CN108603069A - Antifouling paint compositions, film and the base material with film - Google Patents
Antifouling paint compositions, film and the base material with film Download PDFInfo
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- CN108603069A CN108603069A CN201780007934.XA CN201780007934A CN108603069A CN 108603069 A CN108603069 A CN 108603069A CN 201780007934 A CN201780007934 A CN 201780007934A CN 108603069 A CN108603069 A CN 108603069A
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- antifouling paint
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1618—Non-macromolecular compounds inorganic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The present invention is a kind of antifouling paint compositions, is contained：Silylacrylic based copolymer (A), lower alcohol (B), the anti-fouling agent (C) containing copper component and zinc ingredient and the monocarboxylic acid compound (D) that carbon number is 1~3, the silylacrylic based copolymer (A) have：The content of structural unit (a1) from triisopropylsilyl (methyl) acrylate and the structural unit (a2) from the polymerizable monomer with polymeric double bond, the above-mentioned lower alcohol (B) in above-mentioned antifouling paint compositions is 0.1~3 mass %.The present invention is provided to film, the base materials and its manufacturing method with film with above-mentioned film on base material obtained from forming the antifouling paint compositions of film, above-mentioned antifouling paint compositions being made to cure, the consumption of film not only under conditions of the normal-temperature water contact with 25 DEG C or so and also can be inhibited smaller by the film under conditions of high-temperature water contact with 30 DEG C or so, can maintain physical property for a long time.
Description
Technical field
There is the band of the film the present invention relates to antifouling paint compositions, using the film of its formation and on base material
The base material of film.
Background technology
The aouatic structures such as ship, port facilities, piping material and bridge object is due to being exposed in the water of organism existence
And it is attached with the animals and plants such as the microorganisms such as bacterium, barnacle and diatom.If these microorganisms and animals and plants cover aouatic structure object
Surface, then occur that corrosion occurs or lead to the fuel consumption rate of ship because the frictional resistance of itself and seawater, fresh water increases
The problems such as reduction.
As a method of solving this problem, the attached of the animal such as using containing barnacle can be effectively prevent can be enumerated
Cuprous oxide (the Cu2The antifouling paint compositions of anti-fouling agents such as O), in water the surface of works form the side of antifouling coat
Method.
More specifically, patent document 1 proposes a kind of antifouling paint compositions, and it includes copolymer and cuprous oxide etc.
Anti-fouling agent, the copolymer include triisopropylsilyl (methyl) acrylate (a) 55 in 100 parts by weight of monomer component
~75 parts by weight, 2~20 parts by weight of methoxyethyl acrylate (b) and other polymerizable monomer (c) 43~5 parts by weight.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2001-226440 bulletins
Invention content
Problems to be solved by the invention
In the field of antifouling paint compositions, have such silicyl based polymer recorded in patent document 1
The case where as binder resin.However, the film formed by such antifouling paint compositions is in the room temperature with 25 DEG C or so
Under conditions of water contact, the condition that can the consumption of film be inhibited smaller, but be contacted in the high-temperature water with 30 DEG C or so
Under, there are problems that the consumption of film becomes larger, can not maintain film for a long time.
The present invention is carried out in view of above-mentioned actual conditions, and project is, provides the antifouling painting for being used to form film
Feed composition, the film is not only under conditions of the normal-temperature water contact with 25 DEG C or so and in the high-temperature water with 30 DEG C or so
Also can the consumption of film be inhibited smaller under conditions of contact, physical property can be maintained for a long time.
In addition, problem of the present invention is that, provide film obtained from making above-mentioned antifouling paint compositions cure, in base material
The upper base material and its manufacturing method with film with above-mentioned film.
The solution to the problem
The inventors of the present invention have made intensive studies, as a result, it has been found that：In the antifouling paint group comprising silicyl based polymer
It closes in object, the monoacid such as rosin used as dissolution auxiliary agent are formd with such as cuprous oxide, zinc oxide as anti-fouling agent
The ratio of mantoquita and zinc salt, the mantoquita and zinc salt can cause significantly to influence on the water resistance of film and expendable etc..Also, into
One step is distinguished after studying repeatedly：If the ratio of zinc salt is got higher, the film consumption under hot conditions becomes larger, whereas if
The ratio of mantoquita is got higher, then the consumption under hot conditions can be suppressed to journey identical with the consumption under normal temperature condition
Degree.Thus, the inventors of the present invention are studied for the rate control of mantoquita and zinc salt, as a result, it has been found that：By to antifouling paint
Coordinate a small amount of lower alcohol in composition, to which the ratio of the mantoquita in antifouling paint compositions is got higher, not only at 25 DEG C or so
Normal temperature condition under and also can the consumption of film be inhibited smaller under 30 DEG C or so of hot conditions, to complete
The present invention.The purport of the present invention is as follows.
The present invention relates to [1] below~[8].
[1] a kind of antifouling paint compositions, contain：Silylacrylic based copolymer (A), carbon number be 1~3 it is low
Grade alcohol (B), the anti-fouling agent (C) containing copper component and zinc ingredient and monocarboxylic acid compound (D), the silylacrylic
Based copolymer (A) has：Structural unit (a1) from triisopropylsilyl (methyl) acrylate and from having
The structural unit (a2) of the polymerizable monomer of polymeric double bond, above-mentioned lower alcohol (B's) in above-mentioned antifouling paint compositions contains
Amount is 0.1~3 mass %.
[2] antifouling paint compositions according to above-mentioned [1], wherein above structure unit (a1) is relative to above-mentioned knot
The mass ratio [(a1)/(a2)] of structure unit (a2) is 40/60~95/5.
[3] antifouling paint compositions according to above-mentioned [1] or [2], wherein upper in above-mentioned antifouling paint compositions
The content for stating silylacrylic based copolymer (A) is 5~40 mass %.
[4] antifouling paint compositions according to any one of above-mentioned [1]~[3], wherein above-mentioned silicyl propylene
The weight average molecular weight (Mw) of sour based copolymer (A) is 5,000~100,000.
[5] a kind of film is to make the antifouling paint compositions described in any one of above-mentioned [1]~[4] cure to obtain
's.
[6] a kind of base material with film, with the film described in above-mentioned [5] on base material.
[7] base material with film according to above-mentioned [6], wherein above-mentioned base material is ship.
[8] a kind of manufacturing method of the base material with film, has：By will be described in any one of above-mentioned [1]~[4]
Antifouling paint compositions are coated with or are infiltrated in base material, to obtain the process (1) of coated body or impregnated article；And by will be above-mentioned
Coated body or impregnated article are dried, to make above-mentioned antifouling paint compositions carry out cured process (2).
