CN103582657B - Copolymer containing metal, its manufacture method, antifouling paint compositions, antifouling paint and there are the article of film of this antifouling paint - Google Patents
Copolymer containing metal, its manufacture method, antifouling paint compositions, antifouling paint and there are the article of film of this antifouling paint Download PDFInfo
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- CN103582657B CN103582657B CN201280026999.6A CN201280026999A CN103582657B CN 103582657 B CN103582657 B CN 103582657B CN 201280026999 A CN201280026999 A CN 201280026999A CN 103582657 B CN103582657 B CN 103582657B
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- 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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
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- C—CHEMISTRY; METALLURGY
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Abstract
The present invention provides a kind of soil resistance coating composition and antifouling paint, and the copolymer containing metallic atom for them, though this soil resistance coating composition under static condition also can the excellent antifouling property of long term maintenance, do not produce paint film defect.The copolymer containing metal of the present invention has more than one structure selected from the structure shown in the structure shown in formula (1) and formula (2).In formula (1), M represents divalent metal, R1Represent the hydrocarbon of carbon number 2 or 3.N is any integer of 1 to 20.In formula (2), M represents divalent metal, R2～R5Represent hydrocarbon.M is 0 or 1.The antifouling paint compositions of the present invention contains the described copolymer containing metal.Formula (1)-COO-(R1-COO)n-M-formula (2)-COO-(R2-OCO-R3-COO)m-M-OCO-R4-COO-R5-OCO-。
Description
Technical field
The present invention relates to a kind of coating composition with soil resistance and be suitable for preparing this coating composition
Copolymer.In more detail, relating to a kind of coating composition with soil resistance and antifouling paint, this coating composition can be formed
Prevent the film that marine creature and seaweeds are attached on building in water, fishing net, hull bottom.
Background technology
The film formed by antifouling paint, utilizes its contained antifouling medicament dissolution to play anti-fouling effect to marine.
The film formed by the disintegration-type antifouling paint employing rosin series compound, if Long term immersion is marine, then dissolved element by
The fewest, dissolved element does not becomes many, and therewith, coated surface becomes concavo-convex, and its result prevents the biological attachment such as marine creature
Effect significantly reduces.On the other hand, hydrolysis-type antifouling paint the film formed, owing to film coated surface is gradually dissolved, surface is more
Newly (self-grind), film coated surface always exposes anti-fouling composition, thus can play long-term anti-fouling effect.
As hydrolysis-type antifouling paint, For example, Patent Document 1 discloses a kind of containing the resin combination containing metal
Hydrolysis-type antifouling paint compositions, the described resin combination containing metal is had at least by the terminal part at least one side chain
The resin of one group containing zinc, copper or tellurium atom, and the organic solvent composition of this resin of solubilized.Additionally, patent documentation 2
In propose a kind of hydrolysis-type antifouling paint compositions, it contains copolymer and antifouling medicament, and described copolymer is with containing gold
Belong to bond monomeric unit as constituent.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Laid-Open Patent Publication 62-057464 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2002-194270 publication
Summary of the invention
The problem that invention is to be solved
But, employ the antifouling paint of the copolymer containing metallic atom described in patent documentation 1 and patent documentation 2,
Due to water-disintegrable reduction, crack, the tendency having the soil resistance under static condition easily to reduce, exist and be difficult to be stood for a long time
The such problem of anti-fouling effect under state.
Present invention aim to address these problems, it is provided that a kind of antifouling paint compositions and antifouling paint, this is prevented
Even if dirty coating composition under static condition also can the excellent antifouling property of long term maintenance, do not produce paint film defect.Additionally,
The purpose of the present invention is for providing a kind of for this antifouling paint compositions and the copolymer containing metallic atom of antifouling paint.
For the method solving problem
Described purpose is realized by the following present invention (1)～(8).
(1) a kind of copolymer containing metal, it has more than one from shown in the structure shown in formula (1) and formula (2)
Structure in select structure.
Formula (1)
-COO-(R1-COO)n-M-
In formula (1), M represents divalent metal, R1Represent the hydrocarbon of carbon number 2 or 3.N is any integer of 1 to 20.
Formula (2)
-COO-(R2-OCO-RO-COO)m-M-OCO-R4-COO-R5-OCO-
In formula (2), M represents divalent metal, R2～R5Represent hydrocarbon.M is 0 or 1.
(2) copolymer containing metal as described in above-mentioned (1), it has more than one from the structure shown in formula (3), logical
The structure selected in the group that structure shown in formula (4) and the structure shown in formula (5) are formed.
Formula (3)
-COO-(R1-COO)n-M-(OCO-R6)p-OCO-
In formula (3), M represents divalent metal, R1And R6Represent the hydrocarbon of carbon number 2 or 3 independently of one another.N be 1 to 20 arbitrary
Integer, p is any integer of 0 to 20.
Formula (4)
-COO-(R1-COO)n-M-OCO-R4-COO-R5-OCO-
In formula (4), M represents divalent metal, R1Represent the hydrocarbon of carbon number 2 or 3, R4And R5Represent hydrocarbon.N be 1 to 20 arbitrary
Integer.
Formula (5)
-COO-(R1-COO)n-M-R7
In formula (5), M represents divalent metal, R1Represent the hydrocarbon of carbon number 2 or 3, R7Represent organic acid residue.N is 1 to 20
Any integer.
(3) manufacture method of the copolymer containing metal described in above-mentioned (1), it is to include the polymerism containing divalent metal
The monomer mixture of monomer (a) and the polymerizable monomer (b) without divalent metal carries out copolymerization, the described polymerism containing divalent metal
Monomer (a) contains more than one from the polymerizable monomer (a7) shown in the polymerizable monomer (a6) shown in formula (6), formula (7)
And the polymerizable monomer selected in the group that formed of the polymerizable monomer (a8) shown in formula (8).
Formula (6)
CH2=C (R8)-COO-(R1-COO)n-M-(OCO-R6)p-OCO-C(R9)=CH2
In formula (6), M represents divalent metal, R8And R9Represent H or CH independently of one another3, R1And R6Represent carbon number 2 or 3
Hydrocarbon.N is any integer of 1 to 20, and p is any integer of 0 to 20.
Formula (7)
CH2=C (R8)-COO-(R1-COO)n-M-OCO-R4-COO-R5-OCO-C(R9)=CH2
In formula (7), M represents divalent metal, R8And R9Represent H or CH independently of one another3, R1Represent the hydrocarbon of carbon number 2 or 3, R4
And R5Represent hydrocarbon.N is any integer of 1 to 20.
Formula (8)
CH2=C (R8)-COO-(R1-COO)n-M-R7
In formula (8), M represents divalent metal, R8Represent H or CH3, R1Represent the hydrocarbon of carbon number 2 or 3, R7Represent that organic acid is residual
Base.N is any integer of 1 to 20.
(4) manufacture method of the copolymer containing metal described in above-mentioned (1), it is will be containing the polymerism containing divalent metal
The monomer mixture of monomer (a) and the polymerizable monomer (b) without divalent metal carries out copolymerization, the described polymerism containing divalent metal
Monomer (a) contains the polymerizable monomer (a9) shown in formula (9).
Formula (9)
CH2=C (R8)-COO-(R2-OCO-R3-COO)m-M-OCO-R4-COO-R5-OCO-C(R9)=CH2
In formula (9), M represents divalent metal, R8And R9Represent H or CH independently of one another3, R2～R5Represent hydrocarbon.M is 0 or 1.
(5) manufacture method of the copolymer containing metal described in above-mentioned (4), described monomer mixture is possibly together with formula
(10) polymerizable monomer (a10) shown in.
Formula (10)
CH2=C (R8)-COO-R2-OCO-R3-COO-M-R7
In formula (10), M represents divalent metal, R8Represent H or CH3, R2And R3Represent hydrocarbon, R7Represent organic acid residue.
(6) a kind of antifouling paint compositions, it contains the copolymer containing metal described in above-mentioned (1) or (2).
