JP3474672B2 - Paint composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention
Related to coating compositions for preventing adhesion of paint
It is. [0002] 2. Description of the Related Art Ship bottoms, buoys, and fishing nets submerged in seawater
(Cultured nets, fixed nets, etc.), anti-pollution film for water, for cooling
Barnacles,
Various obstacles due to adhesion of Serpula, mussels, algae, etc.
Happens. To prevent pollution by those organisms,
Paint that prevents organisms from attaching to the surface of underwater objects
It is well known to be clothed. [0003] Paints, such as paints, for preventing such fouling.
In other words, as the antifouling paint, the basic bone that forms the antifouling coating film
The rated resin does not dissolve in seawater and is a component of the resin.
As the rosin dissolves, the antifouling agent is extracted from the coating.
And dissolves in seawater to prevent the attachment of marine organisms.
Stop-type paints are known. This type of paint is basically
Generally, the initial antifouling effect due to residual skeleton resin
The result is good, but there is a drawback that the antifouling effect will be insufficient in the long term
Atsuta. [0004] As the above-mentioned improved type, a basic method for forming a coating film is described.
So-called water content in which the skeleton resin is hydrolyzed by seawater
There is a dissolvable self-polishing antifouling paint. This type of paint
Since the film surface elutes, the active antifouling coating surface is always maintained
Therefore, the durability of the antifouling effect is easily obtained.
Such a hydrolyzable self-polishing antifouling paint is useful.
Machine tin polymers have been widely used. However, in recent years
The organotin compounds released as antifouling agents after hydrolysis
Marine pollution caused by waste
Their use has been limited. [0005] Therefore, such a problem of marine pollution is prevented.
Organic tin free hydrolyzable self-polishing protection
Stained paints are strongly desired, for example, Japanese Patent Publication No. 60-50 / 1985.
No. 0452 discloses many examples of various hydrolyzable groups
And an organic silicon (alkoxysilyl group or
By (meth) acrylate having a luganosilyl group
Uses organosilyl group-containing polymer utilizing hydrolysis
Antifouling paints have been proposed. But both are enough
Has not yet been put to practical use. [0006] DISCLOSURE OF THE INVENTION The present inventors have found that
Based on the knowledge, acrylics having an organosilyl group in the side chain
Luster ester resin, methacrylate ester resin, male
Acid ester resin, fumaric acid ester resin and itako
As a result of various studies on acid ester resins, the following
Such facts have been found. That is, in the above various resins,
Hydrolysis-type protection cannot be achieved simply by having a silsilyl group on the side chain.
Rotary test (cylindrical drum), which is the most important
(Consumption rate of film thickness)
Shows no solubility, good in antifouling immersion test
Does not exhibit a high level of antifouling properties,
Does not show good adhesion to paint
Paint film falls off during pickling and does not show suitability as antifouling paint
It has been found. The present invention has been made in view of the above circumstances, and
There is no sticking or peeling, and even underwater at an appropriate speed and evenly
Shows hydrolytic properties that dissolve in
The purpose is to provide a paint composition that exhibits fouling performance
ing. [0009] Means for Solving the Problems The present inventors have set forth the above-mentioned object.
As a result of extensive research to achieve the goal, organosilyl
Group-containing monomers and, Alkoxy or aryloxy in the molecule
Consists of a silalkylene glycol groupContains a specific group
Use a polymer obtained by copolymerizing a monomer and
Rotary test by using a pollutant as an essential component
Stable coating consumption rate is obtained in
Long-lasting performance and no cracking
Good physical properties required for hydrolysis type paint
It was found that a paint composition that could
Was completed. That is, the present invention provides the following general formula
(1);(Where R¹~ R³Are all alkyl groups and aryl groups
Groups selected from among
May also be different groups. X is acryloyloxy
Group, methacryloyloxy group, maleinoyloxy group,
A fumaroyloxy group or an itaconoyloxy group
You. ) And a monomer A represented by the following general formula:(5); (Where R¹³Is a hydrogen atom or a methyl group. R
¹⁴Is an ethylene group, R^FifteenIs an alkylene group having 3 carbon atoms,
R¹⁶Is an alkylene group having 4 carbon atoms. R¹⁷Is al
It is a kill group or an aryl group. m, n, o are 0 or more
It is an integer, and n and o do not become 0 at the same time. )so Copolymer of monomer mixture containing monomer B represented
And an antifouling agent as essential components.
The present invention relates to a coating composition comprising:In addition, the monomer B is a single monomer represented by the general formula (5).
Use the body alone or, if necessary,
The following general formulas (2) to (4) and (6) to
(9); (Wherein, R4 is a hydrogen atom or a methyl group. R5 is
It is an alkylene group. R6 and R7 are both alkyl groups
And the same or different groups
Is also good. ) (Wherein, R8 is a hydrogen atom or a methyl group. R9 is
It is an alkylene group. R10 to R12 are all
Groups that are the same or different from each other.
You may use it. Y is a halogen atom. ) CH2 = CH-Z (4) (In the formula, Z is a group comprising a heterocyclic ring containing a nitrogen atom.
You. ) (Wherein, R18 is a hydrogen atom or a methyl group. R1
9 and R20 are both alkyl groups and are the same as each other.
Or different groups. ) (In the formula, R21 is a hydrogen atom or a methyl group.
⊃Q is a nitrogen-containing saturated or unsaturated cyclic hydrocarbon group.