Invention effect
According to the present invention, it is possible to provide be used to form the antifouling paint compositions of film, the film not only with 25 DEG C of left sides
And it also can be by the consumption of film under conditions of the high-temperature water contact with 30 DEG C or so under conditions of right normal-temperature water contact
Inhibit smaller, physical property can be maintained for a long time.
In addition, according to the present invention, it is possible to provide film obtained from making above-mentioned antifouling paint compositions cure has on base material
There are the base material and its manufacturing method with film of above-mentioned film.
Specific implementation mode
[antifouling paint compositions]
The present invention antifouling paint compositions be containing silylacrylic based copolymer (A), carbon number for 1~3 it is low
Grade alcohol (B), the anti-fouling agent (C) containing copper component and zinc ingredient and the antifouling paint compositions of monocarboxylic acid compound (D), institute
Stating silylacrylic based copolymer (A) has：Structural unit from triisopropylsilyl (methyl) acrylate
(a1) and the structural unit from the polymerizable monomer with polymeric double bond (a2), in above-mentioned antifouling paint compositions
The content of above-mentioned lower alcohol (B) is 0.1~3 mass %.
<Silylacrylic based copolymer (A)>
In the antifouling paint compositions of the present invention, include silylacrylic for the purpose for improving film soil resistance
Based copolymer (A), above-mentioned silylacrylic based copolymer (A) have：From triisopropylsilyl (methyl) propylene
The structural unit (a1) of acid esters and the structural unit (a2) from the polymerizable monomer with polymeric double bond.
It should be noted that in the present invention, constitute " polymerizable monomer with polymeric double bond " of structural unit (a2)
Refer to " there is polymeric double bond other than constituting triisopropylsilyl (methyl) acrylate of structural unit (a1)
Polymerizable monomer ".In addition, in the present invention, " (methyl) acrylate " refers to " acrylate or methacrylate ", " (first
Base) acrylic compounds " refer to " acrylic compounds or methacrylic ", " (methyl) acryloyl group " refers to " acryloyl group or methyl
Acryloyl group ".
(structural unit (a1) for being originated from triisopropylsilyl (methyl) acrylate)
Above structure unit (a1) is derived from the structural unit of triisopropylsilyl (methyl) acrylate.The present invention
In structural unit (a1) can be from triisopropylsilyl acrylate (TIPSA) and triisopropylsilyl first
Any structural unit in base acrylate (TIPSMA), furthermore, it is possible to for from triisopropylsilyl acrylate
It is excellent from the viewpoint of improving film soil resistance with the structural unit of both triisopropylsilyl methacrylates
It is selected as being originated from structure any in triisopropylsilyl acrylate and triisopropylsilyl methacrylate
Unit.
(structural unit (a2) for being originated from the polymerizable monomer with polymeric double bond)
As the polymerizable monomer with polymeric double bond for constituting structural unit (a2), as long as in addition to triisopropyl first
The polymerizable monomer with polymeric double bond except silylation (methyl) acrylate, there is no particular limitation, can enumerate
Such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (first
Base) butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) third
The own ester of olefin(e) acid, (methyl) cyclohexyl acrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid
2- ethylhexyls, (methyl) acrylic acid 3,5, the own ester of 5- trimethyls, (methyl) lauryl acrylate, (methyl) acrylic acid spermaceti
(methyl) alkyl acrylates such as ester, (methyl) stearyl acrylate, (methyl) phenyl acrylate, (methyl) benzyl acrylate,
(methyl) benzyl acrylate or (methyl) acrylic acid aralkyl ester；
(methyl) acrylic acid 2- methoxy acrylates, (methyl) acrylic acid 2- ethoxy ethyl esters, (methyl) acrylic acid 4- methoxies
Base butyl ester, (methyl) acrylic acid 2- methoxyl groups propyl ester, (methyl) acrylic acid 3- methoxyl groups propyl ester, (methyl) acrylic acid 2- propoxyl group
Ethyl ester, (methyl) acrylic acid 2- butoxyethyls, isobutoxy butyldiglycol (methyl) acrylate, (methyl) acrylic acid 2-
(methyl) alkoxyalkyl acrylate such as phenoxy ethyl or (methyl) acrylic acid aryloxy group alkyl base ester；
(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 and (methyl) acrylic acid 2- hydroxyl -3- phenoxy-propyls
Ester；
(methyl) acrylate of the base containing organosiloxane；
(methyl) acrylamide, polyethyleneglycol (methyl) acrylate, methoxy poly (ethylene glycol) list (methyl) acrylic acid
(methyl) acrylate containing hydroxyl, amide groups or ether such as ester；
Styrene, 2-methyl styrene, 3- methyl styrenes, 4- methyl styrenes, 2,4-DMS, the tertiary fourths of 4-
Aromatic ethenyls such as base styrene, 5- tertiary butyls -2-methyl styrene etc..These polymerizable monomers can be used alone,
It can be applied in combination two or more.
It should be noted that in the present invention, " (methyl) acrylamide " refers to " acrylamide or Methacrylamide ".
Among the above-mentioned polymerizable monomer with polymeric double bond, preferably (methyl) alkyl acrylate and (methyl) third
Olefin(e) acid alkoxy alkyl, preferably methyl methacrylate (MMA), ethyl acrylate (EA), butyl acrylate (BA), propylene
Sour 2- methoxy acrylates (MEA), methacrylic acid 2- methoxy acrylates (MEMA).
As the above-mentioned polymerizable monomer with polymeric double bond, can further use anionic property unsaturated monomer,
Cationic unsaturated monomer.
As anionic property unsaturated monomer, can enumerate (methyl) acrylic acid, maleic acid, maleic anhydride, itaconic acid and
The carboxylic unsaturated monomer such as crotonic acid；The third sulphur of styrene sulfonic acid, 3- (methacryloxy) propane sulfonic acid and acrylamide
Acid etc. contain sulfonic unsaturated monomer.
These anionic property unsaturated monomers can be reused through in part and/or all after neutralization.It should be noted that
Neutralization can carry out in the state of monomer, be neutralized again after polymer can also be made.
As alkali used in neutralization, the alkali metal hydroxide such as potassium hydroxide, sodium hydroxide can be enumerated；Ammonia,
The amine compounds such as triethanolamine, trimethylamine.
As cationic unsaturated monomer, can enumerate selected from amino-containing unsaturated monomer and containing quaternary ammonium salt base not
It is saturated one or more of monomer.
As amino-containing unsaturated monomer, (methyl) acrylic acid N, N- dimethylamino ethyl ester, (methyl) can be enumerated
Acrylic acid N, N- diethylamino ethyl ester, (methyl) acrylic acid N, N- dimethylamino propyl ester, (methyl) acrylic acid N, N- diethyl
Base amino propyl ester, N, N- dimethyl aminoethyls (methyl) acrylamide, N, N- diethylaminos ethyl (methyl) acrylamide,
N, N- dimethylaminopropyl (methyl) acrylamide, N, N- diethyl amino propyls (methyl) acrylamide, 2- vinylpyridines
Pyridine, 4-vinylpridine and they are used into H+X-Shown in acid neutralize obtained structure.