(7) a kind of antifouling paint, it contains above-mentioned antifouling paint compositions.
(8) a kind of article, it has the film of above-mentioned antifouling paint.
Invention effect
The copolymer containing metal according to the present invention, using the teaching of the invention it is possible to provide one does not has the paint film defects such as crackle, even if standing
Antifouling paint compositions and the antifouling paint of long term maintenance excellent properties it also is able under state.
Detailed description of the invention
Below, embodiments of the present invention are illustrated.Further, in this specification, (methyl) acrylic acid refers to propylene
Acid or methacrylic acid.
(copolymer containing metal)
The copolymer containing metal of the present invention is the copolymer containing divalent metal, and it has more than one from described formula (1)
The structure selected in structure shown in shown structure and formula (2).Containing employing being total to containing metal with described structure
The antifouling paint of the antifouling paint compositions of polymers, it is possible to give the film obtained water-disintegrable with height.And then, this film resistance to
Anti-thread breakage also excellent, it is possible to the long-term anti-fouling effect playing excellence.From giving the film obtained with long-term soil resistance, resistance to crackle
From the viewpoint of property, the copolymer containing metal preferably has the structure shown in formula (1).
Additionally, the structure shown in formula (1) is preferably from the structure shown in the structure shown in described formula (3), formula (4)
And the structure selected in the group that formed of the structure shown in formula (5).
As the divalent metal contained in described structural formula, can the most suitably select, but from being total to containing metal
From the viewpoint of polymers dissolubility in water, be preferably from the group that zinc, copper, magnesium and calcium are formed select more than one,
From the viewpoint of the resistance to water of film, especially preferably zinc and copper.
The content of the structure shown in formula (1) in the copolymer containing metal, described or formula (2) be preferably 1 mass % with
On, more than especially preferably 2 mass %.More than 1 mass %, then the film obtained water-disintegrable well, and then resistance to crackle
Property good, it is possible to long-term play excellent anti-fouling effect.
(manufacture method of the copolymer containing metal)
The copolymer containing divalent metal of the present invention, can be obtained by the method for such as following (1) or (2).
(1) carry out the polymerizable monomer (a) containing divalent metal with the polymerizable monomer (b) without divalent metal being polymerized
" manufacture method 1 ".
(2) make metallic compound and unitary organic acid as required react with the copolymer (c) containing acidic group, or make
Slaine with unitary organic acid carries out " manufacture method 2 " of ester exchange with the copolymer (c) containing acidic group.
(manufacture method 1 of the copolymer containing divalent metal)
First, to by being polymerized containing the polymerizable monomer (a) of divalent metal and the polymerizable monomer (b) without divalent metal
" manufacture method 1 " that prepare illustrates.
As the polymerizable monomer (a) containing divalent metal, can enumerate containing more than one from gathering shown in described formula (6)
Polymerizable monomer (a7) shown in conjunction property monomer (a6), formula (7), the polymerizable monomer (a8) shown in formula (8), formula (9)
The polymerism list selected in the group that polymerizable monomer (a10) shown in shown polymerizable monomer (a9) and formula (10) is formed
The monomer of body or monomer mixture.From can give film with long-term soil resistance and resistance to anti-thread breakage from the point of view of, be particularly preferably polymerized
Property monomer (a6), (a7) and (a8).
Polymerizable monomer (a6)
As the object lesson of the polymerizable monomer (a6) shown in described formula (6), following polymerizable monomer can be enumerated:
Two (3-acryloxy propionic) zinc, two (3-acryloxy propionic) copper, two (3-acryloxy propionic) magnesium, two (3-first
Base acryloxy 2 Methylpropionic acid) zinc, two (3-methacryloxy 2 Methylpropionic acid) copper, two (3-methacryloxypropyls
Base 2 Methylpropionic acid) magnesium, (methyl) acrylic acid 3-acryloxy propionic zinc, (methyl) acrylic acid 3-acryloxy propionic
Copper, (methyl) acrylic acid 3-acryloxy propionic magnesium, (methyl) acrylic acid 3-methacryloxy 2 Methylpropionic acid zinc,
(methyl) acrylic acid 3-methacryloxy 2 Methylpropionic acid copper and (methyl) acrylic acid 3-methacryloxy 2-first
Base propanoic acid magnesium etc..
Polymerizable monomer (a7)
As the object lesson of the polymerizable monomer (a7) shown in described formula (7), following polymerizable monomer can be enumerated:
Succinic acid 2-(methyl) acryloyl-oxyethyl 3-acryloxy propionic zinc, succinic acid 2-(methyl) acryloyl-oxyethyl 3-
Acryloxy propionic copper, succinic acid 2-(methyl) acryloyl-oxyethyl 3-acryloxy propionic magnesium, succinic acid 2-(first
Base) acryloyl-oxyethyl 3-methacryloxy 2 Methylpropionic acid zinc, succinic acid 2-(methyl) acryloyl-oxyethyl 3-
Methacryloxy 2 Methylpropionic acid copper, succinic acid 2-(methyl) acryloyl-oxyethyl 3-methacryloxy 2-methyl
Propanoic acid magnesium, phthalic acid 2-(methyl) acryloyl-oxyethyl 3-acryloxy propionic zinc, phthalic acid 2-(methyl)
Acryloyl-oxyethyl 3-acryloxy propionic copper, phthalic acid 2-(methyl) acryloyl-oxyethyl 3-acryloxy
Propanoic acid magnesium, phthalic acid 2-(methyl) acryloyl-oxyethyl 3-methacryloxy 2 Methylpropionic acid zinc, O-phthalic
Acid 2-(methyl) acryloyl-oxyethyl 3-methacryloxy 2 Methylpropionic acid copper, phthalic acid 2-(methyl) acryloyl
Epoxide ethyl 3-methacryloxy 2 Methylpropionic acid magnesium, hexahydro-phthalic acid 2-(methyl) acryloyl-oxyethyl 3-
Acryloxy propionic zinc, hexahydro-phthalic acid 2-(methyl) acryloyl-oxyethyl 3-acryloxy propionic copper, six
Hydrogenation phthalic acid 2-(methyl) acryloyl-oxyethyl 3-acryloxy propionic magnesium, hexahydro-phthalic acid 2-(first
Base) acryloyl-oxyethyl 3-methacryloxy 2 Methylpropionic acid zinc, hexahydro-phthalic acid 2-(methyl) acryloyl
Epoxide ethyl 3-methacryloxy 2 Methylpropionic acid copper and hexahydro-phthalic acid 2-(methyl) acryloxy second
Base 3-methacryloxy 2 Methylpropionic acid magnesium etc..
(polymerizable monomer (a8))
As the object lesson of the polymerizable monomer (a8) shown in described formula (8), following polymerizable monomer can be enumerated:
3-(methyl) acryloxy propionic (koch's acid (versatic acid)) zinc, 3-(methyl) acryloxy propionic (sad)
Zinc, 3-(methyl) acryloxy propionic (stearic acid) zinc, 3-(methyl) acryloxy propionic (rosin acid) zinc, 3-(methyl)
Acryloxy propionic (koch's acid) copper, 3-(methyl) acryloxy propionic (sad) copper, 3-(methyl) acryloxy third
Acid (stearic acid) copper, 3-(methyl) acryloxy propionic (rosin acid) copper, 3-(methyl) acryloxy propionic (koch's acid)
Magnesium, 3-(methyl) acryloxy propionic (sad) magnesium, 3-(methyl) acryloxy propionic (stearic acid) magnesium, 3-(methyl) third
Alkene propionic (rosin acid) magnesium, 3-(methyl) acryloxy 2 Methylpropionic acid (koch's acid) zinc, 3-(methyl) acryloyl
Epoxide 2 Methylpropionic acid (sad) zinc, 3-(methyl) acryloxy 2 Methylpropionic acid (stearic acid) zinc, 3-(methyl) acryloyl
Epoxide 2 Methylpropionic acid (rosin acid) zinc, 3-(methyl) acryloxy 2 Methylpropionic acid (koch's acid) copper, 3-(methyl) propylene
Acyloxy 2 Methylpropionic acid (sad) copper, 3-(methyl) acryloxy 2 Methylpropionic acid (stearic acid) copper, 3-(methyl) propylene
Acyloxy 2 Methylpropionic acid (rosin acid) copper, 3-(methyl) acryloxy 2 Methylpropionic acid (koch's acid) magnesium, 3-(methyl) third
Alkene acyloxy 2 Methylpropionic acid (sad) magnesium, 3-(methyl) acryloxy 2 Methylpropionic acid (stearic acid) magnesium and 3-(first
Base) acryloxy 2 Methylpropionic acid (rosin acid) magnesium etc..