Thus, in the structure of Q, -O-, = N-, -S-, -NR2
2- (R22 is an alkyl group)
No. ) (Wherein, R23 is a hydrogen atom or a methyl group. T is
A group consisting of a furan or tetrahydrofuran ring
You. ) CH2 = CH-CN (9) May be used in combination. [0011] In the coating composition of the present invention,
Single component represented by the general formula (1) as one of the essential components
One or more of the body A and a general formulaIn (5)expressed
Containing one or more monomers B, if necessary
One or more of other monomers copolymerizable therewith
(Hereinafter referred to as copolymer A)
B). The monomer A is represented by the general formula (1)
Thus, as an unsaturated group (X) in the molecule, acryloyl
Oxy group, methacryloyloxy group, maleinoyl oxy
Si group [mainly monoalkyl (C1-6) ester male
Inoyloxy group), fumaroyloxy group (mainly
Alkyl (C1-6) ester fumaroyloxy
Group) or itaconoyloxy group (mainly monoalkyl
(C 1-6) ester itaconoyloxy group]
And having a triorganosilyl group.
You. In the triorganosilyl group, three groups
Alkyl group or aryl group (R¹ ~ R^Three ) Is the same group
Or a different group. Specifically,
, Ethyl, n-propyl, n-butyl etc.
20 or less linear alkyl groups, isopropyl,
Cyl, s-butyl, t-butyl, etc. having 20 or less carbon atoms
Branched alkyl groups such as cyclohexyl groups
A kill group; an aryl group or a substituted aryl group;
You. As the substituted aryl group, halogen, about 18 carbon atoms
Up to alkyl, acyl, nitro or amino
Aryl groups substituted with a group, etc.
You. Examples of such a monomer A include intramolecular
Having an acryloyloxy group as
Lucylyl acrylate, triethylsilyl acrylate
Tri-n-propylsilyl acrylate, tri-n-butyl
Tylsilyl acrylate, tri-n-amylsilyl acrylate
Rate, tri-n-hexylsilyl acrylate, tri-n
Octylsilyl acrylate, tri-n-dodecylsilyl
Luacrylate, triphenylsilyl acrylate, g
Ri-p-methylphenylsilyl acrylate, triisoprop
Ropirsilyl acrylate, triisobutylsilyl acrylate
Relate, tri-2-methylisopropylsilyl acryle
-Tri-t-butylsilyl acrylate, ethyldimethyl
Tylsilyl acrylate, n-butyldimethylsilyl acrylate
Acrylate, n-octyldi-n-butylsilyl acryle
― Further, a methacryloyloxy group is present in the molecule.
Have trimethylsilyl methacrylate,
Triethylsilyl methacrylate, tri-n-propyl
Ril methacrylate, tri-n-butylsilyl methacrylate
-Tri-n-amylsilyl methacrylate, tri-n-
Hexylsilyl methacrylate, tri-n-octylsilyl
Rumethacrylate, tri-n-dodecylsilyl methacrylate
-Triphenylsilyl methacrylate, tri-p-meth
Thiphenylsilyl methacrylate, triisopropyl
Silyl methacrylate, triisobutylsilyl methacrylate
Rate, tri-2-methylisopropylsilyl methacrylate
, Tri-t-butylsilyl methacrylate, ethyldi
Methylsilyl methacrylate, n-butyldimethylsilyl
Methacrylate, n-octyldi-n-butylsilylmethyl
There is a takrate. Further, a maleinoyloxy group is added to the molecule.
Having trimethylsilylmethyl maleate,
Triethylsilylethyl maleate, tri-n-propylsi
Ryl n-propyl maleate, tri-n-butylsilyl n-
Butyl maleate, tri-n-amylsilyl n-amyl maleate
-Tri, tri-n-hexylsilyloctyl maleate, tri
n-octyl silyl decyl maleate, tri n-dodecy
Lucylyl methyl maleate, triphenylsilyl methyl male
Rate, tri-p-methylphenylsilylmethyl maleate
, Triisopropylsilylmethyl maleate, triiso
Butylsilylmethyl maleate, tri-2-methylisopro
Pyrsilyl methyl maleate, tri-t-butylsilylmethyl
Lumarate, ethyldimethylsilylmethylmalate, n
-Butyldimethylsilylmethyl maleate, n-octyl
And di-n-butylsilylmethyl maleate. Further, it has a fumaroyloxy group in the molecule.
Trimethylsilylmethyl fumarate, g
Triethylsilylethyl fumarate, tri-n-propyl
Ryl n-propyl fumarate, tri-n-butylsilyl n
-Butyl fumarate, tri-n-amylsilyl n-amyl
Fumarate, tri-n-hexylsilyl n-hexyl fuma
Rate, tri-n-octyl silyl decyl fumarate,
Tri-n-dodecylsilylmethyl fumarate, triphenyl
Lucylyl methyl fumarate, tri-p-methylphenyl
Rylmethyl fumarate, triisopropylsilylmethyl
Fumarate, triisobutylsilylmethyl fumarate,
Tri-2-methylisopropylsilylmethyl fumarate,
Tri-t-butylsilylmethyl fumarate, ethyl dimethyl
Lucylyl methyl fumarate, n-butyldimethylsilyl
Methyl fumarate, n-octyldi-n-butylsilylmethyl
Chill malate and the like. Further, itaconoyloxy group is added to the molecule.
Has trimethylsilylmethylitacone
G, triethylsilylethyl itaconate, tri-n-propyl
Ropirsilyl n-propyl itaconate, tri-n-butyl
Lucylyl n-butyl itaconate, tri-n-amylsilicone
N-amylyltaconate, tri-n-hexylsilyl n
-Hexyl itaconate, tri-n-octylsilyl octane
Chiruita connect, tri-n-dodecylsilyldecyl
Taconate, triphenylsilylmethylitanate,
Tri-p-methylphenylsilylmethylitaconate,
Liisopropylsilylmethyl itaconate, triisobu
Tylsilyl methyl itaconate, tri-2-methyl isop
Ropirsilyl methyl itaconate, tri-t-butylsilicone
Methyl itaconate, ethyl dimethyl silyl methyl i
Taconate, n-butyldimethylsilylmethylitacone
ト, n-octyldi-n-butylsilylmethylitacone
― And the like. The monomer B isSimply represented by the general formula (5)
A monomer is used, but if necessary,
Are represented by the general formulas (2) to (4) and (6) to (9).