In addition, as the unsaturated monomer containing quaternary ammonium salt base, can enumerate with X-(methyl) third as counter ion counterionsl gegenions
Alkene trimethylammonium trimethyl ammonium, (methyl) acryloxypropyl trimethyl ammonium, (methyl) Acryloyl amino ethyl front three
Base ammonium, (methyl) Acryloyl amino oxypropyl trimethyl ammonium, diallyl dimethyl ammonium, 1- ethyls -4-vinylpridine, 1,
2- dimethyl -5- vinylpyridines etc..
X-Indicate anion, preferably halide ion, more preferably chloride ion.
(manufacturing method of silylacrylic based copolymer (A))
Above-mentioned silylacrylic based copolymer (A) can be manufactured for example, by following step.
First, solvent is put into reaction vessel and is heated to 80 DEG C~120 DEG C or so, while maintaining temperature, to
Above-mentioned triisopropylsilyl (methyl) acrylate and the above-mentioned polymerism list with polymeric double bond is wherein added dropwise
The mixed liquor of body, polymerization initiator, chain-transferring agent and solvent etc. carries out polymerisation, and thus, it is possible to obtain silicyl propylene
Sour based copolymer (A).
It should be noted that the structural unit from each monomer in silylacrylic based copolymer (A) respectively contains
The ratio of amount (quality) can be regarded as identical as the ratio of inventory (quality) of above-mentioned each monomer used in polymerisation.
As the polymerization initiator that can be used in manufacturing silylacrylic based copolymer (A), it is not particularly limited, it can
To use various radical polymerization initiators.Specifically, it is different to enumerate benzoyl peroxide, hydrogen peroxide, hydrogen peroxide
Propyl benzene, tert-butyl hydroperoxide, potassium peroxydisulfate, sodium peroxydisulfate, 2,2 '-azos bis- (isobutyronitriles) (AIBN), 2,2 '-azos are double
(2- methylbutyronitriles) (AMBN), 2,2 '-azos bis- (2,4- methyl pentane nitrile) (ADVN) and tert-butyl peroctoate (TBPO) etc..This
A little polymerization initiators may be used alone, can also be used in combination two or more.It should be noted that these free radical polymerizations are drawn
Hair agent can only react start when be added in reaction system, in addition it is also possible to react start when and reaction process in this
Two stages are added in reaction system.
The dosage of polymerization initiator in the manufacture of silylacrylic based copolymer (A) is relative to above-mentioned each monomer
Total 100 mass parts are preferably 0.5~20 mass parts.
As the chain-transferring agent that can be used in manufacturing silylacrylic based copolymer (A), it is not particularly limited, can arranges
Enumerate such as α-methylstyrenedimer, thioacetic acid, two terpenes, terpinolene, γ-terpinenes；Tert-dodecylmercaotan
With the thio-alcohols such as n-dodecyl mercaptan；The halide such as carbon tetrachloride, dichloromethane, chloroform and three sym-chlorobromoethanes；Glycerine etc. is secondary
Alcohol etc..These chain-transferring agents may be used alone, can also be used in combination two or more.
When using chain-transferring agent in the manufacture of silylacrylic based copolymer (A), dosage is relative to above-mentioned each
Total 100 mass parts of monomer are preferably 0.1~5 mass parts.
As the solvent that can be used in manufacturing silylacrylic based copolymer (A), such as propylene glycol list can be enumerated
Methyl ether, dipropylene glycol mono butyl base ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether and tripropylene glycol monobutyl base ether etc.
Polyalcohol monoalky lether；The aromatic hydrocarbon series solvents such as toluene, dimethylbenzene and mesitylene；Water etc..
When using solvent in the manufacture of silylacrylic based copolymer (A), dosage is not particularly limited, relatively
In total 100 mass parts of above-mentioned each monomer, preferably 5~150 mass parts.
Above structure unit (a1) is preferably 40/60 relative to the mass ratio [(a1)/(a2)] of above structure unit (a2)
~95/5, be more preferably 42/58~85/15, further preferably 43/57~75/25, still more preferably be 44/56~70/
30.It should be noted that above-mentioned mass ratio [(a1)/(a2)] can calculate according to the rate of charge of each monomer when manufacturing copolymer
Go out.
(weight average molecular weight of silylacrylic based copolymer (A))
The weight average molecular weight (Mw) of silylacrylic based copolymer (A) is preferably 5,000~100,000, more preferably
For 10,000~90,000, further preferably 15,000~80,000, be still more preferably 17,000~70,000, more into
One step is preferably 18,000~60,000.If the weight average molecular weight (Mw) of silylacrylic based copolymer (A) is above-mentioned
In range, then the spraying operation of antifouling paint compositions improves, and in turn, the physical property of film also improves.
It should be noted that the weight average molecular weight (Mw) of silylacrylic based copolymer (A) refers to passing through embodiment
Described in method measure gel permeation chromatography (GPC) value.
(viscosity of silylacrylic based copolymer (A))
The viscosity of silylacrylic based copolymer (A) is preferably 500~10,000mPas, more preferably 1,000
~7,000mPas, further preferably 1,500~6,000mPas, still more preferably it is 1,800~5,000mPa
S, still more preferably it is 2,000~4,800mPas.If the viscosity of silylacrylic based copolymer (A) is above-mentioned
In range, then the spraying operation of antifouling paint compositions improves.
It should be noted that the viscosity of silylacrylic based copolymer (A) can utilize described in aftermentioned embodiment
Method is measured.
(content of silylacrylic based copolymer (A))
The content of silylacrylic based copolymer (A) in antifouling paint compositions is preferably 5 mass % or more, more
Preferably 10 mass % or more, further preferably 13 mass % or more, it is still more preferably 15 mass % or more, more into one
Step be preferably 16 mass % or more, also, preferably 40 mass % or less, more preferably 35 mass % or less, further preferably
For 30 mass % or less, be still more preferably 25 mass % or less, be still more preferably 23 mass % or less.If first silicon
The content of alkyl acrylic based copolymer (A) within the above range, then can be played the film of excellent stain for a long time,
In turn, it can maintain to apply film strength for a long time.
<Lower alcohol (B)>
In the antifouling paint compositions of the present invention, for the painting under conditions of not only contacting the normal-temperature water with 25 DEG C or so
Film consumption inhibits smaller, and the film consumption under conditions of the high-temperature water with 30 DEG C or so is contacted also inhibits smaller
Purpose, the lower alcohol (B) (hereinafter sometimes referred to simply as " lower alcohol (B) ") for being 1~3 containing carbon number.It should be noted that this hair
Lower alcohol (B) in bright is not included in aftermentioned organic solvent (F).
