CN104053690B - The manufacture method of vinyl based polymer and the water-based antifouling paint resin combination that comprises vinyl based polymer - Google Patents
The manufacture method of vinyl based polymer and the water-based antifouling paint resin combination that comprises vinyl based polymer Download PDFInfo
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- CN104053690B CN104053690B CN201380005769.6A CN201380005769A CN104053690B CN 104053690 B CN104053690 B CN 104053690B CN 201380005769 A CN201380005769 A CN 201380005769A CN 104053690 B CN104053690 B CN 104053690B
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- 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
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- 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
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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
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1668—Vinyl-type polymers
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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
- 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
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Abstract
A kind of manufacture method of vinyl based polymer, it comprises: 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).
Description
Technical field
The present invention relates to have the water-based antifouling paint resin combination of soil resistance. In addition, also relate to and being suitable for for obtainingObtain the manufacture method of the vinyl based polymer of water-based antifouling paint resin combination.
Background technology
Antifouling paint be prevent marine creature and seaweeds adhere to for object coat underwater structures, fishing net,The coating of hull bottom etc. The film being obtained by antifouling paint is brought into play in marine stripping by antifouling drug ingredient contained in coatingAnti-fouling effect. Known have various antifouling paints, for example, by the painting that has used the disintegration-type antifouling paint of rosin series compound to obtainFilm, impregnated in marine in the situation that for a long time, and dissolved element tails off at leisure, dissolved element does not become many. Therefore, antifouling medicineEffect reduce, 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 what obtain from polishing type antifouling paintFilm, in seawater, film coated surface is carried out Surface Renewal (from polishing) lentamente, and antifouling composition always exposes in film coated surface, because ofThis, 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, from closelyVOC (VolatileOrganicCompound, the VOC) problem in year is considered, to replacing their water-basedAntifouling paint has carried out various research.
As from polishing type water-based antifouling paint, for example, in patent documentation 1, record to be dispersed with in water and contained divalent goldThe water-based antifouling paint resin combination of the polymer belonging to.
In patent documentation 2, record the water-based that contains the graft copolymer that comprises the macromonomer that is connected to main chain endCoating composition.
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 to make ethene with the copolymer using in resin combinationThe material that property unsaturated monomer is polymerized by common free radical polymerisation process is random copolymer. By comprising thisAlthough the film that the antifouling paint of the random copolymer of sample obtains has from polishability, hardness is low, and resistance to water is also insufficient, the phaseTreat further improvement.
In addition,, about the coating composition of recording in patent documentation 2, the film being obtained by this coating composition does not haveUtilize hydrolysis from polishability, do not show soil resistance.
The object of the present invention is to provide a kind of water-based antifouling paint resin combination, described water-based antifouling paint is with settingOil/fat composition is the antifouling paint resin combination that has solved the problems referred to above and suppressed organic solvent content, by this resin groupThe film that compound obtains shows good soil resistance, and resistance to water excellence, has sufficient hardness. In addition another order of the present invention,Be to provide a kind of vinyl based polymer and manufacture method thereof, described vinyl based polymer is suitable for for obtaining suchWater-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: make to comprise the second that contains carboxylThe operation (1) of monomer mixture (M1) polymerization of alkene unsaturated monomer (a1) and make to comprise the ethene that contains divalent metalThe operation (2) of monomer mixture (M2) polymerization of unsaturated monomer (a2), aforementioned monomer mixture (M1) and monomer mixture(M2) at least either party in comprises the macromonomer (a3) with free-radical polymerised group, to the polymerization after operation (1)Reactant liquor adds monomer mixture (M2) thereby carries out operation (2), or adds monomer to mix to the polymerization liquid after operation (2)Thing (M1) thus carry out operation (1).
It is the ethene base system obtaining by above-mentioned manufacture method according to the vinyl based polymer of another way of the present inventionPolymer.
To make above-mentioned vinyl based polymer according to the water-based antifouling paint resin combination of another way of the present inventionBe dispersed in the decentralized medium that comprises water and the resin combination obtaining.
The effect of invention
According to the embodiment of the present invention, can provide a kind of antifouling paint resin combination, described antifouling paint is usedResin combination can form demonstration good soil resistance, resistance to water excellence, have the film of sufficient hardness, and has suppressedThe content of organic solvent. According to another embodiment of the present invention, can provide and be suitable for using for obtaining this water-based antifouling paintVinyl based polymer and the manufacture method thereof of resin combination.
Detailed description of the invention
The manufacture method of vinyl based polymer according to the embodiment of the present invention comprises makes to comprise the second that contains carboxylThe operation (1) of monomer mixture (M1) polymerization of alkene unsaturated monomer (a1) and make to comprise the ethene that contains divalent metalThe operation (2) of monomer mixture (M2) polymerization of unsaturated monomer (a2). Below, each operation is described.
< operation (1) >
Operation (1) is the work that makes to comprise monomer mixture (M1) polymerization of the ethylene unsaturated monomer (a1) that contains carboxylOrder.
[ethylene unsaturated monomer (a1) that contains carboxyl]
As the ethylene unsaturated monomer that contains carboxyl (a1), can enumerate for example methacrylic acid, acrylic acid, crotonsMonoacid or the dicarboxylic acid monomer classes such as acid, vinyl benzoic acid, fumaric acid, itaconic acid, maleic acid, citraconic acid; Maleic acid list firstEster, ethyl maleate, butyl maleate, single-ethylhexyl maleate, monomethyl itaconate, itaconic acid mono ethyl ester, itaconic acid listButyl ester, itaconic acid mono octyl ester, monomethyl fumarate, monomethyl ester, fumaric acid mono-n-butylester, fumaric acid mono octyl ester, citraconic acidMono 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) thirdOlefin(e) acid ester, phthalic acid monohydroxy propyl group (methyl) acrylate, mono succinate hydroxyethyl (methyl) acrylate, amberAcid monohydroxy propyl group (methyl) acrylate, maleic acid monohydroxy ethyl (methyl) acrylate, maleic acid monohydroxy propyl group (firstBase) binary acid of the representative such as 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 other ethylene unsaturated monomer copolymerization, used by the antifouling paint that comprises the vinyl based polymer obtainingThe good viewpoint of resistance to water of the film that resin combination obtains is set out, preferable methyl acrylic acid, acrylic acid.
About the content of the ethylene unsaturated monomer that contains carboxyl (a1), at ethene according to the embodiment of the present inventionThe whole monomers that use in the manufacture of base system polymer be (monomer of the monomer of monomer mixture (M1) and monomer mixture (M2)Total amount) in, 1～30 quality % preferably contained, more preferably 3～15 quality %. If the ethene that contains carboxyl is unsaturatedThe content of monomer (a1) is more than 1 quality %, and antifouling paint is good with the storage-stable of resin combination. If this contentBelow 30 quality %, there is inclining of the resistance to water raising of the film being obtained by antifouling paint resin combination in seawaterTo.
