CN107406712A - Antifouling paint compositions, antifouling coat, antifouling base material, the storage practice of the manufacture method of antifouling base material and antifouling paint compositions - Google Patents
Antifouling paint compositions, antifouling coat, antifouling base material, the storage practice of the manufacture method of antifouling base material and antifouling paint compositions Download PDFInfo
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- CN107406712A CN107406712A CN201680013432.3A CN201680013432A CN107406712A CN 107406712 A CN107406712 A CN 107406712A CN 201680013432 A CN201680013432 A CN 201680013432A CN 107406712 A CN107406712 A CN 107406712A
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- 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
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
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- A—HUMAN NECESSITIES
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- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
- A01N55/08—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing boron
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- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
- A01N59/20—Copper
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/24—Cyanogen or compounds thereof, e.g. hydrogen cyanide, cyanic acid, cyanamide, thiocyanic acid
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
- C08L43/04—Homopolymers or copolymers of monomers containing silicon
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- C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
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- 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
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
Abstract
The present invention provides antifouling paint compositions being stained for being used to prevent the base material as caused by aquatile containing silicyl esters (co) polymer and dexmedetomidine and application thereof, and the composition can form the antifouling coat that can play long-term excellent soil resistance and have good storage-stable.The antifouling paint compositions contain silicyl esters (co) polymer (A), dexmedetomidine (B) and at least one composition (C) selected from dehydrating agent (c1) and rosin (c2), and the silicyl lipin polymer (A) has by leading to formula (I)：R1CH=CH COO (SiR2R3O)n‑SiR4R5R6Construction unit derived from shown monomer (a).
Description
Technical field
The present invention relates to antifouling paint compositions and application thereof, more specifically, are related to containing silicyl esters (common)
Polymer as film forming component and the antifouling paint compositions being stained that can be used to preventing the base material as caused by aquatile and
The antifouling coat, antifouling base material, the manufacture method and the antifouling paint group of antifouling base material of the antifouling paint compositions are used
The storage practice of compound.
Background technology
At present, by prevent it is marine be stained as caused by aquatile for the purpose of be used for the anti-of ship, marine works etc.
Dirty coating it is widely used by antifouling coat is assigned film renewal property water-disintegrable resin and to biology have physiologically active prevent
The method that dirty agent is combined.
Resin as this water-disintegrable resin, particularly with suitable renewal property, widely uses silicyl esters
(co) polymer.
On the other hand, such as in Japanese Patent Laid 2002-535255 publications (patent document 1), Mei Tuo is described
Miaow pyridine can be used as preventing the medicament of the marine biological polution of the surface of solids.
Disclosed in International Publication No. 2011/118526 (patent document 2) by these into obtained by subassembly for sudden and violent
The anti-of excellent antifouling property can also be played by being exposed at the high marine site of load and the ship of navigation condition, marine works etc. of being stained
Dirty coating composition, as its specific example, disclose containing with the knot as derived from acrylic acid triisopropylsilyl ester
The coating composition (embodiment 10,11) of silicyl lipin polymer, dexmedetomidine and the bassanite of structure unit etc..
Prior art literature
Patent document
Patent document 1:Japanese Patent Laid 2002-535255 publications
Patent document 2:International Publication No. 2011/118526
The content of the invention
The technical problems to be solved by the invention
It has however been found that in antifouling paint compositions disclosed in patent document 2, thus it is speculated that be total to along with silicyl esters
The decomposition that caused silicyl lipin polymer coexists of polymers and dexmedetomidine can produce specific dope viscosity and rise
Or paint solidification, therefore the problem of coating composition is difficult to store steadily in the long term be present.More specifically, find to contain first silicon
The shelf-life of the coating composition of the aftermentioned comparative example 3 of alkylacrylate copolymer is more than 6 months, and to the coating
The shelf-life that the coating composition of comparative example 1 described later obtained by dexmedetomidine is added in composition is less than 1 month.
In view of this problem, it is an object of the invention to provide contain silicyl esters (co) polymer and dexmedetomidine
Be used for prevent antifouling paint compositions being stained of the base material as caused by aquatile and application thereof, the composition being capable of shape
Into the antifouling coat that can play long-term excellent soil resistance and there is good storage-stable.
Technical scheme used by solution technical problem
The present inventor passes through numerous studies, finds even containing silicyl esters (co) polymer and dexmedetomidine
Antifouling paint compositions, storage-stable can be also improved by being coexisted with specific composition, so as to complete the present invention.The present invention
Main contents it is as described below.
[1] antifouling paint compositions, wherein, containing silicyl esters (co) polymer (A), dexmedetomidine (B) and
At least one composition (C) selected from dehydrating agent (c1) and rosin (c2),
The silicyl esters (co) polymer (A) has by leading to formula (I)：
R1- CH=CH-COO- (SiR2R3O)n-SiR4R5R6
…(I)
Construction unit derived from shown monomer (a),
In formula (I), R2、R3、R4、R5And R6It is separately the 1 valency organic group can with heteroatomic carbon number 1~20
Group,
R1It is hydrogen atom or R7- O-C=O, wherein, R7It is hydrogen atom, there can be 1 valency of heteroatomic carbon number 1~20 organic
Group or R8R9R10Silicyl shown in Si, wherein, R8、R9And R10It is separately can have heteroatomic carbon number 1~20
1 valency organic group,
N is 0 or more than 1 integer.
[2] antifouling paint compositions as described in [1], wherein, the composition (C) contains the dehydrating agent (c1), described
Dehydrating agent (c1) contains at least one composition selected from the organosilan containing hydrolization group, zeolite and ortho esters.
[3] antifouling paint compositions as described in [2], wherein, the dehydrating agent (c1) contains hydrolization group containing described
Organosilan.
[4] antifouling paint compositions as described in [2] or [3], wherein, the dehydrating agent (c1) contains the zeolite.
[5] antifouling paint compositions as any one of [2]~[4], wherein, the dehydrating agent (c1) is containing described
Ortho esters.
[6] antifouling paint compositions as any one of [1]~[5], wherein, the composition (C) contains the pine
Fragrant class (c2).
[7] antifouling paint compositions as any one of [1]~[6], wherein, the solids of antifouling paint compositions into
Divide the dexmedetomidine (B) containing 0.001~10 weight % in 100 weight %.
[8] antifouling paint compositions as any one of [1]~[7], wherein, relative to the silicyl esters
The parts by weight of (co) polymer (A) 100, the dehydrating agent (c1) containing 0.01~200 parts by weight.
[9] antifouling paint compositions as any one of [1]~[8], wherein, relative to the dexmedetomidine (B)
100 parts by weight, the dehydrating agent (c1) containing 1~100000 parts by weight.
[10] antifouling paint compositions as any one of [1]~[9], wherein, relative to the silyl ester
The parts by weight of class (co) polymer (A) 100, the rosin (c2) containing 0.01~500 parts by weight.
[11] antifouling paint compositions as any one of [1]~[10], wherein, relative to the dexmedetomidine
(B) 100 parts by weight, the rosin (c2) containing 1~50000 parts by weight.
[12] antifouling paint compositions as any one of [1]~[11], wherein, in the logical formula (I), R4、R5With
R6It is isopropyl.