The lower alcohol for being 1~3 as carbon number, can enumerate such as methanol, ethyl alcohol, normal propyl alcohol and isopropanol.Among these,
From the viewpoint of the consumption under conditions of contacting the high-temperature water with 30 DEG C or so inhibit it is smaller, preferably ethyl alcohol.
(content of lower alcohol (B))
The content of lower alcohol (B) in antifouling paint compositions is 0.1~3 mass %.If the content of lower alcohol (B) exists
In above range, then the film consumption under conditions of capable of contacting the high-temperature water with 30 DEG C or so inhibits smaller.From same
From the perspective of sample, the content of lower alcohol (B) is preferably 0.2 mass % or more, is more preferably 0.3 mass % or more, further
Preferably 0.4 mass % or more, it is still more preferably 0.5 mass % or more, also, preferably 2.5 mass % or less, more excellent
Be selected as 2.0 mass % or less, further preferably 1.5 mass % or less, still more preferably be 1.0 mass % or less, more into
One step is preferably 0.9 mass % or less, is still more preferably 0.8 mass % or less.
<Anti-fouling agent (C) containing copper component and zinc ingredient>
In the present invention, the anti-fouling agent (C) containing copper component and zinc ingredient is used for the purpose for improving film soil resistance
(hereinafter sometimes referred to simply as " anti-fouling agent (C) ").
Can be in organic system or inorganic system as the copper component in the anti-fouling agent (C) containing copper component and zinc ingredient
Any one, can enumerate such as cuprous oxide, cupric thiocyanate, copper powder, sulphur oxy picolinate copper, thiocyanic acid copper and corronil,
Among these, preferably cuprous oxide, sulphur oxy picolinate copper.On the other hand, as the anti-fouling agent (C) containing copper component and zinc ingredient
In zinc ingredient, can be organic system or it is inorganic system any one of, zinc oxide, zinc pyridinethione, dimethyl two can be enumerated
Zinc thiocarbamate, zinc ethylene bisdithiocarbamate and double dimethyl disulfide are for two sulphur of carbamoyl ethylenebis
For carbaminate etc., among these, preferably zinc oxide.Copper component in anti-fouling agent (C) can be used alone, can also group
Conjunction use is two or more, and the zinc ingredient in anti-fouling agent (C) may be used alone, can also be used in combination two or more.As anti-
Dirty agent (C), preferably cuprous oxide, sulphur oxy picolinate copper and zinc oxide are applied in combination.
From the viewpoint of improving film soil resistance, in antifouling paint compositions of the invention containing copper component and zinc at
The content of the anti-fouling agent (C) divided is preferably 5~70 mass %, more preferably 10~60 mass %.
In anti-fouling agent (C) containing copper component and zinc ingredient, even if from the condition contacted in the high-temperature water with 30 DEG C or so
Under also by the consumption of film inhibit it is smaller from the perspective of, ratio (copper component/zinc ingredient) (matter of copper component and zinc ingredient
Amount ratio) be preferably in 99/1~40/60 range, be more preferably in 97/3~50/50 range, further preferably be in 95/5
~60/40 range.
The antifouling paint compositions of the present invention can contain other than the anti-fouling agent (C) containing copper component and zinc ingredient
Anti-fouling agent (hereinafter sometimes referred to simply as " anti-fouling agent other than anti-fouling agent (C) ").
As the above-mentioned anti-fouling agent other than anti-fouling agent (C), such as bromo- 2- of Medetomidine, 4- (4- chlorobenzenes can be enumerated
Base) -5- (trifluoromethyl) -1H- pyrroles -3- formonitrile HCNs, 4,5-, bis- chloro- Kathons, borine-nitrogen system alkali
Addition product (triphenylboron pyridine alkane, 4- isopropyl pyridine diphenyl methyl borines etc.), (±) -4- [1- (2,3- dimethyl benzenes
Base) ethyl] -1H- imidazoles, N, N- dimethyl-N '-(3,4- dichlorophenyl) urea, N- (2,4,6- trichlorophenyl) maleimide,
2- methyl mercapto -4- tert-butylaminos -6- cyclopropylaminos -1,3,5-triazines, 2,4,5,6- tetrachloro phthalonitriles, double dimethyl
Dithiocarbamyl zinc ethylene bisdithiocarbamate, chloromethyl n-octyl disulphide, N ', N '-dimethyl-
N '-phenyl-(N- fluorine dichloromethyls sulfenyl) sulfonamide, N ', N '-dimethyl-N '-p-methylphenyl-(N- fluorine dichloromethyls sulfenyl)
Sulfonamide, tetraalkyl thiuram disulphide, zinc dimethyl dithiocarbamate, zinc ethylene bisdithiocarbamate,
2,3- bis- chloro- N- (2 ', 6 '-diethyl phenyl) maleimides and 2, bis- chloro- N- of 3- (2 '--6 '-aminomethyl phenyl of ethyl) Malaysia
Acid imide etc..These anti-fouling agents other than anti-fouling agent (C) may be used alone, can also be used in combination two or more.
From the viewpoint of improving film soil resistance, anti-fouling agent (C) in antifouling paint compositions of the invention in addition to
Total content of anti-fouling agent except anti-fouling agent (C) is preferably 5~70 mass %, more preferably 10~60 mass %.
<Monocarboxylic acid compound (D)>
In the present invention, monocarboxylic acid compound (D) is used for the Surface Renewal of film and the purpose of water resistance is improved.
As monocarboxylic acid compound (D), the saturated or unsaturated fat for being for example preferably 10~40 in carbon atom number
Replace the saturated or unsaturated ester ring type for having compound made of 1 carboxyl or being 3~40 in carbon atom number on race's alkyl
Substitution has substitution in compound or their substituent made of 1 carboxyl to have compound made of 1 carboxyl on alkyl.
Wherein, preferably trimethyl isobutenyl cyclohexene carboxylate, versatic acid, palmitic acid, stearic acid, oleic acid, linoleic acid,
Leukotrienes, neoabietic acid, pimaric acid, dehydroabietic acid, 12- hydroxy stearic acids, aphthenic acids and their metal salt.In addition,
Further preferably using rosin acids such as abietic acid, palustric acid, isodextropimaric acids as the rosin of principal component and rosin derivative.
As trimethyl isobutenyl cyclohexene carboxylate, such as 2,6- dimethyl-octas -2,4,6- triolefins and first can be enumerated
The reaction product of base acrylic acid, with 1,2,3- trimethyl -5- (2- methyl propyl- 1- alkene -1- bases) hexamethylene -3- alkene -1- carboxylic acids and
Isosorbide-5-Nitrae, 5- trimethyls -2- (2- methyl propyl- 1- alkene -1- bases) hexamethylene -3- alkene -1- carboxylic acids are as principal component (85 mass % or more).