[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 thisMonomer, can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) propyleneAcid isobutyl ester, (methyl) tert-butyl acrylate, (methyl) 2-EHA, the positive lauryl of (methyl) acrylic acid, (firstBase) the positive stearyl ester of acrylic acid, (methyl) cyclohexyl acrylate, (methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl)Isobornyl acrylates etc. have alkyl (methyl) acrylate; (methyl) acrylic acid 2-methoxyl group ethyl ester, (methyl) propylene(methyl) acrylate that acid 2-ethoxy ethyl ester, (methyl) acrylic acid phenoxy ethyl etc. contain alkoxyl or phenoxy group; (firstBase) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 4-hydroxyl butyl ester, (methyl) propyleneAcid glycerides etc. contain hydroxyl (methyl) acrylate; The ethene base system list that maleic anhydride, itaconic anhydride etc. contain anhydride groupBody; (methyl) glycidyl acrylate, α-ethylacrylate ethylene oxidic ester, (methyl) acrylic acid 3,4-epoxy butyl ester etc. containsThere is the ethene base system monomer of epoxy radicals; (methyl) acrylic acid dimethylamino ethyl ester, (methyl) acrylic acid diethylamino ethyl esterDeng (methyl) acrylic ester ethene base system monomer that contains amino; (methyl) acrylamide, the N-tert-butyl group (methyl) acryloylAmine, N-methylol (methyl) acrylamide, N-methoxy (methyl) acrylamide, N-butoxymethyl (methyl) acryloylThe ethene base system monomer that amine, DAAM, maleic amide, maleimide etc. contain amide groups; Ethenyl pyrrolidoneThe heterocycles such as ketone, vinylpyridine, VCz are alkaline monomer; Styrene, vinyltoluene, AMS, propyleneThe ethene base system monomers such as nitrile, methacrylonitrile, vinyl acetate, propionate; Methoxyl group ethylene glycol allyl ether, methoxyl groupPolyethylene glycol allyl ether, methoxyl group polypropylene glycol allyl ether, butoxy polyethylene glycol allyl ether, butoxy polypropylene glycolThe ends such as allyl ether, methoxy poly (ethylene glycol)-polypropylene glycol allyl ether, butoxy polyethylene glycol-propane diols allyl etherEnd alkoxyl allylation polyether monomer; Ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, three secondGlycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, BDO 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, pentaerythrite four (methyl) acrylic acidEster, dipentaerythritol six (methyl) acrylate, allyl methacrylate, triallyl cyanurate, maleic acid two allylsThe polyfunctional monomers such as ester, polypropylene glycol diallyl ether. Monomer mixture (M1) contained, the ethene that contains carboxyl is unsaturatedMonomer (a1) monomer is in addition one kind or two or more in them of choice for use suitably.
Wherein, " (methyl) acrylate " meaning is " acrylate and/or methacrylate ", " (methyl) acrylic acid "The meaning is " acrylic acid and/or methacrylic acid ", and " (methyl) acryloyl group " meaning is " acryloyl group and/or methacrylBase ", " (methyl) acrylonitrile " meaning is " acrylonitrile and/or methacrylonitrile ", " (methyl) acrylamide " meaning is " acryloylAmine and/or Methacrylamide ".
About monomer mixture (M1) contained, the ethylene unsaturated monomer (a1) that contains carboxyl monomer in addition, itsIn, from the viewpoint good with the copolymerizable of other ethene base system monomers, preferably (methyl) acrylate.
< operation (2) >
Operation (2) is monomer mixture (M2) polymerization that makes to comprise the ethylene unsaturated monomer (a2) that contains divalent metalOperation.
[ethylene unsaturated monomer (a2) that contains divalent metal]
As the ethylene unsaturated monomer that contains divalent metal (a2), can use and there is containing of 2 unsaturated groupsThe unsaturated list of the ethene that contains divalent metal shown in ethylene unsaturated monomer (a2a) or the following general formula (1) of divalent metalBody (a2b).
CH2＝C(R1)-COO-M-R2Formula (1)
(in formula (1), M represents divalent metal, R1Represent hydrogen atom or methyl, R2Represent organic acid residue. )
As the contained divalent metal of the ethylene unsaturated monomer that contains divalent metal (a2), long-term from the film that obtainsPerformance, from the viewpoint of polishability, is preferably at least a kind of metal of the group of selecting free Mg, Ca, Zn and Cu composition. From what obtainThe transparent viewpoint of vinyl based polymer is set out, and is 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 exampleAs Magnesium Acrylate Prepared [(CH2＝CHCOO)2Mg], magnesinm methacrylate [(CH2＝C(CH3)COO)2Mg], calcium acrylate [(CH2＝CHCOO)2Ca], methacrylic acid calcium [(CH2＝C(CH3)COO)2Ca], zinc acrylate resin [(CH2＝CHCOO)2Zn], metering systemAcid zinc [(CH2＝C(CH3)COO)2Zn], acrylic acid copper [(CH2＝CHCOO)2Cu], methacrylic acid copper [(CH2＝C(CH3)COO)2Cu] etc. (methyl) acrylic acid divalent slaine. Aforementioned monomer (a2a) can be as required suitably choice for use two or more.In order to exist the transparency of the vinyl based polymer obtaining to uprise, to use tree by the antifouling paint that comprises this vinyl based polymerThe color of the film that oil/fat composition obtains becomes beautiful tendency, preferably (methyl) zinc acrylate resin. Wherein, " (methyl) acrylic acid " meaningThink of is " acrylic acid " or " methacrylic acid ".