[13] antifouling paint compositions as any one of [1]~[12], wherein, the silicyl esters (common)
Polymer (A) also has construction unit derived from the unsaturated monomer (b) that can be copolymerized with the monomer (a).
[14] antifouling paint compositions as described in [13], wherein, the unsaturated monomer (b), which is contained, is selected from (methyl) third
Monomer, (methyl) alkoxyalkyl acrylate, (methyl) dihydroxypropyl alkane shown in olefin(e) acid Arrcostab, following logical formula (II)s
At least one of (methyl) acrylate of base ester, (methyl) acrylate of the ester group containing metal and the base containing organosiloxane is not
Saturation monomer,
R11- CH=C (CH3)-COO-(SiR12R13O)n-SiR14R15R16
…(II)
In formula (II), R12、R13、R14、R15And R16It is separately that 1 valency that can have heteroatomic carbon number 1~20 has
Machine group,
R11It is hydrogen atom or R17- O-C=O, wherein, R17It is hydrogen atom, can has with 1 valency of heteroatomic carbon number 1~20
Machine group or R18R19R20Silicyl shown in Si, wherein, R18、R19And R20It is separately can have heteroatomic carbon number
1~20 1 valency organic group,
N is 0 or more than 1 integer.
[15] antifouling paint compositions as described in [14], wherein, the unsaturated monomer is to be selected from (methyl) acrylic acid
Methyl esters, (methyl) ethyl acrylate, (methyl) butyl acrylate, methacrylic acid triisopropylsilyl ester, (methyl) third
At least one unsaturated monomer of olefin(e) acid 2- methoxy acrylates and (methyl) acrylic acid 2- hydroxy methacrylates.
[16] antifouling paint compositions as any one of [13]~[15], wherein, the silicyl esters
(co) polymer (A) the also construction unit as derived from the monomer (a) containing 40~80 weight %.
[17] antifouling paint compositions as any one of [1]~[16], wherein, relative to the silyl ester
The parts by weight of class (co) polymer (A) 100, the dexmedetomidine (B) containing 0.001~50 parts by weight.
[18] antifouling paint compositions as any one of [1]~[17], wherein, also containing the dexmedetomidine
(B) anti-fouling agent (E) beyond.
[19] antifouling paint compositions as described in [18], wherein, the anti-fouling agent (E) beyond the dexmedetomidine (B) is
Selected from cuprous oxide, cuprous rhodanide, copper, copper pyrithione, ZPT, the bromo- 2- of 4- (4- chlorphenyls) -5- (fluoroforms
Base) -1H- pyrroles -3- nitriles, DCOIT, borine-nitrogen class alkali addition product, N, N- diformazans
Base-N '-(3,4- dichlorophenyls) urea, N- (2,4,6- trichlorophenyls) maleimide, 2- methyl mercapto -4- tert-butylaminos -
6- cyclopropylamino -1,3,5- triazines, 2,4,5,6- daconil Ms, double (DMDS is for carbamoyl) zinc ethene
Double (dithiocarbamates), chloromethyl-n-octyl disulfide, N, N'- dimethyl-N'- phenyl-(N- fluorine dichloros methyl mercapto)
Sulfonamide, tetraalkylthiuram disulfide, PZ, ethene double (zinc dithiocarbamate), 2,
Chloro- N- (2 ', the 6 '-diethyl phenyl) maleimides of 3- bis- and 2,3- bis- chloro- N- (2 '-ethyl -6 '-aminomethyl phenyl) Malaysia acyl
At least one anti-fouling agent of imines.
[20] antifouling paint compositions as any one of [1]~[19], wherein, also contain monocarboxylic acid compound
(F)。
[21] antifouling paint compositions as any one of [1]~[20], the composition are 1 liquid type coating.
[22] antifouling coat that the antifouling paint compositions recorded by any one of above-mentioned [1]~[21] are formed.
[23] antifouling base material, it has base material and is arranged at the antifouling coat described in above-mentioned [22] of the substrate surface.
[24] with above-mentioned [23] of seawater or fresh water into contact described in antifouling base material.
[25] the antifouling base material described in [24] as described above, wherein, the base material is aouatic structure thing, ship plank or fishing
Tool.
[26] manufacture method of antifouling base material, it, which has to be coated with or be impregnated with above-mentioned [1]~[21] on the surface of base material, appoints
The process of antifouling paint compositions described in one and make to be coated on the base material using the process or be impregnated in the base material
The process of the antifouling paint solidification, or
With form film by the antifouling paint compositions and make the curing of coating and formed antifouling coat process and
The antifouling coat is attached into the process in base material.
[27] storage practice, this method are the storage practices of antifouling paint compositions, wherein, will be anti-described in above-mentioned [21]
Dirty coating composition, which is filled to container, to be stored.
Invention effect
By using the antifouling paint compositions of the present invention, the antifouling painting that can play excellent soil resistance for a long time can be formed
Film.Further, antifouling paint compositions of the invention can be stored steadily in the long term.
Embodiment
Antifouling paint compositions of the present invention etc. are described in detail below.
In addition, weight when carrying out regulation in the present invention to the content of composition as standard, contain dilution with molten in composition
It is the composition that may make up dry coating for eliminating volatile ingredient, i.e. " solid constituent " in the case of the volatile ingredients such as agent
Weight.Solid constituent refer to by the composition comprising volatile ingredients such as solvents or even composition at 105 DEG C in air drier
Middle drying makes the residual component after the volatilization such as solvent for 3 hours.In addition, " (co) polymer " is the general designation of polymer and copolymer
Sentence, " (methyl) acrylate " is the general designation sentence of acrylate and methacrylate.
[antifouling paint compositions]
The antifouling paint compositions of the present invention contain silicyl esters (co) polymer (A), dexmedetomidine (B) and spy
Determine composition (C).
＜ silicyl esters (co) polymer (A) ＞
Silicyl esters (co) polymer (A) is that have by leading to formula (I)：
R1- CH=CH-COO- (SiR2R3O)n-SiR4R5R6
Construction unit derived from shown monomer (a) (is also denoted as " ingredient units ", " Component units ", " repeat unit "
Deng) and arbitrarily as can with monomer (a) be copolymerized unsaturated monomer (b) derived from construction unit (co) polymer.Separately
Outside, if using A1A2C=CA3A4(C=C is polymerism carbon-to-carbon double bond) represents X, then " ingredient units as derived from X " refer to example
As the construction unit shown in following formula.
[changing 1]
In upper formula (I), R2、R3、R4、R5And R6It is separately the 1 valency organic group can with heteroatomic carbon number 1~20
Group, can enumerate straight-chain, branched or ring-type that the hetero atom such as oxygen atom can be between carbon atom and the key of carbon atom
Alkyl and aryl etc..Silicyl esters (co) polymer (A) water at the appropriate speed from the antifouling coat of the present invention
From the point of view of solution, R2、R3、R4、R5And R6The preferably alkyl such as methyl, ethyl, isopropyl, sec-butyl, more preferably isopropyl.