As rosin and rosin derivative, the rosin such as rosin (gum rosin), wood rosin, toll oil rosin can be enumerated；
And rosin derivatives such as hydrogenated rosin, disproportionated rosin etc..
The content of monocarboxylic acid compound (D) in the antifouling paint compositions of the present invention is preferably 0.1~50 mass %, more
Preferably 1~30 mass %, further preferably 2~10 mass %.
<Any ingredient>
In the antifouling paint compositions of the present invention, in addition to silylacrylic based copolymer (A), lower alcohol (B), contain
Except the anti-fouling agent (C) and monocarboxylic acid compound (D) of copper component and zinc ingredient, as needed can also contain pigment (E),
Organic solvent (F), fluidity improver (anti-dripping melt, anti-settling) (G), plasticizer (H) and dehydrating agent (I) etc..
(pigment (E))
In the present invention, for the purpose for making film coloring, masking substrate, in addition, for adjusting to coating strength appropriate
And the purpose of soil resistance is further increased, pigment (E) can be used.
As pigment (E), such as talcum, mica, clay, potassium feldspar, calcium carbonate, kaolin, alumina white, white can be enumerated
The extender pigments such as carbon, aluminium hydroxide, magnesium carbonate, barium carbonate, barium sulfate, calcium sulfate and zinc sulphide；Red iron oxide, titanium white (oxygen
Change titanium), yellow iron oxide, carbon black, the coloring pigments such as phenol red, phthalocyanine blue, wherein preferably talcum, red iron oxide.These face
Material can be used alone, or be applied in combination two or more.
When the antifouling paint compositions of the present invention contain pigment (E), the content of the pigment (E) in antifouling paint compositions is excellent
It is selected as 1~30 mass %, more preferably 4~25 mass %, further preferably 7~20 mass %.
It should be noted that the copper systems such as cuprous oxide, zinc oxide, sulphur oxy picolinate copper and zinc pyridinethione and zinc system anti-fouling agent
Sometimes the function as anti-fouling agent and the function as pigment are had both, but as anti-containing copper component and zinc ingredient in the present invention
Dirty agent (C) is handled.
(organic solvent (F))
In the present invention, relatively low, raising jet atomization and spraying work are kept as by the viscosity of antifouling paint compositions
The purpose of industry can use organic solvent (F).
As organic solvent (F), aromatic series hydrocarbon system, aliphatic hydrocarbon system, alicyclic hydrocarbon system, ketone system, ester system, alcohol can be used
The organic solvent of system etc., the preferably organic solvent of aromatic series hydrocarbon system.These organic solvents can be used alone or group
It closes using two or more.
As the organic solvent of aromatic series hydrocarbon system, can enumerate such as toluene, dimethylbenzene, styrene, mesitylene.
As the organic solvent of aliphatic hydrocarbon system, can enumerate such as pentane, hexane, heptane, octane.
As the organic solvent of alicyclic hydrocarbon system, can enumerate such as hexamethylene, hexahydrotoluene, ethyl cyclohexane.
As the organic solvent of ketone system, such as acetylacetone,2,4-pentanedione, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), carbonic acid can be enumerated
Dimethyl ester etc..
As the organic solvent of ester system, such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether can be enumerated
Deng.
As the organic solvent of alcohol system, can enumerate such as n-butanol, propylene glycol monomethyl ether.
When the antifouling paint compositions of the present invention contain organic solvent (F), the organic solvent (F) in antifouling paint compositions
The content desired viscosity that is consistent according to the coating form etc. with antifouling paint compositions determine preferred amounts, it is often preferred that 1
~50 mass %.When content is excessive, a problem that anti-dripping melt reduces occurs sometimes.
(fluidity improver (anti-dripping melt, anti-settling) (G))
In the present invention, for adjustment antifouling paint compositions viscoplasticity, obtain anti-dripping melt and anti-settling effect purpose,
Fluidity improver (G) can be used.As fluidity improver (G), the organic clay system wax (stearic acid of Al, Ca, Zn can be enumerated
Salt, lecithin salt, alkylsulfonate etc.), organic system wax (polyethylene wax, oxidized polyethylene wax, amide waxe, polyamide wax, hydrogenation
Castor oil wax etc.), the mixture of organic clay system wax and organic system wax, synthesis fine particle silica etc..These fluidity improvers
It can be used alone, or be applied in combination two or more.
As fluidity improver (G), commercially available product can be used, such as this chemical conversion of nanmu Co., Ltd. manufacture can be enumerated
" DISPARLON 305 ", " DISPARLON 4200-20 ", " DISPARLON A630-20X " etc..
When the antifouling paint compositions of the present invention contain fluidity improver (G), the fluidity in antifouling paint compositions improves
The content of agent (G) is preferably generally 0.01~10 mass %, more preferably 0.1~3 mass %.
(plasticizer (H))
In the antifouling paint compositions of the present invention, for the resistance to anti-thread breakage or water resistance for improving film and inhibit discoloration
Purpose, plasticizer (H) can be used.
As plasticizer (H), such as normal paraffin hydrocarbons, chlorinated paraffin, terpene phenol, tricresyl phosphate can be enumerated
(TCP), polyvinyl ethyl ether etc..Wherein, preferably chlorinated paraffin, terpene phenol, more preferably chlorinated paraffin.These increase
Modeling agent can be used alone, or be applied in combination two or more.
As plasticizer (H), it can use commercially available product that can enumerate Japan petroleum for example, as above-mentioned normal paraffin hydrocarbons
" n-paraffin " etc. for learning Co., Ltd.'s manufacture can enumerate TOSOH Co., Ltd's manufacture as above-mentioned chlorinated paraffin
" TOYOPARAXA-40/A-50/A-70/A-145/A-150 " etc..
The antifouling paint compositions of the present invention are when containing plasticizer (H), and plasticizer (H's) in antifouling paint compositions contains
Amount is preferably 0.1~10 mass %.
(dehydrating agent (I))
In the present invention, for the purpose for the storage stability for improving antifouling paint compositions, dehydrating agent (I) can be used.
As dehydrating agent (I), such as alkoxy silane, the known boiling with the adopted name of " molecular sieve " can be enumerated
The ortho esters such as stone, aluminium oxide, alkyl orthoformate, ortho-boric acid, isocyanates, gypsum and silester etc..These dehydrations
Agent can be used alone, or be applied in combination two or more.