Can be used in combination.These are roughly divided
Then, the tertiary amino acids represented by the general formulas (2) to (4)
Groups, quaternary ammonium bases or nitrogen-containing heterocycles
Monomer (hereinafter, referred to as monomer B-1)
Alkoxy or aryloxy within the molecule represented by (5)
Monomers having a silalkylene glycol group (hereinafter referred to as single
And represented by general formulas (6) to (9)
Includes a structure that does not have active hydrogen in the molecule but has polarizability
(Hereinafter referred to as monomer B-3)
Can be Of the above-mentioned monomer B-1, general formula (2)
Are those containing a tertiary amino group in the molecule
Where R^FourIs a hydrogen atom or a methyl group,
R^FiveIs an alkylene group having 8 or less carbon atoms. R⁶And R
⁷Are all alkyl groups, specifically, methyl
, Ethyl, n-propyl, n-butyl etc.
20 or less linear alkyl groups, isopropyl,
Cyl, s-butyl, t-butyl, etc. having 20 or less carbon atoms
A branched alkyl group or a ring such as a cyclohexyl group
Alkyl group and the like. This R⁶And R⁷Are each other
May be the same or different. The monomer represented by the general formula (3) is
It contains a quaternary ammonium base in the molecule, and has the formula
Medium, R⁸Is a hydrogen atom or a methyl group;⁹Is carbon
It is an alkylene group having a number of 8 or less. R^Ten~ R¹²Will eventually
Is also an alkyl group, specifically, methyl, ethyl,
A straight chain having 20 or less carbon atoms, such as n-propyl and n-butyl.
Chain alkyl groups, isopropyl, isobutyl, s-butyl
Branched alkyl having 20 or less carbon atoms such as tyl and t-butyl.
A cyclic alkyl group such as a kill group or a cyclohexyl group
And the like. This R^Ten~ R¹²Are the same groups
Or a different group. Y is a halogen atom
Specifically, of fluorine, chlorine, bromine and iodine
One of the following. Further, a monomer represented by the general formula (4)
Is a compound containing a nitrogen-containing heterocyclic ring in the molecule, and has the formula
Wherein Z is the above-mentioned nitrogen-containing heterocyclic ring,
Is a pyridine ring, pyrimidine ring, pyrazine ring, quinoline
One selected from a ring, an isoquinoline ring, etc.
One. Examples of such a monomer B-1 include dimethylene
Aminoethyl acrylate, diethylaminoethyl acrylate
Acrylate, dimethylaminoethyl methacrylate, di
Ethylaminoethyl methacrylate, dimethylamino n
-Butyl acrylate, dimethylamino n-butyl meta
Acrylate, dimethylamino n-hexyl acrylate
G, di-n-butylamino 2-ethylhexyl methacrylate
-Di-ethyl-2-ethylhexylaminoethyl acryle-
G, didodecylaminoethyl methacrylate, diisobu
Tylaminoethyl acrylate, di-t-butylaminoethyl
Tyl methacrylate, dicyclohexylaminoethyl ethyl
Acrylate, dimethylaminoethyl methyl methacrylate
Chloride and vinylpyridine. The above monomer B-2 has an alkoxy group in the molecule.
Having a silyl or aryloxyalkylene glycol group
A monomer represented by the formula (5):
The aryloxyalkylene glycol group may be an alkyl group having 3 carbon atoms.
Alkylene group (R^Fifteen) Or an alkylene group having 4 carbon atoms
(R¹⁶) Is always included. That is, charcoal
A prime number 2 ethylene group (R¹⁴)
(M), an alkylene group having 3 carbon atoms (R^Fifteen)
And the number of units (n) is an alkylene group having 4 carbon atoms (R¹⁶)
The number of repeating units (o) is an integer of 0 or more.
But an alkylene group having 3 carbon atoms (R^Fifteen)
The number of units (n) and an alkylene group having 4 carbon atoms (R¹⁶)
The number of repeating units (o) cannot be 0 at the same time.
No. The number of repeating units m, n, and o is two or more.
When a mixture of monomers is used, the average
In some cases. In the general formula (5), R¹³Is
It is a hydrogen atom or a methyl group. In addition, C 3
R representing a kylene group^FifteenAnd R representing an alkylene group having 4 carbon atoms
¹⁶May have a branched structure. R¹⁷Is an alkyl group
Or an aryl group, specifically, methyl, ethyl
, N-propyl, n-butyl etc. have 20 or less carbon atoms
Linear alkyl group, isopropyl, isobutyl, s
Branched with less than 20 carbon atoms such as -butyl, t-butyl, etc.
Cyclic alkyl such as alkyl group or cyclohexyl group
Aryl group, aryl group or substituted aryl group, etc.