R1It is hydrogen atom or R7- O-C=O, preferably hydrogen atom, wherein, R7It is hydrogen atom, there can be heteroatomic carbon number 1
~20 1 valency organic group or R8R9R10Silicyl shown in Si, wherein, R8、R9And R10It is separately can have miscellaneous original
1 valency organic group of the carbon number 1~20 of son.
As R7、R8、R9And R10The 1 valency organic group with heteroatomic carbon number 1~20, can separately example
Illustrate straight-chain that such as oxygen atom hetero atom can be between carbon atom and the key of carbon atom, branched or ring-type alkyl with
And aryl etc., preferred isopropyl.
N is 0 or more than 1 integer, preferably 0.N higher limit for example can be 1000.
As the monomer (a) shown in the formula (I), such as acrylic acid trimethyl silyl ester, acrylic acid three can be enumerated
Ethyl silicane base ester, the n-propyl silyl ester of acrylic acid three, acrylic acid triisopropylsilyl ester, three positive fourth of acrylic acid
Base silyl ester, acrylic acid tri-iso-butylsilyl ester, the sec-butyl silyl ester of acrylic acid three, the 2- ethyls of acrylic acid three
Acrylic acid trialkylsilkl ester, the 1- acryloyls such as hexyl silyl ester, propylene acid butyl diisopropylsilyl ester
Methyl tetrasiloxane (the Japanese of epoxide nine：1- ア Network リ ロ イ Le オ キ シ ノ Na メ チ Le テ ト ラ シ ロ キ サ Application), wherein,
From the hydrolysis rate of the silicyl esters (co) polymer (A) in the antifouling coat of the present invention and the antifouling coat of the present invention
Surface Renewal continuation and from the point of view of having excellent water-resistance, preferred acrylic acid triisopropylsilyl ester.
As the unsaturated monomer (b) that can be copolymerized with monomer (a), preferably (methyl) methyl acrylate, (methyl) propylene
Acetoacetic ester, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) i-butyl
Ester, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (first
Base) cyclohexyl acrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-ethylhexyl acrylate,
The own ester of (methyl) acrylic acid 3,5,5- trimethyls, (methyl) lauryl acrylate, (methyl) acrylic acid cetyl, (methyl) propylene
Sour stearate etc. (methyl) alkyl acrylate；
(methyl) phenyl acrylate；
(methyl) benzyl acrylate；
(methyl) methoxyethyl methyl esters, (methyl) acrylic acid 2- methoxy acrylates, (methyl) ethioxy first
Ester, (methyl) acrylic acid 2- ethoxy ethyl esters, (methyl) acrylic acid 4- methoxybutyls, (methyl) methoxypropyl ester,
(methyl) ethioxy propyl ester, (methyl) acrylic acid propoxy ethyl, (methyl) acrylic acid 2- butoxyethyls, (methyl)
(methyl) alkoxyalkyl acrylates such as i-butyl epoxide butyldiglycol ester, (methyl) acrylate；
(methyl) dihydroxypropyl methyl esters, (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters,
(methyl) the dihydroxypropyl alkyl such as (methyl) acrylic acid 4- hydroxybutyls, (methyl) acrylic acid 2- hydroxyl -3- phenoxy-propyls
Ester；
(methyl) zinc acrylate resin, two (methyl) zinc acrylate resins, (methyl) acrylic acid copper, two (methyl) acrylic acid copper etc. are containing gold
Belong to (methyl) acrylates of ester group；
(methyl) acrylate of the base containing organosiloxane, and
Logical formula (II)：
R11- CH=C (CH3)-COO-(SiR12R13O)n-SiR14R15R16
Shown monomer,
[in formula (II), R12、R13、R14、R15And R16It is separately that 1 valency that can have heteroatomic carbon number 1~20 has
Machine group, straight-chain, branched, ring that the hetero atom such as oxygen atom can be between carbon atom and the key of carbon atom can be enumerated
The alkyl of shape, aryl etc..From silicyl esters (co) polymer (A) water at the appropriate speed in the antifouling coat of the present invention
From the point of view of solution, preferably alkyl, more preferably isopropyl.
R11It is hydrogen atom or R7- O-C=O, preferably hydrogen atom, wherein, R17It is hydrogen atom, there can be heteroatomic carbon number
1~20 1 valency organic group or R18R19R20Silicyl shown in Si, wherein, R18、R19And R20It is separately to have
1 valency organic group of heteroatomic carbon number 1~20.
As R17、R18、R19And R20The 1 valency organic group with heteroatomic carbon number 1~20, can be separately
Enumerate straight-chain, branched, ring-type that the hetero atom such as oxygen atom can be between carbon atom and the key of carbon atom alkyl,
Aryl etc., preferably isopropyl.
N is 0 or more than 1 integer, preferably 0.N higher limit for example can be 1000.]
Wherein, more preferably (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl)
Acrylic acid 2- methoxy acrylates, (methyl) acrylic acid 2- hydroxy methacrylates, methacrylic acid triisopropylsilyl ester.From can
From the point of view of manufacturing the particularly excellent antifouling paint compositions of storage-stable, silicyl esters (co) polymer (A) is more
The construction unit as derived from (methyl) acrylic acid 2- methoxy acrylates as unsaturated monomer (b) is preferably comprised, it is especially excellent
Containing 1~30 weight %, construction unit, scope as derived from (methyl) acrylic acid 2- methoxy acrylates can also be 1 for choosing
~40 weight %.
From the point of view of the Surface Renewal continuation of antifouling coat from the present invention etc. is excellent, it is expected in the silyl ester
In class (co) polymer (A), the content of construction unit as derived from monomer (a) is usually 10~100 weight %, is preferably 10
~90 weight %, more preferably 30~80 weight %, the construction unit as derived from unsaturated monomer (b) is remainder,
I.e. content is usually 0~90 weight %, is preferably 10~90 weight %, more preferably 20~70 weight % (wherein, silicyls
The amount of all construction units is 100 weight % in esters (co) polymer (A).).
In addition, from the point of view of viscosity, storage-stable, Physical properties of coating film, the silicyl esters (co) polymer (A)
Number-average molecular weight Mn (polystyrene scaled values.Assay method be embodiment column described later described in method or be equal with this
Method.) it is usually 1,000~200,000, preferably 1,000~100,000.
The content of silicyl esters (co) polymer (A) in the antifouling paint compositions of the present invention is being scaled solid
In the said composition of composition, preferably 0.1~99 weight %, more preferably 5~90 weight %, particularly preferably 10~80 weights
Measure %.
Silicyl esters (co) polymer (A) can by using known polymerization by the monomer (a) with it is arbitrary
The unsaturated monomer (b) polymerize (copolymerization) to prepare.
The construction unit as derived from the monomer (a) that contains in silicyl esters (co) polymer (A) and by institute
Respective content (weight) ratio for stating construction unit derived from unsaturated monomer (b) is tended to and for described in polymerisation
The ratio of the addition of monomer (a) and the unsaturated monomer (b) (weight) is consistent.
<Dexmedetomidine (B)>
Dexmedetomidine is (±) -4- [1- (2,3- 3,5-dimethylphenyls) ethyl] -1H- imidazoles.