The antifouling paint compositions of the present invention are when containing dehydrating agent (I), and dehydrating agent (I's) in antifouling paint compositions contains
Amount is preferably 0.1~10 mass %, more preferably 0.2~2 mass %.If the content of dehydrating agent (I) is within the above range,
The storage stability of antifouling paint compositions can be kept well.
<The manufacturing method of antifouling paint compositions>
The antifouling paint compositions of the present invention can use device identical with well known common antifouling paint, means etc.
It is prepared.Specifically, by the solution of previously prepared silylacrylic based copolymer (A), containing copper component and zinc
The anti-fouling agent (C) of ingredient and monocarboxylic acid compound (D) and other additives etc. as needed mix, and stir on one side
Thus obtained solution or dispersion liquid add lower alcohol (B), futher stir, mix, thus, it is possible to prepare thereto on one side.
[film and the base material with the film]
The film of the present invention is obtained from making the antifouling paint compositions solidification of the present invention.Specifically, for example incite somebody to action this
After the antifouling paint compositions of invention are coated on base material etc., by enabling its solidification to obtain film.
The method of antifouling paint compositions as the coating present invention, can enumerate the side using bristle, roller and sprayer
The known methods such as method.
The antifouling paint compositions being coated with using the above method under conditions of such as 25 DEG C by placing 0.5~14 day
It controls and is cured, so as to form film.It should be noted that in the solidification of antifouling paint compositions, Ke Yi
Cured while blowing under heating.
For example, from the viewpoint of improving coating strength, the thickness of film of the invention after hardening is preferably 30~1,
000 μm or so.As the method for the film for manufacturing the thickness, can enumerate：The thickness that antifouling paint compositions are coated with every 1 time
Degree is usually 10~300 μm, preferably 30~200 μm of mode is coated with 1 time~method more than twice.
The base material with film of the present invention has above-mentioned film on base material.
The manufacturing method of the base material with film as the present invention, is not particularly limited, and can come for example, by following methods
The base material with film of the present invention is manufactured, the method has following process：By making antifouling paint compositions be coated with or infiltration
In base material, the process to obtain coated body or impregnated article；And make to be coated with or be infiltrated in the antifouling of base material by the process
Coating composition carries out cured process；Alternatively, the method has following process：Antifouling paint compositions will be made to cure
Obtained from the film process that is attached at base material.
As the method for obtaining coated body or impregnated article by making antifouling paint compositions be coated with or being infiltrated in base material, tool
For body, it can enumerate：After antifouling paint compositions are sufficiently stirred, it is set to be coated with or be infiltrated in by spraying or other means
The method of base material.
On the other hand, cured method is carried out as making coating or be infiltrated in the antifouling paint compositions of base material, preferably
The method for making coating composition be cured by coated body or impregnated article are dried, specifically, can enumerate：It is logical
It crosses in the air of room temperature, forced air supply 0.5~14 day or so under placement or heating, to make its cured method.Pass through
The base material with film of the present invention with above-mentioned film can be easily manufactured on base material in such method.
As the method that film obtained from antifouling paint compositions will be made to cure is attached at base material, can enumerate for example makes
To include obtained from so that antifouling paint compositions is cured with the known technology described in No. 2013-129724 grade of Japanese Unexamined Patent Publication
The method that the film of film is attached at base material.In this way, the base material with film obtained by base material is covered by film can be manufactured.
The antifouling paint compositions of the present invention can advance in ship, fishery, pipeline, water system equipment, diving gear, water
Anti-pollution function in the extensive industrial field such as body, power generation, harbour/civil construction for maintaining base material for a long time.As such
Base material can be enumerated such as the ship (hull of large-scale steel ship, fishing boat, FRP ships, wooden boat, yacht etc. container ship, oil tanker
Outside plate.New ship or repair ship), fishery material (hawser, fishing net, fishing gear, buoy, lifebuoy etc.), oil pipeline, water guide piping,
The water supply row of circulating water pipe, diving dress, waterproof eyeglasses, oxygen cylinder, swimsuit, torpedo, heat power station or atomic power station
The aouatic structures object such as mouth of a river, seawater utilization equipment class (sea water pump etc.), Very large floating structure formula marine structure, bay bank road
The anti-sludge diffusion barrier etc. of the various ocean civil engineerings such as road, seabed tunnel, bay equipment, canal/air route.Among these, make
For base material, preferably ship.
The antifouling paint compositions of the present invention directly can be coated with or be infiltrated in base material.It is being directly coated at nuclear electric power generation
The raw materials such as water supply and drainage mouth, Very large floating structure formula marine structure, the ship stood are fiber-reinforced plastic (FRP), steel, wood
It, can be with the antifouling paint compositions of the present invention to these base material (raw material) surfaces in the case of the base material of material, aluminium alloy etc.
The good mode of adhesion is adjusted.
In addition, the object base material that be coated with the antifouling paint compositions of the present invention can be that surface is already formed with film
Base material.That is, the antifouling paint compositions of the present invention can be coated on and be pre-coated with the base materials such as antirust agent, priming paint (primary coat)
Base material surface.In turn, application is being carried out using existing coating or combined using the antifouling paint of the present invention
Object has carried out on the surface of the base material of application, as repairing purposes, can also push up the antifouling paint compositions of the present invention
It applies.The type for the film that the antifouling paint compositions of the present invention are in direct contact is not particularly limited.
Embodiment
Hereinafter, the present invention is further illustrated based on embodiment, but the present invention is not limited to these embodiments.
<The manufacture of silylacrylic based copolymer (A)>
(Production Example 1：The manufacture of silylacrylic based copolymer (A1))
Two are put into the reaction vessel for having blender, reflux condenser, thermometer, nitrogen ingress pipe and dropping funel
53 mass parts of toluene stir dimethylbenzene with blender in a nitrogen atmosphere on one side, are heated in reaction vessel under normal pressure on one side
Dimethylbenzene temperature reach 85 DEG C until.The temperature of the dimethylbenzene in reaction vessel is maintained to 85 DEG C on one side, is used on one side
It includes TIPSMA (triisopropylsilyl methacrylate) 45 matter that dropping funel takes 2 hours to be added into reaction vessel
Measure part, MEMA (methacrylic acid 2- methoxy acrylates) 35 mass parts, 15 mass parts of MMA (methyl methacrylate), BA (propylene
Acid butyl ester) 5 mass parts and 2, the monomer mixture of 2 '-azos bis- (2- methylbutyronitriles) 1 mass parts.
Then, 0.5 mass parts of tert-butyl peroctoate are further added into reaction vessel, on one side under normal pressure hold reaction
Liquid temperature in device is kept to 85 DEG C, and after persistently stirring 2 hours with blender on one side, the liquid temperature in reaction vessel is promoted from 85 DEG C
To 110 DEG C, and heat 1 hour.Then, 14 mass parts of dimethylbenzene are added into reaction vessel and makes the liquid temperature drop in reaction vessel
It is low, stop stirring at the time of liquid temperature reaches 40 DEG C, thus prepares silylacrylic based copolymer (A1).By silicyl
The characteristic of acrylic acid series copolymer (A1) etc. is shown in table 1.