You. The above substituted aryl group includes halogen, carbon number
Is up to about 18 alkyl groups, acyl groups, nitro groups or
Is an aryl group substituted with an amino group. As such a monomer B-2, 2-me
Toxipropyl acrylate, methoxydipropylene
Alcohol acrylate, methoxytripropylene glyco
-Rum methacrylate, methoxy polypropylene glyco-
Luacrylate, 2-ethoxypropyl acrylate,
2-ethoxydipropylene glycol acrylate,
Toxiheptapropylene glycol-heptaethyleneg
Alcohol acrylate, octoxypropylene glycol
Ledecaethylene glycol acrylate, 3-methoxy
Cybutyl acrylate, 3-methoxydibutylene glyco
-Luacrylate, 3-methoxytributylene glyco-
Ruacrylate, 3-methoxypolybutylene glycol
Acrylate, 3-ethoxybutyl acrylate, 3-
Ethoxydibutylene glycol acrylate, 3-ethoxy
Xytributylene glycol acrylate, 3-ethoxy
Cipolybutylene glycol acrylate, 2-methoxy
Propyl methacrylate, methoxydipropylene glyco
-Methyl methacrylate, methoxytripropylene glyco-
Methacrylate, methoxy polypropylene glycol
Methacrylate, 2-ethoxypropyl methacrylate
G, 2-ethoxydipropylene glycol methacrylate
G, methoxyheptapropyleneglycol-heptaethyl
Lengglycol methacrylate, octoxypropylene
Glycol-decaethylene glycol methacrylate,
3-methoxybutyl methacrylate, 3-methoxydib
Tylene glycol methacrylate, 3-methoxytrib
Tylene glycol methacrylate, 3-methoxypolybut
Tylene glycol methacrylate, 3-ethoxybutyl
Methacrylate, 3-ethoxydibutylene glycol
Tacrylate, 3-ethoxytributylene glycol
Tacrylate, 3-ethoxypolybutylene glycol
Takylates and the like. Of the above monomer B-3, the compound represented by the general formula (6)
Are those containing a substituted amide group in the molecule
Where R¹⁸Is a hydrogen atom or a methyl group,
Also R¹⁹And R²⁰Is an alkyl group having 8 or less carbon atoms
And specifically, methyl, ethyl, n-propyl
Linear alkyl having 8 or less carbon atoms, such as
Groups, isopropyl, s-butyl, t-butyl, etc.
A branched alkyl group having 8 or less carbon atoms, such as cyclohexyl
Any cyclic alkyl group and the like can be mentioned. This R¹⁹And R²⁰
Are the same or different groups.
No. The monomer represented by the general formula (7) is
It contains a cyclic amide moiety in the molecule and has the formula
Medium, R^{twenty one}Is a hydrogen atom or a methyl group, and N⊂⊃Q is
Nitrogen-containing saturated or unsaturated cyclic carbon having 20 or less carbon atoms
A hydrogen group, and in the structure of Q, -O-, = N-, -S
-, -NR^{twenty two}− (R^{twenty two}Is an alkyl group)
Specifically, aziridine, pyrrolidine,
Nitrogen-containing saturated hydrocarbon rings such as peridine, pyrroline, imine
Nitrogen-containing unsaturated hydrocarbon rings such as dazoline and pyrazoline,
Nitrogen-containing oxygen-containing hydrocarbon rings such as morpholine and pyrrolidone
and so on. Further, a monomer represented by the general formula (8)
Has a furan or tetrahydrofuran ring in the molecule.
Where R^{twenty three}Is a hydrogen atom or methyl
And T is a furan ring or tetrahydrofuran
It is a group consisting of a ring. In addition, the unit represented by the general formula (9)
The monomer is a monomer having a nitrile group in the molecule, that is,
Acrylonitrile. Examples of such a monomer B-3 include N, N
-Dimethylacrylamide, N, N-diethylacryl
Amide, N, N-dimethylmethacrylamide, N, N-
Diethyl methacrylamide, N, N-di-n-butyl
Lilamide, N, N-di-n-hexyl methacrylami
, N, N-di-2-ethylhexylacrylamide,
N, N-diisobutylacrylamide, N, N-di-t-
Butyl methacrylamide, N, N-dicyclohexylme
Tacrylamide, acroylmorpholine, acroylpi
Peridine, acroylimidazoline, N-vinylpyrroli
Don, tetrahydrofurfuryl methacrylate, acryloyl
Nitrile and the like. Monomers copolymerizable with these monomers A and B
For example, acrylic acid and acrylic acid
Chill, ethyl acrylate, butyl acrylate, acrylic
2-ethylhexyl acid, cyclohexyl acrylate,
2-hydroxyethyl acrylate, 2-hydroacrylate
Xypropyl, glycidyl acrylate, acrylic acid 2-
Methoxyethyl, 2-ethoxyethyl acrylate
Acrylic esters, methacrylic acid and methacrylic acid
Methyl acrylate, ethyl methacrylate, butyl methacrylate,
2-ethylhexyl methacrylate, cyclomethacrylate
Hexyl, 2-hydroxyethyl methacrylate, methac
2-hydroxypropyl acrylate, glycidyl methacrylate
, 2-methoxyethyl methacrylate, methacrylic acid 2
Methacrylates such as ethoxyethyl, styrene
Len, vinyl acetate, vinyl propionate, vinyl butyrate,
Vinyl esters such as vinyl benzoate, vinyl toluene
, Α-methylstyrene, crotonic esters, fuma
Luic esters, itaconic esters, etc.
You. In the monomer mixture, the monomers A, B and
And the proportion of other monomers copolymerizable with these
Although it can be appropriately set according to the purpose of use of the composition, generally,
Is 1 to 95% by weight of monomer A and 1 to 95% by weight of monomer B.
%, The other monomer copolymerizable therewith is 0 to 95% by weight
%. The copolymer AB is prepared from such a monomer mixture
In the presence of a vinyl polymerization initiator according to a conventional method.
, Bulk polymerization, emulsion polymerization, suspension polymerization, etc.
Can be obtained by combining them. This copolymer
When AB is used for paint, it is diluted with an organic solvent and
It is convenient to prepare a polymer solution having the appropriate viscosity.
For this purpose, it is desirable to use solution polymerization or bulk polymerization.
Good. As the above-mentioned vinyl polymerization initiator, azobi
Isobutyronitrile, triphenylmethyl azobenze
Compounds such as benzoyl peroxide, di-t
-Butyl peroxide, t-butyl peroxybenzoate
-T, t-butyl peroxyisopropyl carbonate
And the like. In addition, the above-mentioned organic solvent includes
Aromatic solvents such as toluene, toluene, hexane,
Aliphatic hydrocarbon solvents such as heptane, ethyl acetate, vinegar
Ester solvents such as butyl acid, isopropyl alcohol
Alcohol solvents such as alcohol and butyl alcohol,
Ether solvents such as sun and diethyl ether, methyl
Ketones such as ethyl ketone and methyl isobutyl ketone
Solvents, and one or more of these are
Used. The copolymer AB obtained by such a method is
The molecular weight ranges from 1,000 to 300,000 by weight.