The content of the dexmedetomidine (B) of the antifouling paint compositions of the present invention is at antifouling paint compositions (solid constituent)
It is preferably 0.001~10 weight % in 100 weight %.In addition, dexmedetomidine (B's) of the antifouling paint compositions of the present invention contains
Amount is relative to the parts by weight of silicyl esters (co) polymer (A) 100, preferably 0.01~50 parts by weight, more preferably 0.02~
20 parts by weight, further preferred 0.04~10 parts by weight.By making the content of dexmedetomidine (B) within the range, by the present invention
Antifouling paint compositions obtained by antifouling coat can play excellent soil resistance.
<Composition (C)>
The antifouling paint compositions of the present invention contain at least one composition selected from dehydrating agent (c1) and rosin (c2)
(C)。
Any or this two class combination of organic, inorganic can be used in dehydrating agent (c1).
As the dehydrating agent of organic, can enumerate the ortho esters such as the organosilan containing hydrolization group, alkyl orthoformate,
Ortho-boric acid, isocyanates etc., organosilan or alkyl orthoformate preferably containing hydrolization group, further preferably containing water-disintegrable
The organosilan of group.
As the organosilan containing hydrolization group, the compound shown in preferably following logical formula (III)s.
R10 nSiY(4-n)…(III)
In above-mentioned logical formula (III), R10It is independently the alkyl (such as methyl, ethyl) of carbon number 1~6, Y is independently
Hydrolization group (such as methoxyl group, ethyoxyl), n are 0~3 integers.
As this organosilan containing hydrolization group, commercially available product can be used, can enumerate for example as orthosilicic acid
Tetra-ethyl ester " silester 28 " (" エ チ Le シ リ ケ ー ト 28 ") (COLCOAT Co., Ltd. (U ル コ ー ト societies) system), conduct
" KBM-13 " (Shin-Etsu Chemial Co., Ltd's (SHIN-ETSU HANTOTAI's chemical industry (strain)) system) of alkyltrialkoxysilaneand etc..
As the dehydrating agent of inorganic, zeolite, aluminum oxide, silica etc., preferred zeolite can be enumerated.
As this zeolite, the commercially available prod for being commonly referred to as " molecular sieve (モ Le キ ュ ラ ー シ ー Block) " can be used.
If containing these compositions as dehydrating agent (c1), good coating storage-stable can be obtained.
When composition (C) is dehydrating agent (c1) selected from the organosilan containing hydrolization group, zeolite and ortho esters, the present invention
Antifouling paint compositions in dehydrating agent (c1) content relative to the weight of silicyl esters (co) polymer (A) 100
Measure part, preferably 0.01~200 parts by weight, more preferably 1~50 parts by weight, relative to the weight of the dexmedetomidine (B) 100
Amount part, preferably 1~100,000 parts by weight, more preferably 10~10,000 parts by weight.Dehydrating agent (c1) if incorporation exist
In the range of being somebody's turn to do, then good coating storage-stable can be obtained.
As rosin (c2), the rosin such as gum rosin, wood rosin, toll oil rosin, hydrogenated rosin, disproportionation pine can be enumerated
The rosin derivatives such as perfume, rosin metal salt, pine tar etc..
When composition (C) is rosin (c2), the content of the rosin (c2) in antifouling paint compositions of the invention is relative
In the parts by weight of silicyl esters (co) polymer (A) 100, preferably 0.01~500 parts by weight, more preferably 1
~300 parts by weight, particularly preferably 10~200 parts by weight, relative to the parts by weight of the dexmedetomidine (B) 100, preferably 1~
50,000 parts by weight.If containing rosin (c2) with this ratio, it is steady that antifouling paint compositions can obtain good storage
Qualitative, antifouling coat can obtain good soil resistance.
<Any condition>
In the antifouling paint compositions of the present invention, in addition to the composition, it can also mix antifouling beyond dexmedetomidine (B)
Agent (E), monocarboxylic acid compound (F), coloring pigment (G), filler pigment (H), plasticizer (I), thixotropic agent (J), silyl ester
Resinae (K), solvent (L) beyond class (co) polymer (A) etc. are used for the various composition of common coating composition.
Anti-fouling agent (E) beyond dexmedetomidine (B)
The antifouling paint compositions of the present invention are by containing the anti-fouling agent (E) beyond dexmedetomidine (B), can further carry
The high antifouling property as the antifouling coat obtained by antifouling paint compositions.
As the anti-fouling agent (E) beyond dexmedetomidine, inorganic and organic anti-fouling agent can be used, preferably for example oxidation is sub-
Copper, cuprous rhodanide (Japanese：ロ ダ ン Copper), copper, copper pyrithione, ZPT, the bromo- 2- of 4- (4- chlorphenyls) -5- (three
Methyl fluoride) -1H- pyrroles -3- nitriles, DCOIT, borine-nitrogen class alkali addition product (pyridine
Triphenylborane, 4- isopropyl pyridine diphenyl methyl borines etc.), N, N- dimethyl-N '-(3,4- dichlorophenyls) urea, N-
(2,4,6- trichlorophenyls) maleimide, 2- methyl mercapto -4- tert-butylamino -6- cyclopropylamino -1,3,5- triazines, 2,4,
5,6- daconil Ms, double (DMDS is for carbamoyl) zinc ethene double (dithiocarbamate), chloromethyl-
N-octyl disulfide, N, N'- dimethyl-N'- phenyl-(N- fluorine dichloros methyl mercapto) sulfonamide, tetraalkylthiuram disulfide, two
Zine dimethyldithiocarbamate, ethene double (zinc dithiocarbamate), 2,3- bis- chloro- N- (2 ', 6 '-diethyl phenyl) horses
Come acid imide and 2,3- bis- chloro- N- (2 '-ethyl -6 '-aminomethyl phenyl) maleimide, these compositions can be also respectively combined and
Use.
The incorporation of anti-fouling agent (E) beyond dexmedetomidine can be adjusted suitably, such as relative to silicyl esters (common)
The parts by weight of polymer (A) 100 are 0.01~1000 parts by weight.
Monocarboxylic acid compound (F)
The antifouling paint compositions of the present invention are by containing monocarboxylic acid compound (F), it is possible to increase are combined by antifouling paint
The Surface Renewal and water resistance of antifouling coat obtained by thing.
As monocarboxylic acid compound (F), the preferably saturation of carbon number 10~20 or unsaturated fatty hydrocarbons base or carbon
The substitution body of the saturation of atomicity 3~20 or unsaturated alicyclic type hydrocarbon or these compositions.Wherein, preferably trimethyl isobutyl
Alkenyl cyclohexene carboxylate, versatic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, leukotrienes, abietic acid, neoabietic acid, pimaric acid (day
Text：ピ マ Le acid), dehydroabietic acid, 12- hydroxy stearic acids or aphthenic acids and its salt (such as metal salt).As trimethyl isobutyl
Alkenyl cyclohexene carboxylate, such as the reaction product of 2,6- dimethyl -2,4,6- sarohornenes and methacrylic acid can be enumerated, it is led
Composition (more than 85%) is 1,2,3- trimethyls -5- (2- methyl-1-propylene -1- bases) -3- cyclohexene -1- carboxylic acids and 1,4,5-
Trimethyl -2- (2- methyl-1-propylene -1- bases) -3- cyclohexene -1- carboxylic acids.