(polymerizable monomer (a9))
As the object lesson of the polymerizable monomer (a9) shown in described formula (9), following polymerizable monomer can be enumerated:
Two (succinic acid 2-(methyl) acryloyl-oxyethyl) zinc, two (succinic acid 2-(methyl) acryloyl-oxyethyl) copper, two (succinums
Acid 2-(methyl) acryloyl-oxyethyl) magnesium, two (phthalic acid 2-(methyl) acryloyl-oxyethyl) zinc, two (adjacent benzene two
Formic acid 2-(methyl) acryloyl-oxyethyl) copper, two (phthalic acid 2-(methyl) acryloyl-oxyethyl) magnesium, two (hexahydros
Change phthalic acid 2-(methyl) acryloyl-oxyethyl) zinc, two (hexahydro-phthalic acid 2-(methyl) acryloxy second
Base) copper, two (hexahydro-phthalic acid 2-(methyl) acryloyl-oxyethyl) magnesium, succinic acid 2-(methyl) acryloxy second
Base (methyl) zinc acrylate resin, succinic acid 2-(methyl) acryloyl-oxyethyl (methyl) acrylic acid copper, succinic acid 2-(methyl) third
Alkene trimethylammonium (methyl) Magnesium Acrylate Prepared, phthalic acid 2-(methyl) acryloyl-oxyethyl (methyl) zinc acrylate resin, neighbour
Phthalic acid 2-(methyl) acryloyl-oxyethyl (methyl) acrylic acid copper, phthalic acid 2-(methyl) acryloyl-oxyethyl
(methyl) Magnesium Acrylate Prepared, hexahydro-phthalic acid 2-(methyl) acryloyl-oxyethyl (methyl) zinc acrylate resin, hexahydro are adjacent
Phthalic acid 2-(methyl) acryloyl-oxyethyl (methyl) acrylic acid copper and hexahydro-phthalic acid 2-(methyl) propylene
Trimethylammonium (methyl) Magnesium Acrylate Prepared etc..
(polymerizable monomer (a10))
As the object lesson of the polymerizable monomer (a10) shown in described formula (10), following polymerism list can be enumerated
Body: succinic acid 2-(methyl) acryloyl-oxyethyl (koch's acid) zinc, succinic acid 2-(methyl) acryloyl-oxyethyl (sad)
Zinc, succinic acid 2-(methyl) acryloyl-oxyethyl (stearic acid) zinc, succinic acid 2-(methyl) acryloyl-oxyethyl (Colophonium
Acid) zinc, succinic acid 2-(methyl) acryloyl-oxyethyl (koch's acid) copper, succinic acid 2-(methyl) acryloyl-oxyethyl be (pungent
Acid) copper, succinic acid 2-(methyl) acryloyl-oxyethyl (stearic acid) copper, succinic acid 2-(methyl) acryloyl-oxyethyl (pine
Fragrant acid) copper, succinic acid 2-(methyl) acryloyl-oxyethyl (koch's acid) magnesium, succinic acid 2-(methyl) acryloyl-oxyethyl
(sad) magnesium, succinic acid 2-(methyl) acryloyl-oxyethyl (stearic acid) magnesium, succinic acid 2-(methyl) acryloyl-oxyethyl
(rosin acid) magnesium, phthalic acid 2-(methyl) acryloyl-oxyethyl (koch's acid) zinc, phthalic acid 2-(methyl) propylene
Trimethylammonium (sad) zinc, phthalic acid 2-(methyl) acryloyl-oxyethyl (stearic acid) zinc, phthalic acid 2-(first
Base) acryloyl-oxyethyl (rosin acid) zinc, phthalic acid 2-(methyl) acryloyl-oxyethyl (koch's acid) copper, adjacent benzene two
Formic acid 2-(methyl) acryloyl-oxyethyl (sad) copper, phthalic acid 2-(methyl) acryloyl-oxyethyl (stearic acid)
Copper, phthalic acid 2-(methyl) acryloyl-oxyethyl (rosin acid) copper, phthalic acid 2-(methyl) acryloxy second
Base (koch's acid) magnesium, phthalic acid 2-(methyl) acryloyl-oxyethyl (sad) magnesium, phthalic acid 2-(methyl) propylene
Trimethylammonium (stearic acid) magnesium, phthalic acid 2-(methyl) acryloyl-oxyethyl (rosin acid) magnesium, hexahydro neighbour's benzene two
Formic acid 2-(methyl) acryloyl-oxyethyl (koch's acid) zinc, hexahydro-phthalic acid 2-(methyl) acryloyl-oxyethyl
(sad) zinc, hexahydro-phthalic acid 2-(methyl) acryloyl-oxyethyl (stearic acid) zinc, hexahydro-phthalic acid 2-
(methyl) acryloyl-oxyethyl (rosin acid) zinc, hexahydro-phthalic acid 2-(methyl) acryloyl-oxyethyl (koch's acid)
Copper, hexahydro-phthalic acid 2-(methyl) acryloyl-oxyethyl (sad) copper, hexahydro-phthalic acid 2-(methyl) third
Alkene trimethylammonium (stearic acid) copper, hexahydro-phthalic acid 2-(methyl) acryloyl-oxyethyl (rosin acid) copper, hexahydro
Change phthalic acid 2-(methyl) acryloyl-oxyethyl (koch's acid) magnesium, hexahydro-phthalic acid 2-(methyl) acryloyl-oxy
Base ethyl (sad) magnesium, hexahydro-phthalic acid 2-(methyl) acryloyl-oxyethyl (stearic acid) magnesium and hexahydro are adjacent
Phthalic acid 2-(methyl) acryloyl-oxyethyl (rosin acid) magnesium etc..
(manufacture method of the polymerizable monomer (a) containing divalent metal)
Polymerizable monomer (a6), (a7) and (a9) such as can be by making inorganic metal compound and carboxylic polymerism list
The method that body carries out reacting prepares.Additionally, polymerizable monomer (a8) and (a10) such as can by making inorganic metal compound,
(following, sometimes by " the most carboxylic for both merging with carboxylic polymerizable monomer and carboxylic non-polymerization compound
Compound ".) method that carries out reacting prepares.Further " polymerizable monomer " refers to have polymerism unsaturated double-bond, here
Compound, " non-polymerization compound " refers to the compound without polymerism unsaturated double-bond.
As long as the temperature that reaction temperature is not polymerized at carboxylic polymerizable monomer is carried out, preferably less than 120 DEG C.
As reaction method, preferably make inorganic metal compound and carboxylic compound in the organic solvent containing alcohol based compound
The method carrying out reacting.With it, make the polymerizable monomer (a) containing divalent metal and the polymerism list without divalent metal
The intermiscibility of body (b) is good so that the polymerization being used for obtaining the copolymer containing metal becomes easy.As contained in organic solvent
Some alcohol based compounds, can enumerate ethanol, isopropanol, butanol and propylene glycol monomethyl ether etc..
As inorganic metal compound, the metal-oxides such as magnesium oxide, copper oxide, zinc oxide can be enumerated；Magnesium hydroxide, hydrogen
The metal hydroxides such as copper oxide, zinc hydroxide；The metal chlorides etc. such as magnesium chloride, copper chloride, zinc chloride.