(Production Example 2~4：The manufacture of silylacrylic based copolymer (A2)~(A4))
Other than changing the inventory of each monomer according to the record of table 1, it is carried out similarly and polymerize with Production Example 1, to
Obtain silylacrylic based copolymer (A2)~(A4).By the characteristic of silylacrylic based copolymer (A2)~(A4)
Etc. shown in table 1.
It should be noted that the heating residual of silylacrylic based copolymer (A1)~(A4) of gained, divide equally again
Son amount (Mw), the assay method of viscosity are as follows.
<Heat the computational methods of residual (quality NV)>
It measures silylacrylic based copolymer (A) 1g to be placed in plane ware, wire known to use quality will
It is equably sprawled, and after being dried 1 hour with 125 DEG C, weighs the quality of residue and wire, to calculate heating residual (matter
Measure %).
<The measurement of the weight average molecular weight (Mw) of silylacrylic based copolymer (A)>
The weight average molecular weight (Mw) of silylacrylic based copolymer (A) measures as follows：It is used as measurement device
" HLC-8120GPC " of TOSOH Co., Ltd's manufacture, " TSK-gel for using 2 TOSOH Co., Ltd to manufacture as splitter
α classes " (α-M) are measured using dimethylformamide (DMF) as eluent using gel permeation chromatography (GPC) method.First silicon
The weight average molecular weight (Mw) of alkyl acrylic based copolymer (A) is found out according to polystyrene conversion.
<The determination condition of viscosity>
The viscosity of silylacrylic based copolymer (A) uses Brookfield viscometer (Tokyo gauge strain under 25 DEG C of liquid temperature
Formula commercial firm system) it is measured (unit：mPa·s).
[table 1]
Table 1
It should be noted that the abbreviation in table 1 is as follows.
·TIPSMA：Triisopropylsilyl methacrylate
·TIPSA：Triisopropylsilyl acrylate
·MEMA：Methacrylic acid 2- methoxy acrylates
·MEA：Acrylic acid 2- methoxy acrylates
·MMA：Methyl methacrylate
·BA：Butyl acrylate
<The manufacture of antifouling paint compositions>
(embodiment 1~14 and comparative example 1~11)
Gradation composition
Each gradation composition used in antifouling paint compositions is shown in table 2.
[table 2]
Table 2
The manufacture of antifouling paint compositions
According to the cooperation (mass parts) described in table 3~6, each gradation composition is mixed, it is antifouling to obtain
Coating composition.Following evaluations are carried out for each antifouling paint compositions.Show the result in table 3~6.
[the storage stability evaluation at 50 DEG C]
It for each antifouling paint compositions, is placed on after just manufacturing in 50 DEG C of thermostat, is glued every 1 week
Degree measures, and is compared to the viscosity after just manufacturing and the viscosity after storage (adjusting coating material temperature to 23 DEG C), thus
Confirm the rising situation of viscosity.Viscosimetric analysis has used stormer viscosity meter (unit Ku).It is after measuring progress to 4 weeks
Only, using after 4 weeks with the differences in viscosity after 1 week as thickening rate.Thickening rate is lower, then it represents that storage stability is more excellent.
[the expendable evaluation at 25 DEG C]
Device is applied using the film that gap is 0.7mm, by the antifouling paint compositions of embodiment and comparative example at normal temperatures with dry
The mode that dry film thickness reaches 100 μm is coated on the plate (vertical 50mm × horizontal 50mm) of polyvinyl chloride, and places 1 day at normal temperatures,
Thus the breadboard with film is obtained.
By the breadboard with film in adjusting the seawater to 25 DEG C, the water velocity on experiment film is calculated as phase
It is impregnated 1 month when under the velocity conditions in about 15 sections.After dipping 1 month, film is measured using non-contact laser film thickness gauge
Thickness calculates the difference of the film thickness after the film thickness and dipping before dipping, measures consumption.In turn, under these conditions dipping 2~
Breadboard after 6 months, similarly measures consumption.
In the evaluation, numerical value is smaller, indicates that consumption is suppressed smaller.
[the expendable evaluation at 30 DEG C]
Other than being immersed in and being adjusted into 30 DEG C of seawater by the breadboard with film, evaluated with the expendable at 25 DEG C
Similarly measure consumption.
It should be noted that in the evaluation and numerical value is smaller, indicate that consumption is suppressed smaller, [30 DEG C of ratio
Under consumption/25 DEG C at consumption] value it is the more preferred closer to 1.
[table 3]
Table 3
[table 4]
Table 4
[table 5]
Table 5
[table 6]
Table 6
It can be defined by embodiment and the result of comparative example：According to the present invention, it is possible to provide be used to form the antifouling painting of film
Feed composition, the consumption of film under conditions of the film can not only contact the normal-temperature water with 25 DEG C or so inhibit
It is smaller, additionally it is possible to which that the consumption of the film under conditions of contacting the high-temperature water with 30 DEG C or so inhibits smaller, can be long-term
Maintain physical property.
Industrial availability
The present invention antifouling paint compositions the normal-temperature water with 25 DEG C or so can not only be contacted under conditions of film
Consumption inhibit smaller, additionally it is possible to the consumption of the film under conditions of contacting the high-temperature water with 30 DEG C or so inhibits
It is smaller.Therefore, it is possible to maintain for a long time the works that ship etc. advances in water, the works of configuration in water etc. surface, with
And the inner surface of the pipes works such as pipeline is formed by the physical property of film.
Claims (8)
1. a kind of antifouling paint compositions, contain：Silylacrylic based copolymer (A), the lower alcohol that carbon number is 1~3
(B), the anti-fouling agent (C) containing copper component and zinc ingredient and monocarboxylic acid compound (D),
The silylacrylic based copolymer (A) has：Knot from triisopropylsilyl (methyl) acrylate
Structure unit (a1) and structural unit (a2) from the polymerizable monomer with polymeric double bond,
The content of the lower alcohol (B) in the antifouling paint compositions is 0.1 mass of mass %~3 %.
2. antifouling paint compositions according to claim 1, wherein the structural unit (a1) is relative to the structure list
Mass ratio (a1)/(a2) of first (a2) is 40/60~95/5.
3. antifouling paint compositions according to claim 1 or 2, wherein the first in the antifouling paint compositions
The content of silylation acrylic acid series copolymer (A) is 5 mass of mass %~40 %.
4. antifouling paint compositions described in any one of claim 1 to 3, wherein the silylacrylic system
The weight average molecular weight Mw of copolymer (A) is 5,000~100,000.