The incorporation of monocarboxylic acid compound (F) can be adjusted suitably, such as relative to silicyl esters (co) polymer (A)
100 parts by weight are 0.01~1000 parts by weight, preferably 1~500 parts by weight.
Coloring pigment (G)
As coloring pigment (G), the inorganic face such as iron oxide red, titanium white (titanium oxide), yellow iron oxide can be enumerated
The organic pigments such as material, carbon black, naphthol reds, phthalocyanine blue.These coloring pigments be can be used alone a kind, or two or more is combined
Use.In addition, it can also contain the various colouring agents such as dyestuff in coloring pigment.
The incorporation of coloring pigment (G) can be adjusted suitably, such as relative to silicyl esters (co) polymer (A) 100
Parts by weight are 0.05~125 parts by weight.
Filler pigment (H)
Filler pigment (H) be refractive index it is small, with oil and varnish be kneaded in the case of it is transparent without cover be applied face
Pigment.As filler pigment (H), such as talcum, mica, clay, potassium feldspar, zinc oxide, calcium carbonate, kaolin, oxygen can be enumerated
Change aluminium white, white carbon, aluminium hydroxide, magnesium carbonate, barium carbonate, barium sulfate, zinc sulphide etc., wherein, preferably zinc oxide, talcum, cloud
Mother, clay, calcium carbonate, kaolin, barium sulfate, calcium sulfate, potassium feldspar.These filler pigments can be used alone a kind, or by 2
Kind combination of the above uses.
The incorporation of filler pigment (H) can be adjusted suitably, such as relative to silicyl esters (co) polymer (A) 100
Parts by weight are 0.5~250 parts by weight.
Plasticizer (I)
Plasticizer (I) is the crack resistance and water resistance and the composition for suppressing discoloration for improving antifouling coat.As plasticising
Agent, n- paraffin, chlorinated paraffin, terpene phenol, tricresyl phosphate (TCP), polyvinyl ethyl ether etc. can be enumerated, wherein it is preferred that chlorination
Paraffin, terpene phenol, particularly preferred chlorinated paraffin.These plasticizer be can be used alone a kind, or two or more is applied in combination.
As the n- paraffin, " the n- パ ラ Off ィ Application " of Nippon Petrochemicals Company, Limited (Japan petroleum chemistry (strain)) system can be used
Deng commodity, as the chlorinated paraffin, TOSOH Co., Ltd (East ソ ー (strain) can be used) " the ト ヨ パ ラ ッ Network ス A-40/ of system
The commodity such as A-50/A-70/A-145/A-150 ".
The incorporation of plasticizer (I) can be adjusted suitably, such as relative to all solids composition in antifouling paint compositions
For 1~5 weight %.
Thixotropic agent (J)
Thixotropic agent (J) is to confer to coating resist sagging and the composition of anti-settling.As thixotropic agent (J), can enumerate for example
Organobentonite, Al, Ca or Zn stearate, lecithin salt, alkylsulfonate, Tissuemat E, OPE, acid amides
Wax, rilanit special wax, amide waxe/OPE compound system.These thixotropic agent can be used alone a kind, or by 2 kinds
Combination of the above uses.
The incorporation of thixotropic agent (J) can be adjusted suitably, such as relative to the weight of silicyl esters (co) polymer (A) 100
Amount part is 0.25~50 parts by weight.
Other resinaes (K)
The antifouling paint compositions of the present invention are in addition to the silicyl esters (co) polymer (A), as needed also
Contain other one kind or two or more resinaes (K).
Can be used the acrylic resin for example without metal ester bond, the acrylic resin containing metal (except silicon) ester group,
Acrylic acid organic siliconresin, polyester resin, unsaturated polyester resin, fluororesin, polybutene resin, organic silicon rubber, polyurethane
Resin, epoxy resin, polyamide, vinyl (ethlyene dichloride analog copolymer, EVAc etc.),
Chlorinated rubber, chlorinated alkenes resin, styrenebutadiene copolymer resin, ketone resin, alkyd resin, coumarone resin, terpenes
Phenolic resin, Petropols etc. are water-insoluble or are insoluble in the resin of water.
The incorporation of other resinaes (K) can be adjusted suitably, such as relative to silicyl esters (co) polymer (A)
100 parts by weight are 0.01~1000 parts by weight.
Solvent (L)
The various composition of the antifouling paint compositions of the composition present invention is in the same manner as common antifouling paint compositions molten
Dissolved in agent or scattered.Can be used in the present invention common aliphatic category solvent, fragrant same clan's solvent (dimethylbenzene, toluene etc.),
Ketones solvent (MIBK, cyclohexanone etc.), esters solvent, ether solvent (propylene glycol monomethyl ether, propylene glycol monomethyl ether second
Acid esters etc.), the solvent as antifouling paint such as alcohols solvent (isopropanol etc.).
The incorporation of solvent (L) can be adjusted suitably, such as reach all solids component ratio of antifouling paint compositions
20~90 weight % ratio, also can further it be added in application according to operability.
(manufacture methods of antifouling paint compositions)
The device same with known conventional antifouling paint, method etc. can be used to carry out for the antifouling paint compositions of the present invention
Prepare.For example, after silicyl esters (co) polymer (A) has been prepared in advance, using the (co) polymer (A) (as (common)
The form of polymer (A), (co) polymer (A) solution (solution obtained by during preparation (co) polymer (A)) can be enumerated) and it is beautiful
The compositions such as support miaow pyridine (B), composition (C) and other additives as needed are disposable or are added to solvent successively, stirring, mix
Close to manufacture.
In addition, the storage-stable of the antifouling paint compositions of the present invention is high, it can will not only contain silicyl esters
The composition of (co) polymer (A) and composition containing dexmedetomidine (B) are separately stored, and can be also used as and be contained silicyl esters
1 liquid type coating of (co) polymer (A), dexmedetomidine (B) and composition (C) is stored.
[antifouling coat and antifouling base material]
The antifouling coat of the present invention is formed by the solid constituent of the antifouling paint compositions of the present invention.The antifouling painting of the present invention
In the case that film is by the antifouling paint compositions of the present invention are formed, such as antifouling paint compositions contain solvent (L), then it can lead to
The antifouling paint compositions of the invention that cross makes to be coated on base material using the drying device such as natural drying or heater are consolidated
The mode changed and (that is, the solvent (L) removed) is formed.
In addition, the antifouling base material of the present invention is formed by base material with being formed at the antifouling coat of the invention of the substrate surface,
It can manufacture in the following manner：Using the coating tool such as aerial spraying, airless spraying, hairbrush, roller by the present invention's
Antifouling paint compositions are coated on base material (base material can be antifouling purpose thing or coated object), or base material are impregnated with, use example
As the natural drying drying device such as (that is, being dried with the temperature of substantially room temperature) or heater is made coating or is impregnated in base material
Coating composition is dry, solidification, and antifouling coat is formed on base material.
Or antifouling base material of the invention can also manufacture in the following manner：By the present invention on interim substrate surface
Antifouling paint compositions formed antifouling coat, the antifouling coat is peeled off from temporary substrate, stick in should be antifouling base
Material.Now, also antifouling coat can be attached on base material by bond layer.