It is desirable to be in the enclosure. If the molecular weight is too low,
If film formation is difficult and too high, paint
Because the minute becomes low, only one thin coating can be obtained with one coating,
There is a problem that several paintings are required. Also,
The viscosity of the polymer solution comprising the copolymer AB at 25 ° C.
Conveniently less than 150 poise
The solid content of the polymer solution is 5 to 90% by weight, preferably
It is preferable that the content be in the range of 15 to 85% by weight. In the coating composition of the present invention, the essential components
Other known antifouling agents include those known in the art.
Is widely included. Broadly classified, contains inorganic compounds and metals
There are organic compounds and organic compounds containing no metal. As the inorganic compound, for example,
Copper, copper powder, copper thiocyanate, copper carbonate, copper chloride, copper sulfate
Which copper compounds, zinc sulfate, zinc oxide, nickel sulfate, copper
A nickel alloy. As the organic compound containing a metal, for example,
For example, organic copper compounds, organic nickel compounds and organic
There are zinc compounds, etc., other maneb, mansebu,
Propineb can also be used. As an organic copper compound
Is copper oxine, copper nonylphenolsulfonate, cutlet
Perbis (ethylenediamine) -bis (dodecylbenze
Sulfonate), copper acetate, copper naphthenate, bis (pen
Copper (tachlorophenolic acid) is an organic nickel compound
Products include nickel acetate, dimethyldithiocarbamine
Nickel acid is an organic zinc-based compound,
Lead, zinc carbamate, dimethyldithiocarbamate
Lead, zinc pyrithione, ethylenebisdithiocarbamine
Zinc acid and the like are each mentioned. Examples of the organic compound containing no metal include:
For example, N-trihalomethylthiophthalimide, dithioca
Rubamic acid, N-arylmaleimide, 3-substituted amino
-1,3-thiazolidine-2,4-dione, dithiocyanate
Compounds, triazine compounds and others
is there. N-trihalomethylthiophthalimide
N-trichloromethylthiophthalimide, N-phenyl
Such as fluorodichloromethylthiophthalimide,
As carbamic acid, bis (dimethylthiocarbamoy
G) disulphide, N-methyldithiocarbamic acid an
Monium, ethylene bis (dithiocarbamic acid) ammonium
And milneb. N-aryl maleimides include N-
(2,4,6-trichlorophenyl) maleimide, N-
4-tolylmaleimide, N-3-chlorophenylmale
Imide, N- (4-n-butylphenyl) maleimide, N
-(Anilinophenyl) maleimide, N- (2,3-
Silyl) maleimide and the like. 3-Substituted amino-1,3-thiazolidine-
As 2,4-dione, 3-benzylideneamino-
1,3-thiazolidine-2,4-dione, 3- (4-meth
Tylbenzylideneamino) -1,3-thiazolidine-
2,4-dione, 3- (2-hydroxybenzylidenea
Mino) -1,3-thiazolidine-2,4-dione, 3-
(4-dimethylaminobenzylideneamino) -1,3-
Thiazoline-2,4-dione, 3- (2,4-dichloro
Benzylideneamino) -1,3-thiazolidine-2,4
-Dione and the like. Examples of the dithiocyano compound include dithiocyano compounds.
Anomethane, dithiocyanoethane, 2,5-dithiocyan
Notthiophene and the like are triazine-based compounds,
-Methylthio-4-tert-butylamino-6-cyclopro
Pillamino-s-triazine and the like, respectively.
You. Other metal-free organic compounds
Is 2,4,5,6-tetrachloroisophthalonitrile
, N, N-dimethyldichlorophenylurea, 4,5-
Dichloro-2-N-octyl-3- (2H) isothiazo
Ron, N, N-dimethyl-N'-phenyl- (N-fur
Orodichloromethylthio) sulfamide, tetramethyl
Thiuram disulfide, 3-iodo-2-propynylbu
Tyl carbamate, 2- (methoxycarbonylamino)
Benzimidazole, 2,3,5,6-tetrachloro-
4- (methylsulfonyl) pyridine, diiodomethylpa
Latrile sulfone, 2- (4-thiazolyl) benziimi
Dazol, triphenylboronpyridine, etc.
You. In the present invention, various kinds of antifouling as described above are used.
Select and use one or more of these agents
However, the amount used is the percentage of the antifouling agent in the paint solids.
Is usually 0.1 to 80% by weight, preferably 1 to 60% by weight.
It is. If the amount of the antifouling agent is too small, the antifouling effect cannot be expected.
Cracks, peeling and other defects in the formed coating film
It is difficult to obtain effective antifouling properties. The coating composition of the present invention thus constituted
If necessary, red petals, titanium dioxide, talc, acid
Colorants such as pigments and dyes such as zinc fossil, water binders, paints
Anti-sagging agent, anti-separation agent, sedimentation prevention
Various known additives such as anti-foaming agents and defoamers
Can be. Dipping in seawater using the coating composition of the present invention
To form an antifouling coating on the surface of the object to be
After being applied to the surface of the object by appropriate means,
The solvent may be removed by evaporation under heating.
A dry coating film can be easily formed on the surface of the object.
You. [0049] According to the present invention, the coating composition of the present invention
Good stability during dispersion process and storage.
Bottom, fish nets and cooling that need to prevent underwater biofouling
Underwater structures such as water pipes, and sludge expansion in marine civil engineering work
It can be used to prevent scattering, etc.