As carboxylic polymerizable monomer, if generate more than one from described formula (6), (7), (8), (9) and
(10) select in the group that the polymerizable monomer containing metal shown in is formed carries out selection i.e. containing the polymerizable monomer of metal
Can, such as can enumerate following carboxylic polymerizable monomer: acrylic acid 2-carboxyethyl, methacrylic acid 2-carboxyl propyl ester,
Succinic acid 2-(methyl) acryloyloxyethyl ester, phthalic acid 2-(methyl) acryloyloxyethyl ester, hexahydro O-phthalic
Acid 2-(methyl) acryloyloxyethyl ester, (methyl) acrylic acid and β-CEA(Daicel cyanogen special (strain) system) etc..From obtaining
The good aspect of film soil resistance from the point of view of, preferably acrylic acid 2-carboxyethyl, methacrylic acid 2-carboxyl propyl ester and β-CEA
(Daicel cyanogen special (strain) system).
As carboxylic non-polymerization compound, such as following non-polymerization compound can be enumerated: acetic acid, a chloroethene
Acid, a Fluoroethanoic acid, propanoic acid, caproic acid, octanoic acid, 2 ethyl hexanoic acid, capric acid, koch's acid, isostearic acid, Palmic acid, cresotic acid,
Oleic acid, elaidic acid, linoleic acid, linolenic acid, stearolic acid, ricinoleic acid, ricinelaidic acid, brassidic acid, erucic acid, α-naphthoicacid, β-
Naphthoic acid, benzoic acid, 2,4,5 T 2,4,5 trichlorophenoxy acetic acid, 2,4 dichloro benzene ethoxyacetic acid, quinoline carboxylic acid, nitrobenzoic acid, nitre
Base naphthalene-carboxylic acid, pulvinic acid, aphthenic acids, rosin acid, neoabietic acid, dehydroabietic acid, hydroabietic acid, palustric acid, dextropimaric acid, different
Dextropimaric acid, levopimaric acid, dextropimaric acid and sandaracopimaric acid etc..From the resistance to anti-thread breakage of the film obtained and resistance to stripping
From the viewpoint of the physical property such as property, preferred fatty acid system monoacid.
Metallic atom in inorganic metal compound is containing carboxylic relative to 1 mole with the ratio of carboxylic polymerizable monomer
The polymerizable monomer of base, metallic atom is preferably more than 0.3 mole less than 2.5 moles.If metallic atom is more than 0.3 mole,
The not fewest with the quantitative change of the carboxyl of metal reaction, the resistance to water of film easily becomes good.If metallic atom be 2.5 moles with
Under, then many due to the quantitative change of polymerizable monomer in the raw mixture of reaction, the polymerism list containing metal that therefore generates
The quantitative change of body is many, and result is that the dissolving of film continues for a long time.
Metallic atom in inorganic metal compound and the ratio of carboxylic compound are carboxylic relative to 1 mole
Compound, metallic atom is preferably less than 0.6 mole.If metallic atom is less than 0.6 mole, the most not with the metal of carboxyl reaction
Atom tails off, the transparency of the mixture of the polymerizable monomer (a) containing divalent metal and the polymerizable monomer (b) without divalent metal
Easily become good.
(without the polymerizable monomer (b) of divalent metal)
In the present invention, the polymerizable monomer (b) without divalent metal refers to not contain the polymerizable monomer of divalent metal, as long as
It is the monomer with polymerism unsaturated double-bond, is just not particularly limited, can enumerate such as following polymerizable monomer: (first
Base) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) acrylic acid 2-methoxy acrylate, (methyl) n-butyl acrylate,
(methyl) Isobutyl 2-propenoate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) lauryl
Base ester, (methyl) stearyl acrylate base ester, (methyl) benzyl acrylate, (methyl) phenyl acrylate, (methyl) acrylic acid are different
(methyl) acrylate monomers such as norbornene ester, (methyl) cyclohexyl acrylate, (methyl) glycidyl acrylate；(methyl)
Acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 2-hydroxybutyl, (methyl) acrylic acid 4-
(methyl) acrylate monomer of the hydroxyls such as hydroxybutyl；(methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxyl
(methyl) acrylate monomer of the hydroxyls such as base propyl ester and oxirane, expoxy propane, gamma-butyrolacton or 6-caprolactone etc.
Addition product；The carboxylic monomers such as (methyl) acrylic acid, fumaric acid, maleic acid, itaconic acid, sorbic acid；Itaconic anhydride, maleic acid
The monomer containing acid anhydride such as acid anhydride；The dicarboxylic acid monoesters classes such as itaconic acid mono alkyl ester, maleic acid mono alkyl ester；(methyl) acrylic acid
The dimer of (methyl) acrylate monomer of the hydroxyls such as 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester or trimerization
Body；(methyl) glycerol acrylate etc. has (methyl) acrylate monomer of multiple hydroxyl；(methyl) acrylic acid butylamino
(methyl) acrylate monomer containing primary amino radical and secondary amino group such as ethyl ester, (methyl) acrylamide；(methyl) acrylic acid dimethyl
(methyl) acrylate monomer containing amino such as amino ethyl ester, (methyl) acrylic acid diethylamino ethyl ester；(methyl) acryloyl
(methyl) acrylamide monomers such as amine, N-butyl (methyl) acrylamide；Styrene, α-methyl styrene, vinyltoluene,
The ethylene base system monomers such as (methyl) acrylonitrile, vinyl chloride, vinyl acetate；Pi-allyl ethylene glycol, polyethylene glycol allyl, first
Epoxide polyethylene glycol allyl, butoxy polyethylene glycol allyl, polypropylene glycol allyl ether, methoxyl group polypropylene glycol alkene
The monomer containing pi-allyl such as propyl ether, butoxypolypropylene glycol allyl ether；And ethylene glycol bisthioglycolate (methyl) acrylate, diethyl
Multifunctional (the first such as glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, (methyl) allyl acrylate
Base) acrylate monomer etc..These monomers can be used alone or use two or more.
As the method making the polymerizable monomer (a) containing divalent metal be polymerized with the polymerizable monomer (b) without divalent metal,
Such as can use known solution polymerization process.
When using the polymerizable monomer (a) containing divalent metal, in order to generate cullet shape when suppressing to be polymerized, particularly preferably
Use chain-transferring agent.From the point of view of in terms of chain-transferring agent with the intermiscibility of the polymerizable monomer (a) containing divalent metal, as chain tra nsfer
Agent is preferably the chain-transferring agent beyond mercaptan, preferably styrene dimer thing etc..As solvent, it is possible to use known organic molten
Agent, can enumerate such as following organic solvent: dimethylbenzene, methyl proxitol, toluene, methyl iso-butyl ketone (MIBK), n-butyl acetate,
And n-butyl alcohol etc..Solvent can use one, it is also possible to two or more and use.Polymerization temperature is not particularly limited, such as
It it is about 60～180 DEG C.Polymerization time is not particularly limited, for example, about 2～14 hours.
Polymerizable monomer (a) as polymer raw, containing divalent metal and the polymerizable monomer (b) without divalent metal
The ratio of addition is not particularly limited, for 5:95～70:30(mass %) left and right.
(manufacture method 2 of the copolymer containing divalent metal)
" manufacture method 2 " is for make metallic compound and unitary organic acid as required enter with the copolymer (c) containing acidic group
The method of row reaction or the slaine of use unitary organic acid carry out the manufacture method of ester exchange with the copolymer (c) containing acidic group.
As the manufacture method of the copolymer (c) containing acidic group, can enumerate such as by the polymerizable monomer containing acidic group and other
The method of polymerizable monomer copolymerization；By after the polymerizable monomer of hydroxyl and other polymerizable monomer copolymerization, make anhydride etc. and hydroxyl
Base section carries out reacting the method etc. importing acidic group.