As above-mentioned base material, it is not particularly limited, preferably with seawater or the base material of fresh water into contact, can specifically enumerates various generatings
Stand (firepower, nuclear energy) the various oceans such as the discharge mouth of a river, gulf bank road, seabed tunnel, bay equipment or canal or water channel or
The aouatic structure such as sludge nonproliferation film used in rivers and creeks earthwork thing, ship plank are (particularly from the drinking water portion of ship
To boat bottom), fishery goods, materials and equipments (fishing gear such as rope, fishing net, float or buoy etc.).
The material of these base materials, steel, aluminium, timber, FRP etc. can be enumerated especially in ship plank, can example in fishing net etc.
Naturally occurring or synthetic fiber is lifted, or plastic article can be enumerated in float, buoy etc., as long as to soil resistance in water
Deng desired base material being present, then its material is not particularly limited.
In the case that the surface of these base materials, particularly base material are hull bottom etc., generally, antirust is coated with steel substrate surface
On the surface of primer processing base material after the primers such as coating, if method described above coating is one or many of the invention antifouling
Coating composition (antifouling paint), make coating or be impregnated with and (particularly implement impregnation in the case where base material is fishing net etc.) and be antifouling
Coating composition and form antifouling coat, then prevent sea lettuce, barnacle, green laver, Hai Mango (Japaneses for a long time：セルプ
ラ), the characteristic (soil resistance, particularly standing soil resistance) of the attachment of aquatile such as oyster, careless tongue worm is excellent, can be long-term
Interior slowly release anti-fouling composition.
Generally, in the case that substrate surface is treated by primer, the layer with the formation of various bonding agent coating be present
Situation.In the case that base material is ship plank (particularly its hull bottom), aouatic structure thing etc., if repeatedly being applied on its substrate surface
Cloth (also referred to as thick to apply, the dry film thickness of the film of formation is 100~600 μm or so) antifouling paint compositions, then gained is antifouling
Base material can balancedly play appropriate bendability and excellent crack resistance while soil resistance is excellent.
, can in the case that base material is steel plate and fishing net with deterioration antifouling coat etc. when manufacturing above-mentioned antifouling base material
The antifouling paint compositions of the present invention are directly coated with its surface, or in the case where base material is fishing net etc., the present invention can be made
Antifouling paint compositions be impregnated in its surface, or in the case where base material is steel plate blank, can be applied in advance in substrate surface
After the base material such as cloth antirust agent and primer forms basalis, in the antifouling paint group of the surface of the basalis coating present invention
Compound.In addition, also can formed with the present invention antifouling coat or conventional antifouling coat base material surface, to repair as mesh
Further formation the present invention antifouling coat.
Though in addition, it is not particularly limited by 1 painting work and the thickness of the antifouling coat of the invention formed, in base
In the case that material is ship plank and aouatic structure thing, for example, 30~250 μm or so.
The aouatic structure thing of antifouling coat with the present invention is because that can prevent the attachment of aquatile for a long time, so can grow
Phase maintains the function of aouatic structure thing.In addition, with the present invention antifouling coat fishing net because environmental pollution worry seldom and
The attachment of aquatile can be prevented, so the obstruction of mesh can be prevented.
Embodiment
Hereinafter, the present invention is specifically described by embodiment, but the present invention is not limited to these embodiments.
<The viscosity of silicyl esters (co) polymer solution>
Viscosity of the silicyl esters (co) polymer solution at 25 DEG C passes through (the eastern machine industry strain formula meeting of E types viscosimeter
Society's (East Machine industries (strain)) system) it is determined.
<The solid component concentration of silicyl esters (co) polymer solution>
Solid constituent refers to reactant mixture, coating or uncured film comprising resin and solvent etc. etc. at 105 DEG C
Under in air drier dry 3 hours and make solvent etc. volatilize after heating residual component.Solid constituent is generally except resin
Composition is also film forming component containing pigment etc..
<Number-average molecular weight (Mn), the weight average molecular weight (Mw) of silicyl esters (co) polymer>
The equal molecule of number of silicyl esters (co) polymer is determined using GPC (gel permeation chromatography) with following conditions
Measure (Mn) and weight average molecular weight (Mw).
GPC conditions
Device：" HLC-8120GPC " (TOSOH Co., Ltd's system)
Post：" SuperH2000+H4000 " (TOSOH Co., Ltd's system, 6mm (internal diameter), each 15cm (length))
Eluent：Tetrahydrofuran (THF)
Flow velocity：0.500ml/ minutes
Detector：RI
Post thermostat temperature：40℃
Standard substance：Polystyrene
Sample modulator approach：A small amount of calcium chloride is added in the polymer solution modulated in each Production Example to be dehydrated
Afterwards, filtrate sample will be determined as GPC as obtained by filtering filter membrane device.
[Production Example] (manufacture of silicyl lipin polymer solution (A-1))
To be provided with mixer, condenser, thermometer, dropper, nitrogen ingress pipe and heating cooling jacket it is anti-
Answer and 54 parts by weight of xylene are added in container, heating stirring has been carried out with 85 DEG C ± 5 DEG C of temperature conditionss in stream of nitrogen gas.
It has been added dropwise while keeping mutually synthermal by dropper with 2 hours by 60 parts by weight of acrylic acid three into the reaction vessel
The 2,2'- of isopropyl silyl ester, the monomer mixture that 40 parts by weight of methylmethacrylate are formed and 0.75 parts by weight
The mixture that azodiisobutyronitrile is formed.Then, after stirring 2 hours at the same temperature, 0.4 parts by weight 2 are added, 2'- is even
Nitrogen bis-isobutyronitrile, further stir 4 hours at the same temperature, add the dimethylbenzene of 44 parts by weight, obtained water white transparency
Silicyl lipin polymer solution (A-1).
The amount and solution (A-1) of raw material used and the characteristic value of the silicyl lipin polymer wherein contained are shown in
Table 1.
[Production Example 2~4] (silicyl lipin polymer solution (A-2)~(A-4) manufacture)
Except substituting monomer mixture used in Production Example 1, appropriate using the monomer mixture with composition shown in table 1
It has adjusted dimethylbenzene and 2, beyond the addition of 2'- azodiisobutyronitriles, prepared in the same manner as Production Example 1 and contained silicyl
Silicyl lipin polymer solution (A-2)~(A-4) of lipin polymer.
Amount and solution (A-2)~(A-4) of raw material used and the spy of the silicyl lipin polymer wherein contained
Property value is shown in table 1.
[table 1]
<Table 1>The Production Example of silicyl lipin polymer
[embodiment 1~34, comparative example 1~6]
(manufactures of antifouling paint compositions)
By solution (A-1~A-4), the dexmedetomidine of the lipin polymer containing silicyl of the gained of Production Example 1~4
(B), the composition shown in the table 2,3 such as dehydrating agent (c1), rosin (c2) according to the ratio shown in table 2,3, (attach most importance to by the numerical value in table
Amount part) uniformly mixed with paint shaker, antifouling paint compositions are thereby manufactured, implement evaluation as follows.