Dissolves into the sea at a suitable speed and evenly without delamination
Decomposes to hydrolyzate,
To maintain excellent antifouling performance over a long period of time.
it can. [0050] EXAMPLES Next, the present invention will be described with reference to Production Examples, Examples and Comparative Examples.
This will be described in detail using an example. The parts in the examples are weight
Parts, viscosity is measured value of foam viscosity at 25 ° C, molecular weight is GP
It is a weight average molecular weight in terms of polystyrene by C.Note that
In all of the following production examples and examples, the present invention
Using a polymer solution production example according to this polymer solution
Are described as examples of the coating composition of the present invention.
Are included in the claims of the present invention.
These are described in "Production Examples 14 to 26" and "Examples 14 to 2".
6 ", and other production examples and examples are
Described as a reference example, not included in the claims
Things. Production Examples 1 to 13 and Comparative Production Examples 1 and 2
In a flask equipped with a stirrer, according to the formulations in Tables 1 to 3 below
While charging the solvent, stirring and introducing nitrogen gas,
The temperature was raised to 80 ° C. Fluidize the mixture of monomer and polymerization catalyst.
Drops into the sco in 3 hours, and after dropping at the same temperature for 5 hours
Hold to complete polymerization. Finally, add a diluting solvent to dilute
Each polymer solution S₁ ~ S₁₃And T₁, T_TwoGet
Was. The viscosity of these polymer solutions and the molecular weight of the polymer are:
The results were as described in Tables 1 to 3. In Tables 1 to 3, monomer A and monomer A
Abbreviations indicating monomer B and other monomers,
“AIBN” used as the cocatalyst is as follows:
You. TBSA: tri-n-butylsilyl acrylate TESA: triethylsilyl acrylate TPSA: tri-n-propylsilyl acrylate TIPSA: triisopropylsilyl acrylate TBSMA: tri-n-butylsilyl methacrylate TBSMM: tri-n-butylsilylmethyl maleate TBSBF: tri-n-butylsilyl n-butylfumare
―G TBSMI: tri-n-butylsilylmethylitacone
G DMAEMA: dimethylaminoethyl methacrylate DEAEMA: diethylaminoethyl methacrylate DMAEMAMCl: dimethylaminoethyl methacrylate
Luchloride VPy: vinyl pyridine DMAEA: dimethylaminoethyl acrylate MMA: Methyl methacrylate VAc: vinyl acetate AIBN: 2,2'-azobisisobutyronitrile [0053] [Table 1] [0054] [Table 2][0055] [Table 3] Production Examples 14 to 26 and Comparative Production Example 3 Prepare a flask equipped with a stirrer according to the following formulations in Tables 4 to 6.
Charge the solvent, stir and introduce nitrogen gas.
Then, the temperature was raised to 80 ° C. Mixture of monomer and polymerization catalyst
The solution was dropped into the flask in 3 hours, and at the same temperature after the dropping was completed for 5 hours.
Hold for a time to complete the polymerization. Finally, add the diluent solvent
And dilute each polymer solution S₁₄~ S₂₆And T_ThreeI got
The viscosity of these polymer solutions and the molecular weight of the polymer are shown in Table 4.
~ As shown in Table 6. In Tables 4 to 6, monomer B is shown.
The respective abbreviations are as follows. Monomer A and its
Abbreviations indicating other monomers, further used as polymerization catalyst
“AIBN” is the same as in Tables 1 to 3 above.
You. MDPA: methoxydipropylene glycol acryle
G [Kyoeisha Oil & Fat Chemical Co., Ltd. product name "DPM-
A ") MTPA: methoxytripropylene glycol acryle
-G [Osaka Organic Chemical Industry Co., Ltd.
# 320 ") MMBA: 3-methoxybutyl acrylate [Osaka organic
Product name “Viscoat # 158” manufactured by Chemical Industry Co., Ltd.] MHPHEA: methoxyheptapropylene glycol-
Heptaethylene glycol methacrylate [Nippon Oil & Fats
"Blemma-50PMEP800"
B ") OOPDEA: Octoxypropylene glycol-deca
Ethylene glycol acrylate (manufactured by NOF Corporation)
Product name "Blemma-50POEP800B"] [0058] [Table 4] [0059] [Table 5][0060] [Table 6] Production Examples 27 to 39 and Comparative Production Example 4 In a flask equipped with a stirrer, the following formulations in Tables 7 to 9 were applied.
Charge the solvent, stir and introduce nitrogen gas.
Then, the temperature was raised to 80 ° C. Mixture of monomer and polymerization catalyst
The solution was dropped into the flask in 3 hours, and at the same temperature after the dropping was completed for 5 hours.
Hold for a time to complete the polymerization. Finally, add the diluent solvent
And dilute each polymer solution S₂₇~ S₃₉And T_FourI got
The viscosity of these polymer solutions and the molecular weight of the polymer are shown in Table 7
~ Torido also listed in Table 9. In Tables 7 to 9, monomer B is shown.
The respective abbreviations are as follows. Monomer A and its
Abbreviations indicating other monomers, further used as polymerization catalyst
“AIBN” is the same as in Tables 1 to 3 above.
You. DMAA: N, N-dimethylacrylamide ACMO: Acroylmorpholine VPR: N-vinylpyrrolidone THFMA: Tetrahydrofurfuryl methacrylate ANT: Acrylonitrile [0063] [Table 7] [0064] [Table 8][0065] [Table 9] Examples 1 to 10 and Comparative Examples 1 and 2 As polymer solutions, Production Examples 1 to 10 and Comparative Production Example
Using those described in Table 10 below, manufactured in
32.8 parts of these polymer solutions, 57.41 parts of cuprous oxide,
1.19 parts of titanium oxide, anti-sagging agent [Kusumoto Co., Ltd.