As the polymerizable monomer containing acidic group, if obtain having structure shown in formula (1) or (2) containing divalent metal
Copolymer and carry out selecting, such as following polymerizable monomer can be enumerated: acrylic acid 2-carboxyethyl, methacrylic acid 2-
Carboxyl propyl ester, succinic acid 2-(methyl) acryloyloxyethyl ester, phthalic acid 2-(methyl) acryloyloxyethyl ester, hexahydro
Phthalic acid 2-(methyl) acryloyloxyethyl ester, (methyl) acrylic acid and β-CEA(Daicel (strain) cyanogen are special)
Deng.From the film soil resistance obtained good in terms of from the point of view of, preferably acrylic acid 2-carboxyethyl, methacrylic acid 2-carboxyl third
Ester, β-CEA(Daicel cyanogen special (strain) system).
As the polymerizable monomer of hydroxyl, such as following polymerizable monomer can be enumerated: (methyl) acrylic acid 2-hydroxyl
Ethyl ester, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 2-hydroxybutyl, (methyl) acrylic acid 4-hydroxybutyl etc. contain
(methyl) acrylate monomer of hydroxyl；And (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester etc.
The addition product of (methyl) acrylate monomer of hydroxyl and oxirane, expoxy propane, gamma-butyrolacton or 6-caprolactone etc.
Deng.
As the anhydride reacted with hydroxylic moiety, such as following anhydride can be enumerated: phthalic anhydride, hexahydro neighbour's benzene
Dioctyl phthalate, tetrahydrophthalic anhydride, methyl hexahydro phthalic anhydride, methyl nadic anhydride and
The dibasic acid anhydrides etc. such as succinic acid.
As the manufacture method of the copolymer (c) containing acidic group, such as, can use known solution polymerization process.During as polymerization
Solvent, it is possible to use known organic solvent, can enumerate such as following solvent: dimethylbenzene, methyl proxitol, toluene,
Methyl iso-butyl ketone (MIBK), n-butyl acetate and n-butyl alcohol etc..Solvent can use one, it is also possible to two or more and use.Poly-
Conjunction temperature is not particularly limited, for example, about 60～180 DEG C.Polymerization time is not particularly limited, and for example, 2～14 is little
Time about.
As the metallic compound reacted with the copolymer (c) containing acidic group, magnesium oxide, copper oxide, zinc oxide etc. can be enumerated
Metal-oxide；The metal hydroxidess such as magnesium hydroxide, Copper hydrate, zinc hydroxide；The gold such as magnesium chloride, copper chloride, zinc chloride
Belong to chloride etc..
Reaction can use unitary organic acid as required.As unitary organic acid, following compound can be enumerated: second
Acid, chloroacetic acid, a Fluoroethanoic acid, propanoic acid, caproic acid, octanoic acid, 2 ethyl hexanoic acid, capric acid, koch's acid, isostearic acid, Palmic acid, first
Base salicylic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, stearolic acid, ricinoleic acid, ricinelaidic acid, brassidic acid, erucic acid, α-
Naphthoic acid, β-naphthoic acid, benzoic acid, 2,4,5 T 2,4,5 trichlorophenoxy acetic acid, 2,4 dichloro benzene ethoxyacetic acid, quinoline carboxylic acid, nitro
Benzoic acid, nitronaphthalene carboxylic acid, pulvinic acid, aphthenic acids, rosin acid, neoabietic acid, dehydroabietic acid, hydroabietic acid, palustric acid,
Dextropimaric acid, isodextropimaric acid, levopimaric acid, dextropimaric acid and sandaracopimaric acid etc..Resistance to anti-thread breakage from the film obtained
From the viewpoint of the physical property such as peel resistance, preferred fatty acid system monoacid.
Ester-interchange method in " manufacture method 2 " is the slaine using the copolymer (c) containing acidic group with unitary organic acid
Method.Slaine as unitary organic acid, it is possible to use be made up of aforesaid unitary organic acid and the metals such as magnesium, copper, zinc
Compound, can enumerate such as following compound: copper acetate, zinc acetate, magnesium acetate, propanoic acid copper, zinc propionate and propanoic acid magnesium etc..
The solvent used during as ester exchange, can enumerate such as following organic solvent: dimethylbenzene, propylene glycol methyl
Ether, toluene, methyl iso-butyl ketone (MIBK), n-butyl acetate and n-butyl alcohol etc..Solvent can use one, it is also possible to two or more
And use.Reaction temperature is not particularly limited, but preferably carries out below the decomposition temperature of slaine.
(tenor)
In described " manufacture method 1 " or " manufacture method 2 ", preferably by the polymerizable monomer (a) containing divalent metal or containing acid
The tenor that the usage amount of the copolymer (c) etc. of base is set so that in the copolymer containing metal is more than 2 mass % 20 matter
Amount below %.When tenor in copolymer containing metal is more than 2 mass %, the water-disintegrable of film becomes good, soil resistance
Can become good.During additionally, be below 20 mass %, the resistance to anti-thread breakage and resistance to water of film becomes good.If in view of film
Soil resistance, resistance to anti-thread breakage and resistance to water, then tenor is especially preferably below more than 4 mass % 15 mass %.
(content of carboxylic polymerizable monomeric unit)
Additionally, contain in the copolymer of metal, for making the structure shown in more than one described formulas (1) of generation or formula (2)
And the content of the carboxylic polymerizable monomeric unit selected, more than preferably 1 mass %, more than especially preferably 2 mass %.
If more than 1 mass %, then the water-disintegrable of the film obtained becomes good, and then resistance to anti-thread breakage becomes good, it is possible to play for a long time
Excellent anti-fouling effect.Further, the content of carboxylic polymerizable monomeric unit is the amount calculated by following calculating formula.
[mathematical expression 1]
Content (%)=C × D × 100 of carboxylic polymerizable monomeric unit
(antifouling paint compositions)
The antifouling paint compositions of the present invention is containing the described copolymer containing metal and in this copolymer time institute of manufacture
The antifouling paint compositions of the solvent used.The antifouling paint compositions of the present invention is by containing the described copolymerization containing metal
Thing, it is possible to make the film of formation keep the antifouling property of excellence.The antifouling paint of present invention compositions is coordinated by further
Antifouling medicament, it is possible to increase antifouling property.
(antifouling paint)
The antifouling paint of the present invention by coordinating antifouling medicament in the antifouling paint compositions of the present invention, can be used for
The additives such as the solvent of dilution and pigment are prepared.When the antifouling paint of the present invention contains antifouling medicament and pigment composition etc.
, the ratio of copolymer containing metal in antifouling paint, in terms of resinous principle, it is often preferred that 15 mass %(solid constituents change
Calculate) more than.If this use level is more than 15 mass %, then the favorable solubility of the copolymer containing metal in antifouling paint, film
Soil resistance and resistance to anti-thread breakage well.
As antifouling medicament, can performance carry out properly selecting using as requested, such as following preventing can be enumerated
Dirty medicament: the copper system anti-fouling agents such as Red copper oxide, copper rhodanide, copper powders；The metallic compound of lead, zinc, nickel etc.；The amine such as diphenylamines
Derivant；Nitro compound, benzothiazole based compound, maleimide amine compound, pyridine based compound etc..These are permissible
It is used alone or use multiple.
Particularly preferably can be waited the selected antifouling medicament as investigation object by (society) Japanese shipbuilding industry, example can be enumerated
Antifouling medicament as following: ethylidene dithiocarbamate manganese, PZ, 2-methyl mercapto-4-
Tert-butylamino-6-cyclopropylamino-s-triazine, 2,4,5,6-daconil M, N, N-dimethyl Dichlorobenzene base urea, Asia
Ethyl bisdithiocarbamic zinc, cupric thiocyanate, 4,5-bis-chloro-2-n-octyl-3 (2H) isothiazolone, N-(fluorine dichloromethane
Sulfenyl) phthalimide, N, N '-dimethyl-N '-phenyl-(N-fluorine dichloromethane sulfenyl) sulfonamide, 2-mercaptopyridine-1-
Oxidation zinc salt, tetramethylthiuram disulfide, Cu-10%Ni solid solution alloy, 2,4,6-trichlorophenyl maleimide, 2,3,5,
6-tetra-chloro-4-(methyl sulphonyl) pyridine, IPBC, AMICAL 48, double two
Methyl Dithiocarbamyl zinc ethylene bisdithiocarbamate, phenyl (double pyridine radicals) dichloride bismuth, 2-(4-thiazole
Base)-benzimidazole and pyridine-triphenylborane etc..