<Storage-stable>
The storage-stable of antifouling paint compositions is carried out from following shelf-life and viscosity stability these two aspects
Evaluation.
(shelf-life)
The antifouling paint compositions of the embodiment are stored at normal temperatures, 1 month state to coating is often crossed and carries out really
Recognize, the moon number passed through untill one month before coating is formed into gel state or solidification is used as shelf-life, progress
Evaluation.
(viscosity stability)
The antifouling paint compositions of embodiment and comparative example are stored 2 weeks at 50 DEG C, carried out to storing front and rear viscosity
Compare.Value obtained by viscosity before the front and rear viscosity number value difference of storage divided by storage is used as " viscosity rate of rise (%) ", is based on
The value is evaluated the viscosity stability of antifouling paint compositions.In addition, "-" in table 2 represent shelf-life it is extremely short and
It is not carried out determining.
With stormer viscosity meter (manufacturer under 23 DEG C of temperature conditionss：Tai Youji materials Co., Ltd. (helps very much Machine material strain formulas
Commercial firm), product name：Stormer viscosity meter, model 691) determine the viscosity of each composition.
<The standing soil resistance of film>
Epoxies antirusting paint (epoxy AC is coated with blasting treatment steel plate (long 300mm × wide 100mm × thick 3.2mm)
Coating, and trade name " バ ン ノ ー 500 ", Chugoku Marine Paints, Ltd. (Zhong Guo Tu expect (strain)) system), it is 150 μ to make its dry film thickness
M, vinyl adhesive coating (trade name " シ Le バ ッ Network ス SQ-K ", Chugoku Marine Paints, Ltd.'s system) is being coated with thereon afterwards,
It is 40 μm to make its dry film thickness.The antifouling paint compositions of 1 embodiment manufacture are further being coated with thereon, make its drying
Thickness is 100 μm, is dried at room temperature for 7 days, has made the breadboard with antifouling coat.In addition, 3 applications are with 1
Secondary/the mode of 1 day is carried out.
The breadboard made as described above is stood into dipping 3 months in Tokyo Bay during summer, determines antifouling painting
The area (being also denoted as barnacle bond area below) of the part for being attached with barnacle of film.Afterwards, according to following [based on the attached of barnacle
The metewand of the standing soil resistance of area] the standing soil resistance of antifouling coat is evaluated.As a result such as the institute of table 2,3
Show.
[metewand of the standing soil resistance of the bond area based on barnacle]
0：Unattached barnacle
1：Part is attached with barnacle
2：Whole face is attached with barnacle
[table 2]
[table 3]
Claims (27)
1. antifouling paint compositions, it is characterised in that containing silicyl esters (co) polymer (A), dexmedetomidine (B) and
At least one composition (C) selected from dehydrating agent (c1) and rosin (c2),
The silicyl esters (co) polymer (A) has by leading to formula (I)：
R1- CH=CH-COO- (SiR2R3O)n-SiR4R5R6
…(I)
Construction unit derived from shown monomer (a),
In formula (I), R2、R3、R4、R5And R6It is separately the 1 valency organic group can with heteroatomic carbon number 1~20,
R1It is hydrogen atom or R7- O-C=O, wherein, R7It is hydrogen atom, there can be 1 valency organic group of heteroatomic carbon number 1~20
Or R8R9R10Silicyl shown in Si, wherein, R8、R9And R10It is separately can have the 1 of heteroatomic carbon number 1~20
Valency organic group,
N is 0 or more than 1 integer.
2. antifouling paint compositions as claimed in claim 1, it is characterised in that the composition (C) contains the dehydrating agent
(c1), the dehydrating agent (c1) contains at least one composition selected from the organosilan containing hydrolization group, zeolite and ortho esters.
3. antifouling paint compositions as claimed in claim 2, it is characterised in that the dehydrating agent (c1) is containing described containing hydrolysis
The organosilan of property group.
4. antifouling paint compositions as claimed in claim 2 or claim 3, it is characterised in that the dehydrating agent (c1) contains the boiling
Stone.
5. the antifouling paint compositions as any one of claim 2~4, it is characterised in that the dehydrating agent (c1) contains
There is the ortho esters.
6. such as antifouling paint compositions according to any one of claims 1 to 5, it is characterised in that the composition (C) is containing
State rosin (c2).
7. such as antifouling paint compositions according to any one of claims 1 to 6, it is characterised in that antifouling paint compositions
The dexmedetomidine (B) containing 0.001~10 weight % in the weight % of solid constituent 100.
8. such as antifouling paint compositions according to any one of claims 1 to 7, it is characterised in that relative to the monosilane
The parts by weight of base ester class (co) polymer (A) 100, the dehydrating agent (c1) containing 0.01~200 parts by weight.
9. such as antifouling paint compositions according to any one of claims 1 to 8, it is characterised in that relative to the U.S. support miaow
The parts by weight of pyridine (B) 100, the dehydrating agent (c1) containing 1~100000 parts by weight.
10. such as antifouling paint compositions according to any one of claims 1 to 9, it is characterised in that relative to the monosilane
The parts by weight of base ester copolymer (A) 100, the rosin (c2) containing 0.01~500 parts by weight.
11. such as antifouling paint compositions according to any one of claims 1 to 10, it is characterised in that relative to the U.S. support
The parts by weight of miaow pyridine (B) 100, the rosin (c2) containing 1~50000 parts by weight.
12. the antifouling paint compositions as any one of claim 1~11, it is characterised in that in the logical formula (I),
R4、R5And R6It is isopropyl.
13. the antifouling paint compositions as any one of claim 1~12, it is characterised in that the silyl ester
Class (co) polymer (A) also has construction unit derived from the unsaturated monomer (b) that can be copolymerized with the monomer (a).
14. antifouling paint compositions as claimed in claim 13, it is characterised in that the unsaturated monomer (b), which is contained, to be selected from
Monomer, (methyl) alkoxyalkyl acrylate, (methyl) propylene shown in (methyl) alkyl acrylate, following logical formula (II)s
Acrylate is extremely for (methyl) of sour hydroxyalkyl acrylate, (methyl) acrylates of the ester group containing metal and the base containing organosiloxane
A kind of few unsaturated monomer,
R11- CH=C (CH3)-COO-(SiR12R13O)n-SiR14R15R16
…(II)
In formula (II), R12、R13、R14、R15And R16It is separately the 1 valency organic group can with heteroatomic carbon number 1~20
Group,
R11It is hydrogen atom or R17- O-C=O, wherein, R17It is hydrogen atom, there can be 1 valency organic group of heteroatomic carbon number 1~20
Group or R18R19R20Silicyl shown in Si, wherein, R18、R19And R20Be separately can have heteroatomic carbon number 1~
20 1 valency organic group,
N is 0 or more than 1 integer.
15. antifouling paint compositions as claimed in claim 14, it is characterised in that the unsaturated monomer is to be selected from (methyl)
Methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, methacrylic acid triisopropylsilyl ester, (first
Base) acrylic acid 2- methoxy acrylates and (methyl) acrylic acid 2- hydroxy methacrylates at least one unsaturated monomer.
16. the antifouling paint compositions as any one of claim 13~15, it is characterised in that the silyl ester
Class (co) polymer (A) the also construction unit as derived from the monomer (a) containing 30~80 weight %.