"Dispalon A630-20X"] 3 parts, as solvent
Mix 5.6 parts of xylene with a paint shaker
By spraying, 10 kinds of coating compositions of the present invention and
Two comparative coating compositions were prepared. [0067] [Table 10] Embodiment 11 As the polymer solution, the polymer solution S produced in Production Example 11
₁₁32.8 parts of this polymer solution and 30 parts of cuprous oxide
Part, 2,4,5,6-tetrachlorophthalonitrile 5
Parts, titanium dioxide 1.19 parts, anti-sagging agent [Kusumoto Co., Ltd.]
"Daspalon A630-20X"], 3 parts
And 28.01 parts of xylene were added to a paint shaker.
To prepare the coating composition of the present invention.
did. Embodiment 12 As the polymer solution, the polymer solution S produced in Production Example 12
₁₂Using 32.8 parts of this polymer solution and copper thiocyanate
30 parts, titanium dioxide 1.19 parts, anti-sagging agent [Kusumoto
Co., Ltd. “Dayspalon A630-20X”] 3 parts,
33.01 parts of xylene as a solvent was added to a paint shaker.
-By mixing and dispersing, the coating composition of the present invention
Was prepared. Embodiment 13 As the polymer solution, the polymer solution S produced in Production Example 13
₁₃Using 32.8 parts of the polymer solution
15 parts of pyridine urate, 1.19 parts of titanium dioxide, anti-sagging
[Daspalon A630-20 manufactured by Kusumoto Co., Ltd.]
X "], and 48.01 parts of xylene as a solvent.
The present invention is achieved by mixing and dispersing with a
Was prepared. The above Examples 1 to 13 and Comparative Examples 1 and 2
The antifouling performance test for each of the paint compositions
Test, paint wear test, adhesion test and crack resistance test
Went. These results are shown in Tables 11 to 14 below.
It was as it was. <Anti-fouling performance test>
Pre-applied tar vinyl rust preventive paint to blasted steel sheet
Both sides of the painted plate (100mm × 200mm × 1mm)
Spray-coated so that the dry film thickness is 240 μm on one side.
The test piece was prepared by coating twice with the adhesive. This test piece
Aioi City Minister of Hyogo Prefecture
In the raw bay, immerse in seawater for 24 months,
Measure the percentage of the occupied area (attachment area) of the epiphytes over time
Was. <Coating film wear test> Each coating composition was applied to the back side.
Table of steel plates (100mm x 100mm x 1mm) with anti-rust coating
Spray paint on the surface so that the dry film thickness is 200 μm
And dried for 1 week in a room at a temperature of 20 ° C.
Produced. On the outer surface of a cylindrical drum having a diameter of 50 cm,
After fixing the test piece, 1 below sea level in Yura Bay, Sumoto City, Hyogo Prefecture
m so that the peripheral speed of the drum becomes 16 knots.
Rotate with a motor to reduce the exhausted coating thickness to 18
Measured monthly. The average speed of consumption of coating film thickness (μm / month)
Was calculated. The average consumption rate of the coating thickness was 3 μm / month.
Above values correlate with good antifouling performance. <Adhesion test>
A dry film thickness of 125 μm per coating
Spray paint twice, then tarbini
So that the dry film thickness becomes 70 μm.
Painted. On this, each coating composition was dried to a film thickness of 10
Spray paint twice so that it becomes 0 μm,
Dry in a constant temperature and humidity room at a temperature of 20 ° C and a humidity of 75% for one week.
Then, a test piece was prepared. Immerse this test piece in artificial seawater
3 months, 6 months, 9 months, 12 months and
Raised 18 months later, conducted a goban test at 2 mm intervals
gave. The adhesion was evaluated as follows:
個 (pass) when the number of pieces is 25/25 pieces;
The case of / 25 was evaluated as x (fail). <Crack resistance test> Adhesion test
When the test specimen is lifted from artificial seawater,
Visual observation was made to check for the occurrence of cracks. Crack
○ (pass) if there is no, and × (fail) if there is
Was. [0076] [Table 11][0077] [Table 12] [0078] [Table 13][0079] [Table 14] It is clear from the results of Tables 11 to 14 above that
As described above, the coating compositions of the present invention of Examples 1 to 13 are
No biofouling in performance until 24 months
The coating film consumption was good, and no coating film defects were observed.
On the other hand, Comparative Example 1 is a polymer containing an organosilyl group.
It is a coating composition using a body, but has a dissolution rate and antifouling property
Are both unsatisfactory results, and have poor adhesion and crack resistance.
Defects were also seen in the sex. Comparative Example 2 has a tertiary amino group.
Coating composition using a polymer containing
It tends to swell and can not obtain satisfactory properties
I got it. Examples 14 to 23 and Comparative Example 3 As polymer solutions, Production Examples 14 to 23 and Comparative Production Example
Except for using those described in Table 15 below manufactured in 3
Is similar to Examples 1 to 10 and Comparative Examples 1 and 2,
10 paint compositions of the present invention and 1 paint composition for comparison
Was prepared. [0082] [Table 15] Embodiment 24 As the polymer solution, the polymer solution S produced in Production Example 24
_{twenty four}32.8 parts of this polymer solution and 30 parts of cuprous oxide
Part, 4,5-dichloro-2-N-octyl-3 (2H)
Isothiazolone 5 parts, titanium dioxide 1.19 parts, anti-sag
[Daspalon A630-20 manufactured by Kusumoto Co., Ltd.]
X "], 38.0 parts of xylene as a solvent,
The present invention is achieved by mixing and dispersing with a
Was prepared. Embodiment 25 As the polymer solution, the polymer solution S produced in Production Example 25
_{twenty five}32.8 parts of this polymer solution and 30 parts of cuprous oxide
Parts, zinc ethylenebisdithiocarbamate 10 parts, diacid
1.19 parts of titanium oxide, anti-sagging agent [Kusumoto Co., Ltd.