In imparting film coated surface with lubricity, prevent under the purpose of biological attachment, can also in the antifouling paint of the present invention
Coordinate the fluorochemicals etc. such as the silicone compounds such as dimethyl polysiloxane and silicone oil, perfluorocarbon.And then, the antifouling painting of the present invention
Material can also coordinate extender pigment, coloring pigment, plasticizer, various additive for coatings, other resins etc. as required.
The solvent being used for diluting used in antifouling paint as the present invention, can enumerate dimethylbenzene, propylene glycol methyl
The organic solvents such as ether, toluene, methyl iso-butyl ketone (MIBK), n-butyl acetate and n-butyl alcohol.Organic solvent can use one, it is also possible to
Two or more and use.
(there are the article of film)
As the article of the film of the antifouling paint with the present invention, boats and ships, various fishing net, electric station water guide can be enumerated
Pipe, oil fence, bridge, buoy and submarine etc..
The antifouling paint using the present invention forms film, such as, carry out by the method for following (1) or (2).
(1) antifouling paint is coated directly onto the water such as boats and ships, various fishing net, port equipment, oil fence, bridge, base, seabed
The substrate surface of middle works etc..
(2) on base material, it is coated with priming paint and the middle painting coating etc. such as wash printer, chlorinated rubber system, epoxy, it is obtaining
To film on the method coating anti-pollution coating such as brushing, spraying, roller coat, deposition.
The amount that coating weight generally makes the thickness of dry coating be 50～400 μm.Being dried the most at room temperature of film
Carry out but it also may be thermally dried.
Embodiment
Hereinafter, by embodiment and comparative example, the present invention is described in detail further.Additionally, before embodiment,
To various evaluation methodologys and the manufacture example 1 of the copolymer containing metal～20 and the manufacture example 28～53 of varnish illustrate.And
And, " part " expression " mass parts " in embodiment.Additionally, the shorthand notation of the compound etc. used in embodiment is shown in table 1
In.
(evaluation methodology)
[the 1. solid constituent of varnish]
By about 0.5g sample after 105 DEG C of heat dryings 2 hours, measure the quality of its residue, by following calculating formula
Calculate.
[mathematical expression 2]
Quality (g) × 100 of quality (the g)/sample of solid constituent (quality %)=residual volume
[the 2. acid number of the solid constituent of varnish]
Mg number with the potassium hydroxide in titration determination and required for the solid constituent of 1g varnish.The value that will obtain
(mgKOH/g) as the acid number of solid constituent of varnish.
[the 3. consumption degree test of film]
Vertical 50mm, horizontal 50mm, thickness 2mm hard vinyl chloride plate on formed thickness about 300 μm film, will
To test film be installed on the going barrel that is arranged in sea water.Then rotate under so that it is save in peripheral speed 7.7m/s(15),
Consumption thickness after measuring 3 months, after 6 months and after 12 months.
[the 4. soil resistance test of film]
The plate of sandblasting steel being pre-coated with antirusting paint is formed the film of thickness about 300 μm, the examination that will obtain
Test sheet in gulf, Hiroshima, Hiroshima county, stand dipping 12 months, the bond area of the aufwuch after studying 6 months and after 12 months
(%).Judge to carry out with following benchmark.
The bond area of the aufwuch after A:12 month is 0% less than 10%.
The bond area of the aufwuch after B:12 month is 10% less than 40%.
The bond area of the aufwuch after C:12 month is 40% less than 80%.
The bond area of the aufwuch after D:12 month is less than more than 80% 100%.
[the 5. resistance to anti-thread breakage test of film]
The plate of sandblasting steel being pre-coated with antirusting paint is formed the film of thickness about 300 μm, the examination that will obtain
Test in sheet sea water after sterilising filtration, after 20 DEG C of dippings 6 months and 12 months, be dried 1 week at 20 DEG C.Then, painting is observed
Film surface.Evaluate and carry out with following benchmark.
A: entirely without observing crackle and stripping.
B: somewhat observe crackle.
C: partially observable crackle and stripping.
D: crackle and stripping are observed in whole face.
(manufacture example)
[manufacture example 1: the manufacture of the mixture M 1 of the polymerizable monomer (a) containing metal]
In the four-hole boiling flask possessing condenser, thermometer, Dropping funnel and agitator, add 142 parts of conducts the most molten
The PGM(methyl proxitol of agent) and 41 parts of zinc oxide, stir and the temperature of liquid in flask is warming up to 75 DEG C.Separately
On the one hand, in Dropping funnel, load the mixture (reaction raw materials) being made up of 144 parts of acrylic acid 2-carboxyethyl and 5 parts of water.
Make this mixture addition within the unit interval certain, be added drop-wise in flask in 3 hours.And then, by the liquid in flask
After stirring 2 hours, add 10 parts of PGM, obtain the mixture M 1 of the transparent polymerizable monomer (a) containing metal.Mixture M 1
Solid constituent is 51.4 mass %.The tenor of mixture M 1 is 9.6 mass %.Further, under the tenor of mixture passes through
State calculating formula to calculate.
[mathematical expression 3]
[manufacture example 2～20: the manufacture of the mixture M 2～M20 of the polymerizable monomer (a) containing metal]
By kind and the usage amount of the reaction raw materials in the usage amount of the initial solvent in four-hole boiling flask and Dropping funnel
It is changed to the condition shown in table 2 or table 3, in addition, manufactures mixing of the polymerizable monomer containing metal in the same manner as manufacturing example 1
Compound M2～M20.Solid constituent and the tenor (value of calculation) of mixture M 2～M20 are shown in table 2 or table 3.
[manufacture example 21: the manufacture of varnish C1]
In the four-hole boiling flask possessing condenser, thermometer, dropping bath and agitator, add 66.4 parts of dimethylbenzene, 15 parts
PGM(methyl proxitol), 4 parts of ethyl acrylate, stir and the temperature of liquid in flask be warming up to 100 DEG C.Separately
On the one hand, preparation is by 30 parts of methyl methacrylates, 22.7 parts of ethyl acrylate, 20 parts of n-butyl acrylates, 53.1 parts of mixing
Thing M1(solid constituent 27.3 parts), 10 parts of dimethylbenzene, 1 part of chain-transferring agent (Nippon Yushi (Co., Ltd.) Nofmer MSD), 2 parts
AIBN, the transparent mixture of 8 parts of AMBN compositions, and load in dropping bath.Make the mixture in this dropping bath within the unit interval
Addition certain, be added drop-wise in four-hole boiling flask in 6 hours.After being added dropwise to complete, further in 30 minutes in four-hole boiling flask
Drip the mixture of 0.5 part of tert-butyl peroctoate and 15 parts of dimethylbenzene, and then stir 1 hour 30 minutes.Then, 300 purposes are used
Mixture in nylon net filter four-hole boiling flask, obtains having gardner viscosity QR and do not have the varnish C1 of insoluble matter.Varnish C1
Solid constituent be 46.2 mass %, the tenor in copolymer is 5.1 mass %.Further, the tenor in copolymer leads to
Cross following calculating formula to calculate.
[mathematical expression 4]
[manufacture example 22～46: the manufacture of varnish C2～C26]
Kind and the usage amount of the material in the usage amount of initial solvent and dropping bath are changed to shown in table 4 or table 5
Condition, in addition, manufactured varnish C2～C26 with manufacturing in the same manner as example 21.By solid constituent and the copolymer of each varnish
In tenor (value of calculation) be shown in table 4 or table 5.