The ethylene unsaturated monomer that contains divalent metal (a2a) with 2 unsaturated groups is by making inorganic metalCompound and the ethylene unsaturated monomer (for example acrylic acid, methacrylic acid) that contains carboxyl are at for example organic solvent or etheneThe method of reacting in property unsaturated monomer obtains. Contain the ethene that contains divalent metal being obtained by preceding method unsaturatedThe compatibility excellence of the mixture of monomer (a2a) composition and organic solvent, other monomers, can make to comprise the polymerization of 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 0.01The scope of～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 fluoroacetic acid, acetic acid, propionic acid, sad, neodecanoic acid (Versaticacid), isostearic acid, palm fibrePalmitic acid acid, cresotinic acid, α-naphthoicacid, β-naphthoic acid, benzoic acid, 2,4,5-trichlorophenoxyacetic acid, 2,4-dichlorophenoxyacetic acid,The derivative residues of monobasic organic acid such as quinoline carboxylic acid, nitrobenzoic acid, nitronaphthoic acid, pyruvic acid. They can be as requiredSuitably select. Can prevent for a long time crackle, the film that the durability of peeling off is high in order to obtain, preference is as carbon number 1～20Aliphatic acid (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 monochloroMagnesium acetate (methyl) acrylate, monochloro calcium acetate (methyl) acrylate, monochloro zinc acetate (methyl) acrylate, monochloro secondAcid copper (methyl) acrylate; Single fluoroacetic acid magnesium (methyl) acrylate, single fluoroacetic acid calcium (methyl) acrylate, single fluoroacetic acidZinc (methyl) acrylate, single fluoroacetic acid copper (methyl) acrylate; Magnesium acetate (methyl) acrylate, calcium acetate (methyl) thirdOlefin(e) acid ester, zinc acetate (methyl) acrylate, copper acetate (methyl) acrylate; Propionic acid magnesium (methyl) acrylate, calcium propionate(methyl) acrylate, zinc propionate (methyl) acrylate, propionic acid copper (methyl) acrylate; Sad magnesium (methyl) acrylic acidEster, calcium octoate (methyl) acrylate, zinc octoate (methyl) acrylate, cupric octoate (methyl) acrylate; Neodecanoic acid magnesium (firstBase) acrylate, neodecanoic acid calcium (methyl) acrylate, zinc neodecanoate (methyl) acrylate, neodecanoic acid copper (methyl) propyleneAcid esters; Isostearic acid magnesium (methyl) acrylate, isostearic acid calcium (methyl) acrylate, isostearic acid zinc (methyl) acrylic acidEster, isostearic acid copper (methyl) acrylate; Magnesium palmitate (methyl) acrylate, calcium palmitate (methyl) acrylate, palm fibrePalmitic acid acid zinc (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) thirdOlefin(e) acid ester; β-naphthoic acid magnesium (methyl) acrylate, β-naphthoic acid calcium (methyl) acrylate, β-naphthoic acid zinc (methyl) propyleneAcid esters, β-naphthoic acid copper (methyl) acrylate; Magnesium benzoate (methyl) acrylate, calcium benzoate (methyl) acrylate,Zinc benzoate (methyl) acrylate, copper benzoate (methyl) acrylate; 2,4,5-trichlorophenoxyacetic acid magnesium (methyl) thirdOlefin(e) acid ester, 2,4,5-trichlorophenoxyacetic acid calcium (methyl) acrylate, 2,4,5-trichlorophenoxyacetic acid zinc (methyl) propyleneAcid esters, 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-bis-Tomatotone copper (methyl) acrylate; Quinoline carboxylic acid's magnesium (methyl) acrylate, quinoline carboxylic acid's calcium (methyl) acrylic acidEster, quinoline carboxylic acid's zinc (methyl) acrylate, quinoline carboxylic acid's copper (methyl) acrylate; Nitrobenzoic acid magnesium (methyl) acrylic acidEster, nitrobenzoic acid calcium (methyl) acrylate, nitrobenzoic acid zinc (methyl) acrylate, nitrobenzoic acid copper (methyl) thirdOlefin(e) acid ester; Nitronaphthoic acid magnesium (methyl) acrylate, nitronaphthoic acid calcium (methyl) acrylate, nitronaphthoic acid zinc (firstBase) 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 in them a kind of choice for useOr two or more. Wherein, if use the monomer that contains zinc, the transparency of the vinyl based polymer obtaining uprises, by comprisingThe color of the film that the antifouling paint resin combination of the vinyl based polymer obtaining obtains smartens up, so preferably.And then, from the viewpoint of the durability of the film that obtains, more preferably use fatty acid zinc (methyl) acrylate (M of formula (1)For zinc, R2For fatty acid residue). Wherein, " (methyl) acrylate " meaning is " acrylate " or " methacrylate ".
The ethylene unsaturated monomer that contains divalent metal (a2b) shown in general formula (1) by make inorganic metal compound,The ethylene unsaturated monomer that contains carboxyl and corresponding to the organic acid residue R in formula (1)2Non-polymerization organic acid existDiluent or the ethylene unsaturated monomers etc. such as organic solvent have in the reactive diluent of polymerism unsaturated group and reactMethod obtain.
Wherein, as the ethylene unsaturated monomer that contains divalent metal (a2), from the film that can long term maintenance obtainsFrom polishability, can obtain the viewpoint of good soil resistance, preferably and by aforementioned monomer (a2a) and aforementioned monomer (a2b).Be more preferably as (methyl) zinc acrylate resin of aforementioned monomer (a2a) with as the fatty acid zinc (methyl) of aforementioned monomer (a2b)(M of formula (1) is zinc, R to acrylate2For fatty acid residue) combination.
Also by aforementioned monomer (a2a) and aforementioned monomer (a2b) in the situation that, in monomer mixture (M2), (be that monomer is mixedIn whole monomers of compound (M1) and monomer mixture (M2)), the mol ratio of aforementioned monomer (a2a) and aforementioned monomer (a2b)(a2a/a2b) preferably in 10/90～90/10 scope, more preferably in 20/80～80/20 scope, most preferably 30/In 70～70/30 scope. If this ratio (a2a/a2b), below 90/10, can obtain resistance to cracking line, adaptation excellenceFilm, if more than 10/90, there is the tendency from polishability of the film can long term maintenance obtaining.
In addition the monomer mixture that, contains aforementioned monomer (a2a) and aforementioned monomer (a2b) is by making inorganic metal chemical combinationThing, the ethylene unsaturated monomer that contains carboxyl and corresponding to the organic acid residue R in formula (1)2Non-polymerization organic acidWith aforementioned method of similarly reacting in the diluents such as organic solvent or ethylene unsaturated monomer isoreactivity diluent etc.Obtain.
Now, preferably non-polymerization organic acid content is 0.01～3 times mole with respect to inorganic metal compound. More excellentElect 0.01～0.95 times mole as, more preferably 0.1～0.7 times mole. If non-polymerization organic acid content isMore 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 3 times moles withUnder, there is the tendency that can longer-term maintains the soil resistance of the film obtaining.
The content of the ethylene unsaturated monomer (a2) that contains divalent metal, preferably according to the embodiment of the present inventionMonomer (the monomer of the amount of monomer of monomer mixture (M1) and monomer mixture (M2) used in the manufacture of vinyl based polymerTotal amount) in, in the scope of 1～40 quality %, more preferably in the scope of 7～25 quality %. If contain divalent metalThe content of ethylene unsaturated monomer (a2) be more than 1 quality %, the film obtaining become good from polishability for a long time.If this content is below 40 quality %, exist the antifouling paint storage-stable of resin combination, film adaptation,The tendency that the balance of the resistance to water in seawater and hardness and resistance to cracking improves.