ISPARON A630-20X "], 3 parts
23.01 parts of ren were mixed with a paint shaker.
By spraying, a coating composition of the present invention was prepared. Embodiment 26 As the polymer solution, the polymer solution S produced in Production Example 26
₂₆Using 32.8 parts of this polymer solution and N, N-dimethyl
Lechlorophenyl urea 20 parts, zinc white 5 parts, talc 5
Parts, titanium dioxide 1.19 parts, anti-sagging agent [Kusumoto Co., Ltd.]
"Daspalon A630-20X"], 3 parts
Then, 33.01 parts of xylene was added to a paint shaker.
To prepare the coating composition of the present invention.
did. In the above Examples 14 to 26 and Comparative Example 3,
About each coating composition, the said Examples 1-13 and ratio
As in Comparative Examples 1 and 2, the antifouling test and the consumption of the coating film were performed.
Tests, adhesion tests and crack resistance tests were performed. This
The results are as shown in the following Tables 16-19.
Atsuta. [0087] [Table 16][0088] [Table 17] [0089] [Table 18][0090] [Table 19] It is clear from the results of Tables 16 to 19 above that
As such, the coating compositions of the present invention of Examples 14-26
As in the case of the coating compositions of Examples 1 to 13 described above,
No biofouling in performance until 24 months
The coating film consumption was good, and no coating film defects were observed.
On the other hand, Comparative Example 3 is an alkoxyalkylene glyco
-A paint composition using a copolymer containing
Tend to swell early in the experiment
I couldn't. Examples 27 to 36 and Comparative Example 4 Production Examples 27 to 36 and Comparative Production Examples as Polymer Solutions
Except for using those described in Table 20 below manufactured in 4
Is similar to Examples 1 to 13 and Comparative Examples 1 and 2,
10 paint compositions of the present invention and 1 paint composition for comparison
Was prepared. [0093] [Table 20] Embodiment 37 As the polymer solution, the polymer solution S produced in Production Example 37
₃₇Using 32.8 parts of this polymer solution and copper thiocyanate
30 parts, titanium dioxide 1.19 parts, anti-sagging agent [Kusumoto
Co., Ltd. “Dayspalon A630-20X”] 3 parts,
33.01 parts of xylene as a solvent was added to a paint shaker.
-By mixing and dispersing, the coating composition of the present invention
Was prepared. Embodiment 38 As the polymer solution, the polymer solution S produced in Production Example 38
₃₈32.8 parts of this polymer solution and 30 parts of cuprous oxide
Parts, zinc pyrithione 10 parts, titanium dioxide 1.19
Part, anti-sagging agent [Duspalon A63 manufactured by Kusumoto
0-20X "] 3 parts, xylene as a solvent 23.01 parts
Are mixed and dispersed by a paint shaker.
Thus, a coating composition of the present invention was prepared. Embodiment 39 As the polymer solution, the polymer solution S produced in Production Example 39
₃₉32.8 parts of this polymer solution and 30 parts of cuprous oxide
Part, dithio 2,2'-bisbenzmethylamide 5 parts,
1.19 parts of titanium oxide, anti-sagging agent [Kusumoto Co., Ltd.
"Dispalon A630-20X"] 3 parts, as solvent
Mix 28.01 parts of xylene with a paint shaker
By mixing and dispersing, the coating composition of the present invention is prepared.
Was. In the above Examples 27 to 39 and Comparative Example 4,
About each coating composition, the said Examples 1-13 and ratio
As in Comparative Examples 1 and 2, the antifouling test and the consumption of the coating film were performed.
Tests, adhesion tests and crack resistance tests were performed. This
These results are shown in Tables 21 to 24 below.
It was. [0098] [Table 21][0099] [Table 22] [0100] [Table 23][0101] [Table 24] It is clear from the results of Tables 21 to 24 above that
As described above, the coating compositions of the present invention in Examples 27 to 39
Antifouling properties as in the case of the coating compositions of Examples 1-26
No attachment of organisms in Noh was observed until 24 months,
The coating film consumption was good, and no coating film defects were observed. this
On the other hand, Comparative Example 4 uses a polymer having a substituted amide group.
Paint composition, but tends to swell at the beginning of the test.
And satisfactory characteristics could not be obtained.

──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Masayasu Ito 2-86 Senju, Itami-shi, Hyogo (72) Inventor Kenichi Arakawa 6-23, Kadotookada-cho, Nishinomiya-shi, Hyogo (72) Inventor Yasuhide Akiba, Nishinomiya, Hyogo 6-23, Okada-cho, Ichido (56) References JP-A-1-146969 (JP, A) JP-A-53-124538 (JP, A) JP-A-5-320539 (JP, A) JP-A-62-1 275113 (JP, A) JP-A-4-264169 (JP, A) JP-A-3-31372 (JP, A) JP-A-7-102193 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 5/14 C09D 5/16 C09D 133/14 C09D 143/04

Claims (1)

(57) [Claims] [Claim 1] The following general formula (1): (Wherein, R ^{1 to} R ³ are all groups selected from an alkyl group and an aryl group, and may be the same or different groups. X is acryloyloxy Group, methacryloyloxy group, maleinoyloxy group,
It is a fumaroyloxy group or an itaconoyloxy group. And a monomer A represented by the following general formula (5) : (Wherein, R ¹³ is a hydrogen atom or a methyl group.
¹⁴ is an ethylene group, R ¹⁵ is an alkylene group having 3 carbon atoms,
R ¹⁶ is an alkylene group having 4 carbon atoms. R ¹⁷ is an alkyl group or an aryl group. m, n, and o are integers greater than or equal to 0, and n and o do not become 0 at the same time. ) A copolymer of a monomer mixture containing a monomer B represented by the coating composition characterized by containing the antifouling agent as essential components.