5. a kind of film is obtained from so that antifouling paint compositions according to any one of claims 1 to 4 is cured.
6. a kind of base material with film, with the film described in claim 5 on base material.
7. the base material according to claim 6 with film, wherein the base material is ship.
8. a kind of manufacturing method of the base material with film, has：
By being coated with or being infiltrated in base material by antifouling paint compositions according to any one of claims 1 to 4, to be applied
The process (1) of cloth body or impregnated article；And
By the way that the coated body or impregnated article to be dried, to make the cured process of the antifouling paint compositions (2).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-015838 | 2016-01-29 | ||
| JP2016015838 | 2016-01-29 | ||
| PCT/JP2017/001967 WO2017130864A1 (en) | 2016-01-29 | 2017-01-20 | Antifouling coating composition, coating film, and coating-film-attached base material |
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|---|---|
| CN108603069A true CN108603069A (en) | 2018-09-28 |
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| CN201780007934.XA Pending CN108603069A (en) | 2016-01-29 | 2017-01-20 | Antifouling paint compositions, film and the base material with film |
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| Country | Link |
|---|---|
| JP (1) | JP6737456B2 (en) |
| KR (1) | KR102263211B1 (en) |
| CN (1) | CN108603069A (en) |
| SG (1) | SG11201806405VA (en) |
| WO (1) | WO2017130864A1 (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005082725A (en) * | 2003-09-09 | 2005-03-31 | Nitto Kasei Co Ltd | Antifouling coating composition and submarine articles coated with the composition, and antifouling method using the composition |
| CN101166801A (en) * | 2005-09-01 | 2008-04-23 | 中国涂料株式会社 | 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-proo |
| CN102083925A (en) * | 2008-06-11 | 2011-06-01 | 佐敦集团 | Binder for antifouling coating composition and antifouling coating composition comprising binder |
| CN103917614A (en) * | 2011-11-14 | 2014-07-09 | 中国涂料株式会社 | Antifouling coating composition, antifouling coating film, anti-foul base material, and process for manufacturing anti-foul base material |
| WO2014141927A1 (en) * | 2013-03-15 | 2014-09-18 | 日東化成株式会社 | Antifouling coating composition, antifouling coating film formed using said composition, and coated article having antifouling coating film on surface |
| WO2014175246A1 (en) * | 2013-04-23 | 2014-10-30 | 中国塗料株式会社 | Antifouling paint composition, antifouling paint film, antifouling substrate, and method for manufacturing antifouling substrate |
| CN104487479A (en) * | 2012-07-12 | 2015-04-01 | 日立化成高分子有限公司 | Polyester resin for antifouling coating materials, method for producing same, antifouling coating material composition, antifouling coating film, and antifouling base |
| WO2015156073A1 (en) * | 2014-04-10 | 2015-10-15 | 関西ペイント株式会社 | Antifouling coating material composition and coated article coated with same |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06172683A (en) * | 1992-12-09 | 1994-06-21 | Nippon Paint Co Ltd | Antifouling coating compound composition |
| JP2006183059A (en) * | 1996-04-17 | 2006-07-13 | Basf Coatings Japan Ltd | Coating composition |
| JP3857010B2 (en) * | 2000-02-17 | 2006-12-13 | 日本ペイント株式会社 | Copolymer and coating composition |
| JP2003277680A (en) * | 2002-03-27 | 2003-10-02 | Kansai Paint Co Ltd | Aqueous pollution-preventing resin composition |
| KR20160066002A (en) * | 2008-08-13 | 2016-06-09 | 아크조노벨코팅스인터내셔널비.브이. | Polymer with salt groups and antifouling coating composition comprising said polymer |
| JP5142150B2 (en) * | 2008-10-02 | 2013-02-13 | Ｎｋｍコーティングス株式会社 | Copolymer composition, antifouling paint composition, construction method and structure |
| JP4521589B2 (en) * | 2008-12-19 | 2010-08-11 | 日東化成株式会社 | Antifouling paint composition, antifouling coating film formed using the composition, coated product having the coating film on the surface, and antifouling treatment method for forming the coating film |
| KR102239172B1 (en) * | 2013-04-24 | 2021-04-09 | 닛토 가세이 가부시끼 가이샤 | Antifouling paint composition, copolymer for antifouling paint composition and method for manufacturing same, and painted object having on surface antifouling paint film formed using said composition |
-
2017
- 2017-01-20 KR KR1020187020856A patent/KR102263211B1/en active IP Right Review Request
- 2017-01-20 SG SG11201806405VA patent/SG11201806405VA/en unknown
- 2017-01-20 CN CN201780007934.XA patent/CN108603069A/en active Pending
- 2017-01-20 WO PCT/JP2017/001967 patent/WO2017130864A1/en active Application Filing
- 2017-01-20 JP JP2017564214A patent/JP6737456B2/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005082725A (en) * | 2003-09-09 | 2005-03-31 | Nitto Kasei Co Ltd | Antifouling coating composition and submarine articles coated with the composition, and antifouling method using the composition |
| CN101166801A (en) * | 2005-09-01 | 2008-04-23 | 中国涂料株式会社 | 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-proo |
| CN102083925A (en) * | 2008-06-11 | 2011-06-01 | 佐敦集团 | Binder for antifouling coating composition and antifouling coating composition comprising binder |
| CN103917614A (en) * | 2011-11-14 | 2014-07-09 | 中国涂料株式会社 | Antifouling coating composition, antifouling coating film, anti-foul base material, and process for manufacturing anti-foul base material |
| CN104487479A (en) * | 2012-07-12 | 2015-04-01 | 日立化成高分子有限公司 | Polyester resin for antifouling coating materials, method for producing same, antifouling coating material composition, antifouling coating film, and antifouling base |
| WO2014141927A1 (en) * | 2013-03-15 | 2014-09-18 | 日東化成株式会社 | Antifouling coating composition, antifouling coating film formed using said composition, and coated article having antifouling coating film on surface |
| WO2014175246A1 (en) * | 2013-04-23 | 2014-10-30 | 中国塗料株式会社 | Antifouling paint composition, antifouling paint film, antifouling substrate, and method for manufacturing antifouling substrate |
| WO2015156073A1 (en) * | 2014-04-10 | 2015-10-15 | 関西ペイント株式会社 | Antifouling coating material composition and coated article coated with same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6737456B2 (en) | 2020-08-12 |
| WO2017130864A1 (en) | 2017-08-03 |
| SG11201806405VA (en) | 2018-08-30 |
| KR20180091926A (en) | 2018-08-16 |
| KR102263211B1 (en) | 2021-06-09 |
| JPWO2017130864A1 (en) | 2018-10-11 |
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