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, go out from the viewpoint of copolymerizableSend out, preferably (methyl) acrylate. Viewpoint from antifouling paint with the storage-stable of resin combination, preferred monomers is mixedThe ethylene unsaturated monomer that does not contain carboxyl in compound (M2).
[macromonomer (a3)]
In manufacture method according to the embodiment of the present invention, aforementioned monomer mixture (M1) and aforementioned monomer mixture(M2) at least either party in comprises the macromonomer (a3) with free-radical polymerised group. By making to comprise large molecule listThe monomer mixture polymerization of body (a3), can not make the resistance to cracking of the film obtaining worsen, and can improve hardness of film, further alsoCan improve resistance to water.
The number-average molecular weight (Mn) of the polystyrene conversion of passing through gel permeation chromatography of macromonomer (a3)Preferably, in 200～16000 scope, more preferably, in 300～15000 scope, the scope below 10000 is suitable, entersOne step is preferably in 400～8000 scope, in 500～6000 scope. If macromonomer (a3)Mn is more than 200, further, if more than 300, and the hardness of the film that existence obtains, the resistance to water in seawater and closeThe tendency that closing property improves. If the Mn of macromonomer (a3), below 16000, further, if below 15000, depositsThe tendency improving with the storage-stable of resin combination at antifouling paint.
(monomer mixes whole monomers used in the manufacture of vinyl based polymer according to the embodiment of the present inventionThe total amount of the monomer of the monomer of thing (M1) and monomer mixture (M2)) in, the content of macromonomer (a3) is preferably 1～35In the scope of quality %, more preferably in the scope of 5～25 quality %. If the content of macromonomer (a3) is 1 quality %Above, the tendency that the hardness of the film that existence obtains, the resistance to water in seawater and adaptation improve, 35 quality % ifBelow, the tendency that exists storage-stable to improve.
As macromonomer (a3), can use to there is the main chain shown in following formula, there is terminal double bond as freedomThe monomer of base polymerizable group:
-(C(X)(COOR)-CH2)n-H
(in formula, X is hydrogen atom or methyl, and R is hydrogen atom, silicyl, replacement or unsubstituted alkyl, replacement or notThe cycloalkyl or replacement or the unsubstituted aryl that replace, the integer that n is 1～150)
N is preferably 3～150. The carbon number of the alkyl of R is preferably 1～12. The silicyl of R is preferably tributyl firstThe trialkylsilkls such as silylation, triisopropyl silicyl. Here, replace the meaning be have epoxy radicals, hydroxyl, cyano group,The substituting groups such as amino, carboxyl, substituted cycloalkyl and substituted aryl can also have alkyl as replacement except these substituting groupsBase, the carbon number of this alkyl is preferably 1～6.
As macromonomer (a3), can use at the vinyl from ethene base system monomer shown in following formula (A)The end of based polymer has the macromonomer of (methyl) acryloyl group.
[changing 1]
In formula (A), X, Y are hydrogen atom or methyl independently of one another, RnBe hydrogen atom, silicyl independently of one another, getGeneration or unsubstituted alkyl, replacement or unsubstituted cycloalkyl or replacement or unsubstituted aryl, R ' is for having carbon numberThe group of 1～12 alkylidene, the integer that n is 1～150. N is preferably 3～150. RnThe carbon number of alkyl be preferably 1～12。RnSilicyl be preferably the trialkylsilkl such as tributyl silicyl, triisopropyl silicyl. Here get,In generation,, the meaning was to have the substituting groups such as epoxy radicals, hydroxyl, cyano group, amino, carboxyl, and substituted cycloalkyl and substituted aryl are got except theseBeyond Dai Ji, can also have alkyl as substituting group, the carbon number of this alkyl is preferably 1～6.
As the macromonomer shown in formula (A), for example can be by making under the existence of chain-transferring agent with carboxylEthylene unsaturated monomer polymerization, synthetic end has the prepolymer of carboxyl, then, makes carboxyl and the metering system of this prepolymerAcid glycidyl ester generation addition reaction and obtaining, but be not particularly limited.
As macromonomer (a3), can use the end shown in following formula (B) to there is α, β-ethene unsaturated groupThe macromonomer of group.
[changing 2]
In formula (B), Z is hydrogen atom or methyl, and R is hydrogen atom, silicyl, replacement or unsubstituted alkane independently of one anotherBase, replacement or unsubstituted cycloalkyl or replacement or unsubstituted aryl, the integer that n is 1～150. N is preferably more than 2,More preferably more than 3, be preferably in addition below 149. The carbon number of the alkyl of R is preferably 1～12. The silicyl of R is preferredFor trialkylsilkls such as tributyl silicyl, triisopropyl silicyls. Here, replace the meaning be have epoxy radicals,The substituting groups such as hydroxyl, cyano group, amino, carboxyl, substituted cycloalkyl and substituted aryl can also have except these substituting groupsAlkyl is as substituting group, and the carbon number of this alkyl is preferably 1～6.
As the macromonomer shown in formula (B), for example can be by making ethylene unsaturated monomer at 150～350 DEG CCarry out radical polymerization and obtain.
In addition, the macromonomer shown in formula (B) for example can make ethylene unsaturated monomer by using cobalt complex(the chain transfer polymerization method of the catalyst) polymerization of CCTP method and obtain.
As cobalt complex, for example, can use the cobalt complex shown in following formula. For example, can use Japan PatentNo. 3587530 communiques, Japanese Patent Publication 6-23209 communique, Japanese Patent Publication 7-35411 communique, USP45269945 public affairsReport, USP4694054 communique, USP4837326 communique, USP4886861 communique, USP5324879 communique, WO95/The cobalt complex of recording in No. 17435 communiques, the flat 9-510499 communique of Japanese Unexamined Patent Application Publication etc.
[changing 3]
(in formula, R1～R4Be alkyl, cycloalkyl or aryl independently of one another, X is F atom, Cl atom, Br independently of one anotherAtom, OH base, alkoxyl, aryloxy group, alkyl or aryl. )
Particularly, can enumerate two (boron difluoro dimethyl two oxyimino group cyclohexanes) cobalts (II), two (boron difluoro diformazanBase glyoxime root closes) cobalt (II), two (boron difluorodiphenyl base glyoxime root closes) cobalt (II), adjacent imino group oxyimino compoundCobalt (II) complex compound, cobalt (II) complex compound, the N of four azepine tetraalkyl ring 14 carbon tetraenes, N '-bis-(salicylidene) second diaminoCobalt (II) complex compound of base cobalt (II) complex compound, dialkyl group diaza dioxo dialkyl group 12 carbon diene, cobalt (II) porphyrin networkThe cobalt complexs such as compound.