[manufacture example 47: the manufacture of varnish C27]
(reaction 1)
In the four-hole boiling flask possessing condenser, thermometer, dropping bath and agitator, as initial solvent, add 60 parts
Dimethylbenzene, 15 parts of PGM(methyl proxitols), stir and the temperature of liquid in flask is warming up to 100 DEG C.The opposing party
Face, prepares kind as shown in Table 6 and the polymerizable monomer containing acidic group of amount, other polymerizable monomers and polymerization initiator composition
Transparent mixture, and load in dropping bath.Make the addition within the unit interval of the mixture in this dropping bath certain, 4
It is added drop-wise in four-hole boiling flask in hour.After being added dropwise to complete, in 30 minutes, in four-hole boiling flask, dropping 0.5 part is the saddest further
The tert-butyl ester and the mixture of 25 parts of dimethylbenzene, and then stir 1 hour 30 minutes, obtain varnish.4g varnish is taken out in this flask,
Measure solid constituent and the acid number of solid constituent.Evaluation result is shown in Table 6.
(reaction 2)
Then, the kind shown in input table 6 and the metallic compound of amount, organic acid and solvent (diformazan in above-mentioned flask
Benzene) mixture.Temperature of liquid in flask is warming up to reflux temperature, from flask, removes water and the mixed solution of solvent,
While supplementing and the dimethylbenzene of the mixed solution equivalent removed, reaction is continued 18 hours.Then, with the nylon of 300 mesh
Mixture in net filtration flask, obtains having gardner viscosity ZZ1 and do not have the varnish C27 of insoluble matter.The solid of varnish C27
Composition is 45.9 mass %, and the tenor (value of calculation) in copolymer is 7.7 mass %.
[manufacture example 48～53: the manufacture of varnish C28～C33]
(reaction 1)
Kind and the usage amount of the mixture material in the usage amount of initial solvent and dropping bath are changed to shown in table 6
Condition, in addition, obtain varnish with manufacturing in the same manner as example 47.The evaluation result of each varnish (product of reaction 1) is shown in
In table 6.
(reaction 2)
Then, the kind shown in input table 6 and the metallic compound of amount, organic in above-mentioned each flask containing each varnish
Acid and each mixture of solvent (dimethylbenzene), obtain varnish C28～C33 in the same manner as manufacturing example 47.By the evaluation result of varnish
It is shown in Table 6.Further, the varnish 30 manufacturing example 50 is the most muddy, but other varnish are the varnish not having insoluble matter.
[embodiment 1]
Mix following 5 kinds of materials to prepare antifouling paint.Further, appropriate dimethylbenzene is added to regulate viscosity so that use
Stormer viscosity meter (25 DEG C) is determined as 80～90KU.
Varnish C1:40 part,
Red copper oxide: 50 parts,
Ferrum oxide: 1.5 parts,
Powdered silica: 3 parts,
Disparlon4200-20(this chemical conversion of nanmu (strain) system, sagging inhibitor): 1 part.
The antifouling paint obtained is applied on the substrate of regulation so that dry film thickness is about 300 μm, is dried at room temperature for
1 week.The film obtained is carried out the test of consumption degree, soil resistance test and resistance to anti-thread breakage test.Evaluation result is shown in Table 7.
[embodiment 2～4,6～14 and 16～28]
The kind of material is set to the condition shown in table 7～table 9, in addition, prepares antifouling painting similarly to Example 1
Material, is applied on substrate obtain film.Evaluation result is shown in table 7～table 9.
[embodiment 5]
Mix following 6 kinds of materials to prepare antifouling paint.Further, appropriate dimethylbenzene is added to regulate viscosity so that use
Stormer viscosity meter (25 DEG C) is determined as 80～90KU.
Varnish C4:40 part,
Cupric thiocyanate: 40 parts,
2-mercaptopyridine-1-aoxidizes zinc salt: 3 parts,
Titanium oxide: 10 parts,
Powdered silica: 3 parts,
Disparlon 4200-20:1 part.
The antifouling paint obtained is applied on substrate similarly to Example 1, obtains film.Evaluation result is shown in table
In 7.
[embodiment 15]
The kind of material is set to the condition shown in table 7, in addition, prepares antifouling paint similarly to Example 5, be coated with
Cloth obtains film on substrate.Evaluation result is shown in Table 8.
[comparative example 1～6]
The kind of material is set to the condition shown in table 7～table 9, in addition, prepares coating similarly to Example 1,
It is applied on substrate obtain film.Evaluation result is shown in table 7～table 9.In comparative example 1～6, due to the copolymerization containing metal
Not containing the structure of the present invention in thing, therefore film consumption degree is insufficient or crackle stripping is grade D, and result can not get sufficiently
Soil resistance.
Table 1
Table 2
Table 3
Table 4
Table 5
Table 6
Table 7
Table 8
Table 9
Claims (7)
1. an antifouling paint compositions, it is characterised in that it contains the copolymer containing metal, the described copolymer containing metal
There is more than one structure selected from the structure shown in the structure shown in formula (1) and formula (2),
Formula (1)
-COO-(R1-COO)n-M-
In formula (1), M represents divalent metal, R1Representing the hydrocarbon of carbon number 2 or 3, n is any integer of 1 to 20；
Formula (2)
-COO-(R2-OCO-R3-COO)m-M-OCO-R4-COO-R5-OCO-
In formula (2), M represents divalent metal, R2～R5Representing hydrocarbon, m is 0 or 1.
Antifouling paint compositions the most according to claim 1, it is characterised in that the described copolymer containing metal has one
Individual above choosing from the group that the structure shown in the structure shown in formula (3), formula (4) and the structure shown in formula (5) are formed
The structure selected,
Formula (3)
-COO-(R1-COO)n-M-(OCO-R6)p-OCO-
In formula (3), M represents divalent metal, R1And R6Independently of one another represent carbon number 2 or 3 hydrocarbon, n be 1 to 20 arbitrary whole
Number, p is any integer of 0 to 20；
Formula (4)
-COO-(R1-COO)n-M-OCO-R4-COO-R5-OCO-
In formula (4), M represents divalent metal, R1Represent the hydrocarbon of carbon number 2 or 3, R4And R5Representing hydrocarbon, n is any integer of 1 to 20；
Formula (5)
-COO-(R1-COO)n-M-R7
In formula (5), M represents divalent metal, R1Represent the hydrocarbon of carbon number 2 or 3, R7Represent organic acid residue, n be 1 to 20 arbitrary
Integer.
Antifouling paint compositions the most according to claim 1, it is characterised in that the manufacture of the described copolymer containing metal
Method is by containing the polymerizable monomer (a) containing divalent metal and the monomer mixture of the polymerizable monomer (b) without divalent metal
Carrying out copolymerization, the described polymerizable monomer (a) containing divalent metal contains more than one from the polymerizable monomer shown in formula (6)
(a6), the group that the polymerizable monomer (a7) shown in formula (7) and the polymerizable monomer (a8) shown in formula (8) are formed is selected
The polymerizable monomer selected,
Formula (6)
CH2=C (R8)-COO-(R1-COO)n-M-(OCO-R6)p-OCO-C(R9)=CH2
In formula (6), M represents divalent metal, R8And R9Represent H or CH independently of one another3, R1And R6Represent carbon number 2 independently of one another
Or the hydrocarbon of 3, n is any integer of 1 to 20, and p is any integer of 0 to 20；
Formula (7)
CH2=C (R8)-COO-(R1-COO)n-M-OCO-R4-COO-R5-OCO-C(R9)=CH2
In formula (7), M represents divalent metal, R8And R9Represent H or CH independently of one another3, R1Represent the hydrocarbon of carbon number 2 or 3, R4And R5
Representing hydrocarbon, n is any integer of 1 to 20；
Formula (8)
CH2=C (R8)-COO-(R1-COO)n-M-R7
In formula (8), M represents divalent metal, R8Represent H or CH3, R1Represent the hydrocarbon of carbon number 2 or 3, R7Representing organic acid residue, n is
Any integer of 1 to 20.
