomer (a3).
7. a vinyl based polymer, it obtains by the manufacture method described in any one in claim 1 to 6.
8. a water-based antifouling paint resin combination, it obtains by vinyl based polymer claimed in claim 7 is dispersed in the dispersion medium that comprises water.
9. water-based antifouling paint resin combination according to claim 8, the content of described vinyl based polymer is in the scope of 20～60 quality %.
10. water-based antifouling paint resin combination according to claim 8 or claim 9, the content of organic solvent is below 20 quality %.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012008250 | 2012-01-18 | ||
| JP2012-008250 | 2012-01-18 | ||
| PCT/JP2013/050951 WO2013108880A1 (en) | 2012-01-18 | 2013-01-18 | Method for producing vinyl polymer and resin composition for water-based antifouling paint containing vinyl polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104053690A true CN104053690A (en) | 2014-09-17 |
| CN104053690B CN104053690B (en) | 2016-05-25 |
Family
ID=48799301
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380005769.6A Active CN104053690B (en) | 2012-01-18 | 2013-01-18 | The manufacture method of vinyl based polymer and the water-based antifouling paint resin combination that comprises vinyl based polymer |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6056751B2 (en) |
| CN (1) | CN104053690B (en) |
| TW (1) | TWI585110B (en) |
| WO (1) | WO2013108880A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108137760A (en) * | 2015-09-25 | 2018-06-08 | 三菱化学株式会社 | (methyl) acrylic acid series copolymer, polymer solution, the manufacturing method containing polymer composition, antifouling paint compositions and (methyl) acrylic acid series copolymer |
| CN109952328A (en) * | 2016-11-17 | 2019-06-28 | 三菱化学株式会社 | The forming method of (methyl) acrylic acid series copolymer, coating composition, painting object and multilayer coating film |
| CN110506064A (en) * | 2017-03-29 | 2019-11-26 | 三菱化学株式会社 | (methyl) acrylic acid series copolymer, its manufacturing method, resin combination and antifouling paint compositions |
| CN110520452A (en) * | 2017-03-29 | 2019-11-29 | 三菱化学株式会社 | (methyl) acrylic acid series copolymer, its manufacturing method, resin combination and antifouling paint compositions |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6351035B2 (en) * | 2014-08-12 | 2018-07-04 | 関西ペイント株式会社 | Contamination-resistant matte water-based coating composition and stain-resistant matte coating film forming method |
| RU2564677C1 (en) * | 2014-09-16 | 2015-10-10 | Игорь Иванович Зоткин | Zinc or copper (ii) salt and use thereof as biocide |
| WO2018097260A1 (en) | 2016-11-25 | 2018-05-31 | 学校法人早稲田大学 | Polymer, resin composition, antifouling coating material composition, method for producing polymer, method for forming structure for stabilizing carbamate on surface of coating film, and method for regenerating structure for stabilizing carbamate on surface of coating film |
| JP7019972B2 (en) * | 2017-06-06 | 2022-02-16 | 三菱ケミカル株式会社 | Resin composition, antifouling paint, coating film, underwater friction reduction method, and method for manufacturing resin composition |
| KR102528764B1 (en) | 2018-06-01 | 2023-05-08 | 미쯔비시 케미컬 주식회사 | antifouling paint composition |
| CN113214434B (en) * | 2021-04-16 | 2022-04-01 | 浙江大学 | Preparation of core-shell acrylic acid antifouling resin and application of core-shell acrylic acid antifouling resin in copper-free antifouling paint |
| JP7330324B1 (en) * | 2022-03-30 | 2023-08-21 | 大日本塗料株式会社 | Coating composition for forming surface protective layer, method for forming surface protective layer, and coated body |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1069505A (en) * | 1991-08-15 | 1993-03-03 | 永记造漆工业股份有限公司 | Self-abrasion anti-foul paint compound |
| CN1761727A (en) * | 2003-03-14 | 2006-04-19 | 三菱丽阳株式会社 | Antifouling paint composition |
| CN101663600A (en) * | 2007-02-09 | 2010-03-03 | 三菱丽阳株式会社 | Transparent molded body and reflection preventing article using the same |
| WO2011080821A1 (en) * | 2009-12-28 | 2011-07-07 | 三菱レイヨン株式会社 | Method for producing resin dispersion for antifouling coating |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2648853B2 (en) * | 1987-04-22 | 1997-09-03 | 日本ペイント株式会社 | Composite three-dimensional resin particles and their manufacturing method |
| JP2622855B2 (en) * | 1988-06-03 | 1997-06-25 | 日本ゼオン 株式会社 | Vulcanizable rubber composition |
| JP5144389B2 (en) * | 2008-06-20 | 2013-02-13 | 三菱レイヨン株式会社 | Resin composition for water-based antifouling paint |
| JP5379699B2 (en) * | 2010-01-06 | 2013-12-25 | 三菱レイヨン株式会社 | Method for producing metal-containing ethylenically unsaturated monomer mixture |
-
2013
- 2013-01-18 TW TW102102036A patent/TWI585110B/en active
- 2013-01-18 CN CN201380005769.6A patent/CN104053690B/en active Active
- 2013-01-18 WO PCT/JP2013/050951 patent/WO2013108880A1/en active Application Filing
- 2013-01-18 JP JP2013503683A patent/JP6056751B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1069505A (en) * | 1991-08-15 | 1993-03-03 | 永记造漆工业股份有限公司 | Self-abrasion anti-foul paint compound |
| CN1761727A (en) * | 2003-03-14 | 2006-04-19 | 三菱丽阳株式会社 | Antifouling paint composition |