Cobalt complex is one or more in them of choice for use suitably. Wherein, preferably can in polymerizationStable existence, in ethylene unsaturated monomer high two (boron difluorodiphenyl base glyoxime root closes) cobalt (the II) (R of dissolubility1～R4: phenyl, X:F atom).
The content of cobalt complex is preferably with respect to the unsaturated list of ethene using in order to obtain macromonomer (a3)Body 100g is 20 to 350ppm. 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) acrylic acid firstEster, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate,(methyl) 2-EHA, the positive lauryl of (methyl) acrylic acid, the positive stearyl ester of (methyl) acrylic acid, (methyl) acrylic acidCyclohexyl, (methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) isobornyl acrylate, 2-methoxy ethyl (firstBase) (methyl) acrylic acid such as acrylate, 2-ethoxyethyl group (methyl) acrylate, phenoxy group ethyl (methyl) acrylateEster; 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, 4-hydroxybutyl (methyl) acrylic acid(methyl) acrylate that ester, glycerine (methyl) acrylate etc. contain hydroxyl; (methyl) acrylic acid, 2-(methyl) acryloyl-oxyBase ethyl hexahydrophthalic acid, 2-(methyl) acryloxy propyl group hexahydrophthalic acid, 2-(methyl) acryloxyEthyl phthalic acid, 2-(methyl) acryloxy propyl group phthalic acid, 2-(methyl) acryloxy ethyl maleic acid,2-(methyl) acryloxy propyl group maleic acid, 2-(methyl) acryloxy ethyl butanedioic acid, 2-(methyl) acryloxyPropyl group butanedioic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, monomethyl itaconate etc. contain carboxylEthene base system monomer; The ethene base system monomer that maleic anhydride, itaconic anhydride etc. contain anhydride group; (methyl) acrylic acid glycidolEster, α-ethylacrylate ethylene oxidic ester, (methyl) acrylic acid 3, the ethene base system monomer that 4-epoxy butyl ester etc. contains epoxy radicals;Dimethyl aminoethyl (methyl) acrylate, diethylamino ethyl (methyl) acrylate etc. contain amino (methyl) thirdOlefin(e) acid ester is ethene base system monomer; (methyl) acrylamide, the N-tert-butyl group (methyl) acrylamide, N-methylol (methyl) propyleneAcid amides, N-methoxy (methyl) acrylamide, N-butoxymethyl (methyl) acrylamide, DAAM, horseCarry out the ethene base system monomer that acid amides, maleimide etc. contain amide groups; Vinyl pyrrolidone, vinylpyridine, vinylThe heterocycles such as carbazole are alkaline monomer, styrene, vinyltoluene, AMS, acrylonitrile, methacrylonitrile, acetic acid secondThe ethene base system monomers such as alkene ester, propionate; Methoxyl group ethylene glycol allyl ether, methoxy poly (ethylene glycol) allyl ether, firstOxygen base polypropylene glycol allyl ether, butoxy polyethylene glycol allyl ether, butoxy polypropylene glycol allyl ether, the poly-second of methoxyl groupThe end alkoxy group allylation polyethers such as glycol-polypropylene glycol allyl ether, butoxy polyethylene glycol-propane diols allyl etherMonomer; Ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylic acidEster, polyethylene glycol two (methyl) acrylate, BDO two (methyl) acrylate, 1,6-hexylene glycol two (methyl) propyleneAcid esters, neopentyl glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, 1,10-decanediol two (methyl)Acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six(methyl) acrylate, allyl methacrylate, triallyl cyanurate, diallyl maleate, polypropylene glycol dieneThe polyfunctional monomers such as propyl ether. Suitably choice for use is one kind or two or more for they.
Wherein, " (methyl) acrylate " meaning is " acrylate and/or methacrylate ", " (methyl) acrylic acid "The meaning is " acrylic acid and/or methacrylic acid ", and " (methyl) acryloyl group " meaning is " acryloyl group and/or methacrylBase ", " (methyl) acrylamide " meaning is " acrylamide and/or Methacrylamide ".
As the manufacture method of macromonomer (a3), for example, can apply suspension polymerization, mass polymerization, solution poly-The known polymerizations such as legal, emulsion polymerization. Wherein, preferably after polymerization by filtering, washing, dehydration, dry canEasily obtain the suspension polymerization of 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) polymerizationObtain with the operation (2) that makes monomer mixture (M2) polymerization. Now, in monomer mixture (M1) and monomer mixture (M2) extremelyFew either party comprises macromonomer (a3). To by a polymerization liquid that operation obtains in operation (1) and operation (2)In add by the monomer mixture of another operation polymerization, carry out polymerization. By carrying out such polymerization technique, the ethene obtainingBase system polymer becomes block copolymer. The resistance to water of the film obtaining like this, and hardness improve.
The polymerization of operation (1) and operation (2) can be used known polymerization initiator to be undertaken by known method. From controlThe viewpoint of the molecular weight of the vinyl based polymer making is set out, preferred solution polymerization.
The polymerization initiator using in polymerization as operation (1) and operation (2), can enumerate for example t-butyl peroxyChange-2 ethyl hexanoic acid ester, two-tert-butyl peroxide, lauroyl peroxide, benzoyl peroxide, the peroxidation acid tert-butyl esterDeng organic peroxide, 2,2 '-azobis isobutyronitrile (AIBN), 2,2 '-azo two (2-methylbutyronitriles) azo system such as (AMBN)Compound. Polymerization initiator can be used alone or two or more kinds may be used. The not special limit of the content of polymerization initiatorFixed, can suitably set.
The polymerization temperature of operation (1) and operation (2) is preferably 60～180 DEG C. About the polymerization of operation (1) and operation (2)The total of time, preferred reaction 5～14 hours.