Antifouling paint compositions the most according to claim 1, it is characterised in that the manufacture of the described copolymer containing metal
Method is by containing the polymerizable monomer (a) containing divalent metal and the monomer mixture of the polymerizable monomer (b) without divalent metal
Carrying out copolymerization, the described polymerizable monomer (a) containing divalent metal contains the polymerizable monomer (a9) shown in formula (9),
Formula (9)
CH2=C (R8)-COO-(R2-OCO-R3-COO)m-M-OCO-R4-COO-R5-OCO-C(R9)=CH2
In formula (9), M represents divalent metal, R8And R9Represent H or CH independently of one another3, R2～R5Representing hydrocarbon, m is 0 or 1.
Antifouling paint compositions the most according to claim 4, it is characterised in that described monomer mixture is possibly together with formula
(10) polymerizable monomer (a10) shown in,
Formula (10)
CH2=C (R8)-COO-R2-OCO-R3-COO-M-R7
In formula (10), M represents divalent metal, R8Represent H or CH3, R2And R3Represent hydrocarbon, R7Represent organic acid residue.
6. an antifouling paint, it is characterised in that it contains the antifouling paint compositions described in claim 1 or 2.
7. article, it is characterised in that it has the film of the antifouling paint described in claim 6.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011123308 | 2011-06-01 | ||
| JP2011-123308 | 2011-06-01 | ||
| JP2011209375 | 2011-09-26 | ||
| JP2011-209375 | 2011-09-26 | ||
| PCT/JP2012/064313 WO2012165628A1 (en) | 2011-06-01 | 2012-06-01 | Metal-containing copolymer, manufacturing method therefor, antifouling-paint composition, antifouling paint, and article having coating thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103582657A CN103582657A (en) | 2014-02-12 |
| CN103582657B true CN103582657B (en) | 2016-08-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280029125.6A Pending CN103608366A (en) | 2011-06-01 | 2012-06-01 | Metal-containing polymerizable monomer and manufacturing method therefor |
| CN201280026999.6A Active CN103582657B (en) | 2011-06-01 | 2012-06-01 | Copolymer containing metal, its manufacture method, antifouling paint compositions, antifouling paint and there are the article of film of this antifouling paint |
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| CN201280029125.6A Pending CN103608366A (en) | 2011-06-01 | 2012-06-01 | Metal-containing polymerizable monomer and manufacturing method therefor |
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| JP (2) | JP5949549B2 (en) |
| KR (2) | KR101668909B1 (en) |
| CN (2) | CN103608366A (en) |
| WO (2) | WO2012165618A1 (en) |
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| CN109311284B (en) * | 2016-07-01 | 2021-07-13 | 中国涂料株式会社 | Laminated antifouling coating film, antifouling substrate, and ship |
| JP6809231B2 (en) | 2016-07-05 | 2021-01-06 | 三菱ケミカル株式会社 | Polymer-containing composition and antifouling coating composition |
| CN110607109B (en) * | 2019-09-16 | 2021-08-03 | 浙江鱼童新材料股份有限公司 | Environment-friendly anticorrosive paint and preparation method thereof |
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| US5391666A (en) * | 1989-09-27 | 1995-02-21 | Jujo Paper Co., Ltd. | Light-responsive plate containing the metal salt of a phthalic acid derivative |
| CN1511909A (en) * | 2000-06-28 | 2004-07-14 | 三菱丽阳株式会社 | Mono soluble mixture containing metal, composition containing metal resin and dirt-proof paint |
| CN101688074A (en) * | 2007-07-20 | 2010-03-31 | 赢创罗姆有限责任公司 | Coating formulation with improved metal adhesion |
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| DE3681829D1 (en) | 1985-05-17 | 1991-11-14 | Nippon Paint Co Ltd | MIXTURE BASED ON HYDROLISABLE RESIN AND ANTI-GROWING PAINT COMPOSITION CONTAINING IT. |
| JPH05505836A (en) * | 1990-03-08 | 1993-08-26 | デーエスエム ナムローゼ フェンノートシャップ | radiation curable liquid formulations |
| JP2002105135A (en) * | 2000-10-02 | 2002-04-10 | Nippon Shokubai Co Ltd | Reaction product containing metal salt-having vinylic monomer and polymer using the same |
| JP2002105127A (en) * | 2000-10-02 | 2002-04-10 | Nippon Shokubai Co Ltd | Reaction product containing metal salt-having vinylic monomer and polymer using the same |
| JP4846093B2 (en) | 2000-12-25 | 2011-12-28 | 三菱レイヨン株式会社 | Method for producing metal-containing copolymer |
| CN100473698C (en) * | 2003-03-14 | 2009-04-01 | 三菱丽阳株式会社 | Antifouling paint composition |
| JP2006008730A (en) * | 2004-06-22 | 2006-01-12 | Kyoeisha Chem Co Ltd | Enhancer for adhesiveness between oil film coated steel material and foamed cured epoxy resin filler |
| KR100965733B1 (en) * | 2005-09-01 | 2010-06-24 | 주고꾸 도료 가부시키가이샤 | Stain-proof coating composition, stain-proof coating film, substrate having coating film, stain-proof substrate, method for formation of coating film on surface of substrate, and method for stain-proofing of substrate |
| US20100278876A1 (en) * | 2005-12-28 | 2010-11-04 | Chugoku Marine Paints, Ltd. | High-solid antifouling paint composition, antifouling coating film, base material with coating film, antifouling base material, method for forming coating film on surface of base material, antifouling method for base material, and high-solid multi-package antifouling paint composition set |
| JP5497351B2 (en) * | 2009-07-10 | 2014-05-21 | 三菱レイヨン株式会社 | Method for producing metal-containing copolymer for antifouling paint and antifouling paint composition |
-
2012
- 2012-06-01 KR KR1020137032792A patent/KR101668909B1/en active IP Right Grant
- 2012-06-01 JP JP2012526772A patent/JP5949549B2/en active Active
- 2012-06-01 JP JP2012526773A patent/JPWO2012165618A1/en active Pending
- 2012-06-01 CN CN201280029125.6A patent/CN103608366A/en active Pending
- 2012-06-01 WO PCT/JP2012/064285 patent/WO2012165618A1/en active Application Filing
- 2012-06-01 KR KR1020137032793A patent/KR20140009558A/en not_active Application Discontinuation
- 2012-06-01 WO PCT/JP2012/064313 patent/WO2012165628A1/en active Application Filing
- 2012-06-01 CN CN201280026999.6A patent/CN103582657B/en active Active
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| US4835231A (en) * | 1986-08-26 | 1989-05-30 | Nippon Paint Co., Ltd. | Disintegration type, crosslinked acrylic resin particles |
| US5391666A (en) * | 1989-09-27 | 1995-02-21 | Jujo Paper Co., Ltd. | Light-responsive plate containing the metal salt of a phthalic acid derivative |
| CN1511909A (en) * | 2000-06-28 | 2004-07-14 | 三菱丽阳株式会社 | Mono soluble mixture containing metal, composition containing metal resin and dirt-proof paint |
| CN101688074A (en) * | 2007-07-20 | 2010-03-31 | 赢创罗姆有限责任公司 | Coating formulation with improved metal adhesion |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2012165628A1 (en) | 2015-02-23 |
| JP5949549B2 (en) | 2016-07-06 |
| KR101668909B1 (en) | 2016-10-24 |
| CN103582657A (en) | 2014-02-12 |
| CN103608366A (en) | 2014-02-26 |
| WO2012165628A1 (en) | 2012-12-06 |
| KR20140009558A (en) | 2014-01-22 |
| JPWO2012165618A1 (en) | 2015-02-23 |
| WO2012165618A1 (en) | 2012-12-06 |
| KR20140009557A (en) | 2014-01-22 |
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