17. the antifouling paint compositions as any one of claim 1~16, it is characterised in that relative to the first silicon
The parts by weight of alkyl esters (co) polymer (A) 100, the dexmedetomidine (B) containing 0.001~50 parts by weight.
18. the antifouling paint compositions as any one of claim 1~17, it is characterised in that also containing the U.S. support
Anti-fouling agent (E) beyond miaow pyridine (B).
19. antifouling paint compositions as claimed in claim 18, it is characterised in that antifouling beyond the dexmedetomidine (B)
Agent (E) is selected from cuprous oxide, cuprous rhodanide, copper, copper pyrithione, ZPT, the bromo- 2- of 4- (4- chlorphenyls) -5-
(trifluoromethyl) -1H- pyrroles -3- nitriles, DCOIT, borine-nitrogen class alkali addition product,
N, N- dimethyl-N '-(3,4- dichlorophenyls) urea, N- (2,4,6- trichlorophenyls) maleimide, the tertiary fourths of 2- methyl mercaptos -4-
Base amino -6- cyclopropylamino -1,3,5- triazines, 2,4,5,6- daconil Ms, double (DMDS is for carbamyl
Base) zinc ethene double (dithiocarbamate), chloromethyl-n-octyl disulfide, N, N'- dimethyl-N'- phenyl-(N- fluorine two
Chloromethane sulfenyl) sulfonamide, tetraalkylthiuram disulfide, PZ, double (the dithiocarbamates first of ethene
Sour zinc), chloro- N- (2 ', the 6 '-diethyl phenyl) maleimides of 2,3- bis- and chloro- N- (the 2 '-ethyls -6 '-methylbenzene of 2,3- bis-
Base) maleimide at least one anti-fouling agent.
20. the antifouling paint compositions as any one of claim 1~19, it is characterised in that also contain mono-carboxylic acid
Compound (F).
21. the antifouling paint compositions as any one of claim 1~20, it is characterised in that the composition is 1 liquid
Type coating.
22. antifouling coat, it is characterised in that formed as the antifouling paint compositions any one of claim 1~21.
23. antifouling base material, it is characterised in that there is base material and be arranged at the antifouling painting described in the claim 22 of the substrate surface
Film.
24. antifouling base material as claimed in claim 23, it is characterised in that with seawater or fresh water into contact.
25. antifouling base material as claimed in claim 24, it is characterised in that the base material be aouatic structure thing, ship plank or
Fishing gear.
26. the manufacture method of antifouling base material, it is characterised in that have and be coated with or be impregnated with claim 1~21 in substrate surface
The process of antifouling paint compositions described in any one and make to be coated with using the process or be impregnated in the described antifouling of the base material
The process of coating composition, or
The process of antifouling coat is formed with forming film by the antifouling paint compositions and making the curing of coating and by institute
State antifouling coat and attach process in base material.
27. storage practice, this method is the storage practice of antifouling paint compositions, it is characterised in that by described in claim 21
Antifouling paint compositions fill to container and stored.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-104839 | 2015-05-22 | ||
| JP2015104839 | 2015-05-22 | ||
| PCT/JP2016/065010 WO2016190242A1 (en) | 2015-05-22 | 2016-05-20 | Antifouling coating composition, antifouling coating film, non-fouling base, process for producing non-fouling base, and method for storing antifouling coating composition |
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| CN107406712A true CN107406712A (en) | 2017-11-28 |
| CN107406712B CN107406712B (en) | 2019-05-21 |
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| CN201680013432.3A Active CN107406712B (en) | 2015-05-22 | 2016-05-20 | Antifouling paint compositions, antifouling coat, antifouling substrate, the manufacturing method of antifouling substrate and antifouling paint compositions storage practice |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6067200B1 (en) |
| KR (1) | KR101817486B1 (en) |
| CN (1) | CN107406712B (en) |
| WO (1) | WO2016190242A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110835486A (en) * | 2018-08-17 | 2020-02-25 | 佐敦有限公司 | Antifouling composition |
| CN111886304A (en) * | 2018-04-20 | 2020-11-03 | 日东化成株式会社 | Antifouling coating composition |
| CN112105697A (en) * | 2018-05-11 | 2020-12-18 | 中国涂料株式会社 | Antifouling coating composition, antifouling coating film, substrate with antifouling coating film, and antifouling method |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2808800T3 (en) * | 2016-12-22 | 2021-03-01 | Evonik Operations Gmbh | Isocyanate Adduct Compounds for Coating Compositions |
| CN110114426B (en) * | 2016-12-28 | 2021-08-24 | 中国涂料株式会社 | Antifouling coating composition, antifouling coating film, substrate with antifouling coating film, method for producing substrate with antifouling coating film, and antifouling method |
| KR102613892B1 (en) * | 2017-01-25 | 2023-12-13 | 닛토 가세이 가부시끼 가이샤 | A copolymer for an antifouling paint composition, an antifouling paint composition, an antifouling coating film formed using the composition, a painted object having the coating film on its surface, and an antifouling treatment method for forming the coating film. |
| KR101961933B1 (en) * | 2018-09-17 | 2019-03-25 | 주식회사 에코웨이브 | Self-polishing antifouling paint |
| JP7182497B2 (en) | 2019-03-12 | 2022-12-02 | 株式会社日立製作所 | Sludge treatment system |
| JP7323980B2 (en) * | 2019-03-20 | 2023-08-09 | 関西ペイント株式会社 | antifouling paint composition |
| KR20230135450A (en) | 2022-03-16 | 2023-09-25 | 주식회사 케이씨씨 | Coat composition for antifouling |
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| IN2014DN03423A (en) * | 2011-11-14 | 2015-06-05 | Chugoku Marine Paints | |
| SG11201508319QA (en) * | 2013-04-23 | 2015-11-27 | Chugoku Marine Paints | Antifouling coating composition, antifouling coating film, antifouling substrate, and method for producing antifouling substrate |
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- 2016-05-20 KR KR1020177023346A patent/KR101817486B1/en active IP Right Grant
- 2016-05-20 WO PCT/JP2016/065010 patent/WO2016190242A1/en active Application Filing
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| CN102083925A (en) * | 2008-06-11 | 2011-06-01 | 佐敦集团 | Binder for antifouling coating composition and antifouling coating composition comprising binder |
| CN102791812A (en) * | 2010-03-23 | 2012-11-21 | 中国涂料株式会社 | Antifouling coating composition and use for same |
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| CN111886304A (en) * | 2018-04-20 | 2020-11-03 | 日东化成株式会社 | Antifouling coating composition |
| CN112105697A (en) * | 2018-05-11 | 2020-12-18 | 中国涂料株式会社 | Antifouling coating composition, antifouling coating film, substrate with antifouling coating film, and antifouling method |
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| WO2016190242A1 (en) | 2016-12-01 |
| CN107406712B (en) | 2019-05-21 |
| JPWO2016190242A1 (en) | 2017-06-08 |
| JP6067200B1 (en) | 2017-01-25 |
| KR101817486B1 (en) | 2018-01-10 |
| KR20170100671A (en) | 2017-09-04 |
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