In the polymerization of operation (1) and operation (2), can use as required known chain-transferring agent. Shift as chainAgent, can enumerate thioglycolic acid ester class, the Alpha-Methyl benzene such as the thio-alcohols such as such as n-dodecyl mercaptan, thioglycolic acid monooctyl esterEthylene dimerization thing, 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, as object lesson, and canEnumerate the unary alcohols such as methyl alcohol, ethanol, isopropyl alcohol; The polyalcohols such as ethylene glycol, 1,2-PD; Acetone, methyl ethyl ketone, secondThe ketones such as acyl acetone; The ethers such as methyl ethyl ether, diox; Ethylene glycol monoethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether,Propane diols list n-propyl ether, glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, DPG list propyl ether etc.Glycol ethers; The ethyl glycol acetate classes such as ethylene glycol acetate, ethylene acetate, ethylene glycol monomethyl ether acetate; Positive pentaThe fatty family hydro carbons such as alkane, n-hexane; The fragrant family hydro carbons such as toluene, dimethylbenzene, solvent naphtha; Aforementioned allylation polyethersMonomer. These solvents can use separately a kind, or also two or more kinds may be used. Wherein, in order to make to comprise the ethene obtainingThe water-based antifouling paint of base system polymer is good with manufacture stability and the dispersion stability of resin combination, preferably contains alcoholBased compound.
Be not particularly limited preferred mass as monomer mixture (M1) and the ratio of the use level of monomer mixture (M2)Ratio (M1/M2) is in 15/85～85/15 scope, more preferably in 20/80～80/20 scope. If in this scopeIn, the tendency that exists the storage-stable 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 list to the polymerization liquid after operation (1)Body mixture (M2) and carry out operation (2), also can add monomer mixture (M1) and enter to the polymerization liquid after operation (2)Row operation (1). Become well from the dispersion stabilization of the vinyl based polymer that obtains, preferably carrying out after operation (1)Carry out operation (2).
The molecular weight of the vinyl based polymer obtaining in addition, can suitably be determined according to desired characteristic. For example, canThe weight average molecular weight of the polystyrene conversion by gel permeation chromatography (Mw) is set in to 1,000～50,000Scope.
[water-based antifouling paint resin combination]
The vinyl based polymer obtaining by the polymerization that comprises operation (1) and operation (2) is dispersed in to water or bagIn the decentralized medium that moisture and mixture organic solvent forms, thereby can obtain water according to the embodiment of the present inventionProperty antifouling paint resin combination. From the viewpoint of film forming, soil resistance, the water-based antifouling paint group preferably obtainingIn compound, contain vinyl based polymer with the scope of 20～60 quality %. After polymerization finishes, before dispersion step, can be by logicalNormal method is removed the desolventizing operation of polymerization organic solvent used.
After part or all neutralization that will the carboxyl in the vinyl based polymer obtaining, being dispersed in aforementioned dispersion is situated betweenIn matter, be preferred from the viewpoint of the smooth transfer to water.
Aforementioned neutralization can be undertaken by add alkali compounds in vinyl based polymer. As the alkalescence usingCompound is not particularly limited, for example, and the alkane such as preferred ammoniacal liquor (aqueous solution), trimethylamine, triethylamine, diisopropylethylamine, butylamineBase amine; Dimethylethanolamine (DMEA), dimethylisopro panolamine, methyl diethanolamine, diethyl ethylene diamine, triethanolamine,The alcamines such as butanolamine; Morpholine, IPD etc. Alkali compounds can use a kind, and also two or more kinds may be used.
These alkali compounds preferably with the mole of the carboxyl contained with respect to vinyl based polymer become 40～The mode of 150% mol ratio coordinates, and more preferably 60～120%. By neutralizing with alkali compounds, can be byAntifouling paint is made as preferred 6.0～11.0 with the pH of resin combination, and more preferably 6.5～9.0.
As aforementioned decentralized 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, go out from dispersed viewpointSend out the alcohol based compounds such as preferred alcohols, glycol ethers. Wherein, as alcohol, can suitably use carbon number 1～6 that boiling point is lower,The preferably monohydric alcohol of carbon number 2～4, as glycol ethers, can suitably use carbon number 3～11, preferably carbon number 3～8 glycol ethers.
Content as aforementioned water-based antifouling paint with aforementioned organic solvent in resin combination, be preferably 20 quality % withUnder, more preferably below 10 quality %.
Water-based antifouling paint according to the embodiment of the present invention can coordinate anti-fouling agent as required with resin combination.As this anti-fouling agent, the suitable choice for use of performance as requested, for example, with copper such as cuprous oxide, cupric thiocyanate, copper powdersBe headed by anti-fouling agent, can enumerate lead, zinc, nickel etc. other the amine derivative such as metallic compound, diphenylamine, nitrile compound,Benzothiazole based compound, maleimide amine compound, pyridine based compound etc. They can use separately a kind or combinationUse two or more. More specifically, can enumerate ethylidene dithiocarbamate manganese, dimethyl dithiocarbamic acidZinc, 2-methyl sulfo--4-tert-butyl group amino-6-cyclopropylamino-s-triazine, 2,4,5,6-daconil M, N, N-diformazanBase dichlorophenyl urea, zinc ethylene bisdithiocarbamate, cuprous sulfocyanide, 4, the different thiophene in the chloro-2-of 5-bis-n-octyl-3 (2H)Oxazolone, N-(fluorine dichloromethyl sulfo-) phthalimide, N, N '-dimethyl-N '-phenyl-(N-fluorine dichloromethyl sulfo-)Sulphamide, 2-mercaptopyridine-1-oxide zinc salt, tetramethyl thiuram disulfide, Cu-10%Ni solid solution alloy, 2,4,6-Trichlorophenyl maleimide 2,3,5,6-tetrachloro-4-(mesyl) pyridine, the iodo-2-propynyl butyl of 3-carbamic acid, twoIodomethyl to three sulfones, two DMDS for carbamoyl zinc ethylenebis dithiocarbamate, phenyl (two pyridinesBase) bismuth dichloride, 2-(4-thiazolyl)-benzimidazole, pyridine-triphenylborane etc.
Water-based antifouling paint is according to the embodiment of the present invention with in resin combination, for giving profit to film coated surfaceSlip, prevent from the object of biological attachment from can coordinating the fluorinated such as the silicon compound such as dimethyl polysiloxane, silicone oil, fluorocarbonsCompound etc.
And then, water-based antifouling paint according to the embodiment of the present invention with resin combination can contain various pigment,Defoamer, pigment dispersing agent, levelling agent, antisag agent, delustering agent, ultra-violet absorber, antioxidant, heat resistance improving agent, refreshingLubrication prescription, anticorrisive agent, plasticizer, other latex resins, water-soluble resin, viscosity controlling agent etc.
Used water-based antifouling paint resin combination according to the embodiment of the present invention film can boats and ships,On various fishing nets, bay base coating film, be coated with. As this base coating film, can use wash primer, chlorinated rubber system, epoxy system etc.The formation such as priming paint, floating coat paint. The film being obtained by resin combination according to the embodiment of the present invention can be at baseOn base coating film on material surface or base material, be coated with fabric aqueous antifouling paint by methods such as brushing, spraying, roller coat, the coatings of heavy stain and use treeOil/fat composition. Generally speaking coating weight can be set as counting with dry coating the amount of the thickness of 10～400 μ m. Being dried of filmConventionally can at room temperature carry out, also can carry out as required heat drying.