| CN101663600A (en) * | 2007-02-09 | 2010-03-03 | 三菱丽阳株式会社 | Transparent molded body and reflection preventing article using the same |
| WO2011080821A1 (en) * | 2009-12-28 | 2011-07-07 | 三菱レイヨン株式会社 | Method for producing resin dispersion for antifouling coating |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108137760A (en) * | 2015-09-25 | 2018-06-08 | 三菱化学株式会社 | (methyl) acrylic acid series copolymer, polymer solution, the manufacturing method containing polymer composition, antifouling paint compositions and (methyl) acrylic acid series copolymer |
| CN108137760B (en) * | 2015-09-25 | 2022-03-15 | 三菱化学株式会社 | (meth) acrylic copolymer and method for producing same, polymer solution, polymer-containing composition, and antifouling paint composition |
| US11643489B2 (en) | 2015-09-25 | 2023-05-09 | Mitsubishi Chemical Corporation | (Meth)acrylic copolymer, polymer solution, polymer-containing composition, anti-fouling coating composition, and method for producing (meth)acrylic copolymer |
| CN109952328A (en) * | 2016-11-17 | 2019-06-28 | 三菱化学株式会社 | The forming method of (methyl) acrylic acid series copolymer, coating composition, painting object and multilayer coating film |
| US11767446B2 (en) | 2016-11-17 | 2023-09-26 | Mitsubishi Chemical Corporation | (Meth)acrylic copolymer, coating material composition, coated article and method for forming multilayer coating film |
| CN110506064A (en) * | 2017-03-29 | 2019-11-26 | 三菱化学株式会社 | (methyl) acrylic acid series copolymer, its manufacturing method, resin combination and antifouling paint compositions |
| CN110520452A (en) * | 2017-03-29 | 2019-11-29 | 三菱化学株式会社 | (methyl) acrylic acid series copolymer, its manufacturing method, resin combination and antifouling paint compositions |
| CN110506064B (en) * | 2017-03-29 | 2022-06-03 | 三菱化学株式会社 | (meth) acrylic copolymer, method for producing same, resin composition, and antifouling coating composition |
| CN110520452B (en) * | 2017-03-29 | 2022-08-02 | 三菱化学株式会社 | (meth) acrylic copolymer, method for producing same, resin composition, and antifouling coating composition |
| US11414508B2 (en) | 2017-03-29 | 2022-08-16 | Mitsubishi Chemical Corporation | Resin composition with a (meth)acrylic copolymer, antifouling paint composition, and method for producing same |
| US11499069B2 (en) | 2017-03-29 | 2022-11-15 | Mitsubishi Chemical Corporation | (meth)acrylic copolymer, method for producing same, resin composition and antifouling paint composition |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2013108880A1 (en) | 2013-07-25 |
| TW201341410A (en) | 2013-10-16 |
| JPWO2013108880A1 (en) | 2015-05-11 |
| JP6056751B2 (en) | 2017-01-11 |
| TWI585110B (en) | 2017-06-01 |
| CN104053690B (en) | 2016-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104053690A (en) | Method for producing vinyl polymer and resin composition for water-based antifouling paint containing vinyl polymer | |
| KR101991228B1 (en) | (meth)acrylic copolymer, polymer solution, polymer-containing composition, antifouling coating composition, and method for producing (meth)acrylic copolymer | |
| JP7341514B2 (en) | Antifouling paint composition | |
| KR101003602B1 (en) | Antifouling paint composition | |
| CN102686680B (en) | The manufacture method of antifouling paint resin dispersion | |
| CN112513207B (en) | Antifouling coating composition, antifouling coating film, substrate with antifouling coating film, method for producing same, and method for repairing same | |
| CN104284949B (en) | Antifouling paint resin combination, antifouling paint and antifouling coat | |
| CN116490575A (en) | Antifouling coating composition | |
| CN109153840B (en) | Polymer-containing composition and antifouling coating composition | |
| CN102369250A (en) | Antifouling coating composition, antifouling coating film formed from the composition, coated object having the coating film on surface, and method of antifouling treatment by forming the coating film | |
| JP6511944B2 (en) | Resin composition for antifouling paint and antifouling coating film | |
| JP4154344B2 (en) | Coating composition and copolymer | |
| JP2002012630A (en) | Metal-containing resin composition and antifouling coating composition | |
| CN109311284B (en) | Laminated antifouling coating film, antifouling substrate, and ship | |
| JP2009256471A (en) | Coating composition and copolymer | |
| JP5162066B2 (en) | Method for producing aqueous antifouling paint composition | |
| JP4154345B2 (en) | Coating composition and copolymer | |
| KR20230161937A (en) | Compounds, polymers and antifouling paint compositions | |
| WO2022191100A1 (en) | Antifouling coating composition | |
| JP2017075329A (en) | Metal-containing copolymer for antifouling coating and antifouling coating composition | |
| KR20010050655A (en) | Process for Preparing Metal-Containing Resins and Their Compositions | |
| JPH1121326A (en) | Graft copolymer, resin composition, slightly water-soluble paint and production of graft copolymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: Tokyo, Japan, Japan Patentee after: Mitsubishi Kasei Corporation Address before: Tokyo, Japan, Japan Patentee before: Mitsubishi Reiyon Co., Ltd. |
|
| CP01 | Change in the name or title of a patent holder |