Embodiment
Below, by embodiment and comparative example, the present invention is described in further detail. Wherein, part in embodimentRepresent 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 name: HLC-8220). Pillar uses businessThe name of an article: TSKgel α-M (TOSOH Co., Ltd's system, 7.8mm × 30cm), trade name: TSKguardcolumn α (eastern Cao's strain formula meetingSociety's system, 6.0mm × 4cm). Calibration curve use polystyrene standard (TOSOH Co., Ltd's system, trade name: F288, F128,F80, F40, F20, F2, A1000) and styrene monomer make. Modulation makes sample (polymer) to become the side of 0.4 quality %DMF (DMF) solution that formula is dissolved, uses the DMF solution 100 μ l that modulate, and measures at 40 DEG C. Pass throughPolystyrene standard converts, and calculates number-average molecular weight (Mn).
(storage-stable evaluation)
Water-based antifouling paint is preserved 1 month at normal temperatures with resin combination P1～P17, confirmed sediment by range estimationHave or not. Evaluate and undertaken by following benchmark:
Zero: resinous principle does not precipitate, separates, there is no coagulative formation,
△: there is a small amount of sediment, but can disperse through stirring,
×: resinous principle precipitates, separates, solidifies, and no longer disperses even if stir also.
(Martens hardness)
On glass substrate, be coated with respectively fabric aqueous antifouling paint resin combination P1～P17 with 4mil applicator, in chamberLower dry 2 weeks of temperature, produces breadboard, for the film of these breadboards, utilizes the super micro-hardness tester (Fisher of Co., Ltd.Instruments sample processed, trade name: HM2000) mensuration Martens hardness. Wherein, Martens hardness is preferably 2.0～15.0N/mm2Scope, more preferably 2.5～10.0N/mm2Scope.
(Water Resistance Test)
On glass substrate, be coated with respectively fabric aqueous antifouling paint resin combination P1～P17 with 4mil applicator, in chamberLower dry 1 week of temperature, produces breadboard. The breadboard obtaining is flooded after 1 month in sterilising filtration seawater, by these testsPlate is dried 1 week under the room temperature of 20 DEG C of temperature. Measure with mist degree instrument (color technical research institute system, trade name: HM-150 in village)The albefaction degree of the film coated surface of dried breadboard. 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.
(fissility test)
The breadboard of similarly making with aforementioned Water Resistance Test is flooded after 1 month in sterilising filtration seawater, by thisA little breadboards are dried 1 week under the room temperature of 20 DEG C of temperature, carry out disbonded test. About disbonded test, on film, pasteCELLOTAPE (registration mark) also peels rapidly, evaluates 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(TiO2) 1 part of 20 part, surfactant (Asahi Denka Co., Ltd.'s system, trade name: ADEKACOLW193), stir, obtainComplex. Respectively the complex obtaining is become with dry film thickness on the hard vinyl chloride plate of 50mm × 50mm × 2mm (thickness)The mode applicator that is 120 μ m is coated with, and produces breadboard. These breadboards are arranged on the rotating cylinder of being located in seawater,Make its rotation with peripheral speed 7.7m/s (15knot). After 1 month, take out breadboard, measure thickness. Obtain 1 by following formulaThe consumption degree (μ m/M) of the film after month:
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 dispersant 1)
Possessing in the polyplant of mixer, cooling tube, thermometer, add 900 parts of deionized waters, methacrylic acid 2-60 parts of sulfo group ethyl sodiums, 10 parts, methacrylic acid potassium and 12 parts of methyl methacrylates (MMA) also stir, on one side to polymerizationIn device, carry out nitrogen replacement, be warming up to 50 DEG C on one side. Add therein 0.08 part 2, two (the 2-methyl-prop amidine) disalts of 2 '-azoHydrochlorate, as polymerization initiator, is further warming up to 60 DEG C. After intensification, use dropping liquid pump is the speed with 0.24 part/minute by MMADrip 75 minutes continuously. Reaction solution is kept, after 6 hours, being cooled to room temperature at 60 DEG C, obtain consolidating as transparent aqueous solutionThe dispersant 1 of body composition 10 quality %.
(manufacture of chain-transferring agent 1)
In the synthesizer that possesses agitating device, under nitrogen atmosphere, add cobalt acetate (II) tetrahydrate 1.00g andDiphenyl glyoxime 1.93g, the diethyl ether 80ml that has carried out in advance deoxidation by nitrogen gas foaming, at room temperature stir 30 minutes.Then, add boron trifluoride diethyl ether complex compound 10ml, further stir 6 hours. Filtering mixt, solid with diethyl ether washingBody, vacuum drying 15 hours, obtains the chain-transferring agent 1 of 2.12g as bronzing solid.
(modulation of macromonomer)
Possessing in the polyplant of mixer, cooling tube, thermometer, add 145 parts of deionized waters, 0.1 part, sodium sulphateWith 0.25 part of dispersant 1 (solid constituent 10 quality %) stirring, make the uniform aqueous solution. Then, add 100 parts of MMA,1 and 0.2 part 1,1,3 of 0.002 part of chain-transferring agent, 3-tetramethyl butyl peroxidating 2 ethyl hexanoic acid ester (Japan Oil Co's system, businessThe name of an article: PEROCTAO), obtain aqueous suspension.
Then,, to carrying out nitrogen replacement in polyplant, be warming up to 80 DEG C and react 1 hour. Poly-in order further to improveClose rate, be warming up to 90 DEG C and keep 1 hour. Afterwards, make reactant liquor be cooled to 40 DEG C, the water-based that obtains macromonomer is suspendedLiquid. Nylon filter-cloth filtering by this aqueous suspension with mesh 45 μ m, washs filtrate and dewaters by deionized water,Be dried 16 hours at 40 DEG C, obtain being equivalent to the macromonomer (a3-1) of the macromonomer shown in formula (B). This large molecule listMn=7000, the Mw/Mn=2.0 of body (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), systemMake 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 materialMn with 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,
PEROCTAO (trade name): 1,1,3,3-tetramethyl butyl peroxidating 2 ethyl hexanoic acid ester (Japan Oil CoSystem).
[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 mixer, temperature adjuster, dropper, add MMA70 part and zinc oxide (ZnO)41 parts, stir while be warming up to 75 DEG C. Dripped and comprise 34 parts of methacrylic acids (MAA), acrylic acid wherein with 3 hours(AA) mixture that 29 parts, sad 29 parts, water are 5 parts. After dropping finishes, reaction solution becomes transparent from milky state. Enter oneStep stirred after 2 hours, added MMA39.7 part, obtained the ethylene unsaturated monomer (a2-1) that transparent comprising contains divalent metalMonomer mixture (m2-1). Table 2 represents the contained second that contains metal in the input amount, monomer mixture (m2-1) of each raw materialThe concentration of alkene unsaturated monomer (a2-1). Its concentration is set as 50 quality % by adjustment by amount of moisture.
[comprise respectively the ethylene unsaturated monomer (a2-2) that contains divalent metal, the monomer mixture (m2-of (a2-3)2), 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), makeReplace MMA with PGM. Table 2 represents the contained metal that contains in the input amount, monomer mixture (m2-2), (m2-3) of each raw materialThe concentration of ethylene unsaturated monomer (a2-2), (a2-3). Their concentration is set as 50 matter by adjustment by amount of moistureAmount %. 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 mixer, temperature adjuster, dropper, drop into organic solvent (trade name:SOLVESSO100, exxonmobil chemical company's system) 15 parts, stir while be warming up to 130 DEG C. Then, as described below enterRow comprises the polymerization of operation 1 and operation 2.
< operation 1 >
Then, the monomer mixture (M1) that comprises following raw material with dropping in 2 hours, further carries out copolymerization in 0.5 hour anti-Should.
The composition of monomer mixture (M1):
Macromonomer (a3-1): 15 parts,
N-BA:20 part,
MAA:7 part,
Tert-butyl hydroperoxide 2 ethyl hexanoic acid ester (PERBUTYLO, 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 copolymerization in 0.5 hour anti-Should.
The composition of monomer mixture (M2):
M2-1:20 part (wherein, 10 parts of the ethene unsaturated ethylene base system monomer solid constituents that contains divalent metal),
MMA:7.8 part,
N-BA:23 part,
2-methoxy ethyl methacrylate (2-MTMA): 7.2 parts,
Chain-transferring agent (trade name: NOFMERMSD, Japan Oil Co's system): 1.5 parts,
Tert-butyl hydroperoxide 2 ethyl hexanoic acid ester (trade name: PERBUTYLO, Japan Oil Co's system): 5 parts.
Then, further add 0.5 part of PERBUTYLO (trade name), further continue to carry out 1 hour polymerisation,To vinyl based polymer A1.
100 parts of vinyl based polymer A1 that obtain are stirred while be heated to 80 DEG C, add dimethylethanolamine(DMEA) 5.7 parts, mix until evenly, then, slowly add 90 parts of deionized waters, obtain vinyl based polymer A1 and divideBe dispersed in the water-based antifouling paint resin combination P1 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 A2Resin combination P2～P17 for～A17 and water-based antifouling paint. Evaluation result is shown in to table 3.
In monomer mixture (M1), (M2), all do not use the ratio of the macromonomer (a3) with free-radical polymerised group, in example 1, the vinyl based polymer obtaining is random copolymer, therefore, and the film that comprises this vinyl based polymer hardDegree, resistance to water is insufficient. And in embodiment 1～15, obtain resistance to water 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 does not fillPoint, do 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 mixture that comprises the ethylene unsaturated monomer that contains divalent metal(m2) amount
The numerical value of hypomere in the m2 of operation 2, a2 hurdle: the ethene that contains divalent metal contained in mixture m2 is unsaturatedThe content of monomer (a2).
Claims (9)
1. a manufacture method for vinyl based polymer, it comprises: make to comprise the ethylene unsaturated monomer that contains carboxyl(a1) operation (1) of monomer mixture (M1) polymerization and make to comprise the ethylene unsaturated monomer (a2) that contains divalent metalThe operation (2) of monomer mixture (M2) polymerization,
At least either party in described monomer mixture (M1) and monomer mixture (M2) comprises and has free-radical polymerised groupMacromonomer (a3),
Described macromonomer (a3) has the main chain shown in following formula, and has terminal double bond as described free-radical polymerisedGroup,
-(C(X)(COOR)-CH2)n-H
In formula, X is hydrogen atom or methyl, and R is hydrogen atom, silicyl, replacement or unsubstituted alkyl, replacement or unsubstitutedCycloalkyl or replacement or unsubstituted aryl, the integer that n is 1～150,
Add monomer mixture (M2) to the polymerization liquid after operation (1) thus carry out operation (2), or to after operation (2)Polymerization liquid adds monomer mixture (M1) thereby carries out operation (1).
2. the manufacture method of vinyl based polymer according to claim 1, passing through of described macromonomer (a3) is solidifyingThe polystyrene conversion number-average molecular weight Mn of glue penetration chromatography determination is 300～15000.
3. the manufacture method of vinyl based polymer according to claim 1 and 2, described macromonomer (a3) is by followingFormula (A) expression,
In formula (A), X, Y are hydrogen atom or methyl independently of one another, RnBe hydrogen atom, silicyl, replacement or not independently of one anotherAlkyl, replacement or the unsubstituted cycloalkyl or replacement or the unsubstituted aryl that replace, R ' is for having carbon number 1～12The group of alkylidene, the integer that n is 1～150.
4. the manufacture method of vinyl based polymer according to claim 1 and 2, described macromonomer (a3) is by followingFormula (B) expression,
In formula (B), Z is hydrogen atom or methyl, R be independently of one another hydrogen atom, silicyl, replacement or unsubstituted alkyl,Replace or unsubstituted cycloalkyl or replacement or unsubstituted aryl the integer that n is 1～150.
5. the manufacture method of vinyl based polymer according to claim 1 and 2, mixed at monomer mixture (M1) and monomerIn whole monomers of compound (M2), in the scope of 1～35 quality %, coordinate described macromonomer (a3).
6. a vinyl based polymer, it obtains by the manufacture method described in any one in claim 1 to 5.
7. a water-based antifouling paint resin combination, it is by disperseing vinyl based polymer claimed in claim 6In the decentralized medium that comprises water and obtain.
8. water-based antifouling paint resin combination according to claim 7, the content of described vinyl based polymer existsIn the scope of 20～60 quality %.
9. according to the water-based antifouling paint resin combination described in claim 7 or 8, the content of organic solvent is 20 quality %Below.
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| 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 |
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| 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 |
| SG11201802099YA (en) * | 2015-09-25 | 2018-04-27 | Mitsubishi Chem Corp | (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 |
| 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 |
| 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 |
| SG11201908632RA (en) | 2017-03-29 | 2019-10-30 | Mitsubishi Chem Corp | (meth)acrylic copolymer, method for producing same, resin composition and antifouling paint composition |
| 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 |
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