JPS6197374A - Fluorocarbon resin-containing antifouling coating - Google Patents

Abstract

PURPOSE:To provide a normal temp. curing antifouling coating containing a fluorine-contg. block copolymer obtained by copolymerization of a specified peroxy or azo bond-contg. copolymer and a (fluorine-contg.) vinyl monomer and exhibiting a perfect antifouling effect without environmental pollution. CONSTITUTION:A peroxy or azo bond-contg. copolymer (A) is prepared by copolymerizing 0.5-20pts.wt. polymeric peroxide of formula I where R1 is 1-18C (substituted) alkylene, 3-15C (substituted) cycloalkylene, formula II, etc.: n is 2-30) or polyazo compd. of formula III (where R7 is CH3 or CN: m is 0-1) and 100 pts. wt. (fluorine-contg.) vinyl monomer. Then (A) and vinyl monomer (B) when A contains fluorine) or fluorine-contg vinyl monomer (when A contains no fluorine) are block copolymerizied to produce a fluorine-contg. block copolymer in which the ratio of a polymer not contg. fluorine to a fluorine-contg. polymer is 1/19-19/1 by weight. The coating contains the block copolymer in an amt. of 0.1 wt. % or more.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a fluorine-containing resin antifouling paint containing a specific fluorine-containing block copolymer.

(Prior art) Structures and equipment that come into contact with seawater, such as ships, offshore structures, power plant cooling water systems, etc., have animals and plants that adhere to them, such as sea lettuce, blue laver, Fujitbo, mussel, and cellupa. This may damage the original functions of structures and equipment (called contamination).

On the other hand, there are conventional methods to prevent attachment of these animals and plants (
There have been various attempts at antifouling (hereinafter referred to as antifouling), but the current mainstream method is to coat equipment and structures with paints containing chemicals such as triorganotin compounds, copper 1ffi alide, and cuprous Rodan. , or a method of injecting chlorine and its compounds (for example, sodium hypochlorite) into seawater (hereinafter referred to as a pharmaceutical antifouling method).

(Problems to be Solved by the Invention) However, with this type of chemical antifouling method, if uncontrolled, like chlorine, it will be released in high concentrations and kill useful marine organisms, and like copper compounds, it will decompose and become non-toxic. Therefore, it is often impossible to completely avoid environmental pollution, such as gradual accumulation in specific sea areas and metastasis to living organisms.

The essence of fouling is that plant spores or animal larvae are
The spores and larvae grow by adhering to the seawater contact surfaces of equipment, and drug-based antifouling methods are achieved by using eluted or dissolved drugs to kill or escape these spores and larvae. Therefore, pharmaceutical antifouling methods inherently have the potential for environmental pollution.

On the other hand, demand for fluorine-containing resin paints such as polytetrafluoroethylene has increased in recent years due to their excellent properties.

However, these fluorine-containing resin paints use a polytetrafluoroethylene travel base that is insoluble in organic solvents, so they must be heated above the melting temperature of polytetrafluoroethylene, making them difficult to use as room-temperature curing paints. Cannot be used.

Copolymers with vinyl ether have been proposed to improve upon these limitations, but the coating films obtained from these copolymers cannot be said to have sufficient antifouling properties.

(Means for Solving the Problems) The present invention provides a fluorine-containing resin antifouling paint to which a specific fluorine-containing block copolymer is added, as a solution to these conventional problems and antifouling without the use of chemicals. This is based on the knowledge that it exhibits excellent antifouling properties.

The present invention involves copolymerizing a polymeric peroxide or a polyazo compound with a fluorine-containing vinyl monomer or a fluorine-free vinyl monomer that forms a fluorine-containing polymer portion to contain a peroxy bond or an azo bond. The first step is to obtain a copolymer, and then the peroxy bond- or azo bond-containing copolymer obtained in the first step and, if a fluorine-containing vinyl monomer is used in the first step, a fluorine-free vinyl monomer. A second step of copolymerizing with a fluorine-containing vinyl monomer that forms a fluorine-containing polymer portion if a fluorine-free vinyl monomer is used in the first step. A fluorine-containing resin antifouling paint containing a fluorine-containing block copolymer obtained by.

The proportion of the fluorine-containing block copolymer in the solid content of the resin constituting the antifouling paint of the present invention is preferably 0.1 wt. 1% or more. This is because if the amount is less than 0.1% by weight, the antifouling properties will be insufficient.

Although the fluorine-containing block copolymer used in the present invention can impart antifouling properties even in such a small amount,
This is thought to be due to the fact that the fluoropolymer portions, which have a small intermolecular cohesive force and a significantly low surface tension, are oriented on the coating surface.

The type of paint to which the fluorine-containing block copolymer used in the present invention is added is not particularly limited, but the resin component constituting the paint and the vinyl monomer of the fluorine-containing block copolymer used in the present invention Preferably, the polymer moieties are compatible or miscible.

In particular, when using room-temperature curing paints such as acrylic resin paints and alkyd resin paints (including two-component reactive paints such as polyurethane resin paints and epoxy resin paints), the It does not require high-temperature baking, cures at room temperature, exhibits the characteristics of a fluorine-containing resin paint, and exhibits excellent antifouling effects.

In addition, by appropriately selecting the type of vinyl monomer in the fluorine-containing block copolymer, it can be mixed with various commonly used paint resins, making it easy to use as an antifouling paint. You can.

Furthermore, as constituent components of the fluorine-containing resin antifouling paint of the present invention, pigments such as coloring pigments and extender pigments, additives, organic solvents, etc. necessary for constructing ordinary paints can be blended.

The polymerization step of the fluorine-containing block copolymer is carried out as follows.

First, in the first step, when a polymeric peroxide or a polyazo compound is polymerized with a fluorine-free vinyl monomer or a fluorine-containing vinyl monomer,
A peroxy bond or an azo bond is introduced into the chain,
A so-called peroxy bond-containing copolymer or azo bond-containing copolymer is obtained. Next, in the second step, if a fluorine-containing vinyl monomer was used in the first step, a vinyl monomer that does not contain fluorine is added to these copolymers, or a vinyl monomer that does not contain fluorine is added to the copolymer in the first step. When a vinyl monomer is used, if a fluorine-containing vinyl monomer is added and polymerized, the peroxy bond-containing copolymer or azo bond-containing copolymer will be cleaved at the peroxy bond or azo bond contained therein. , a fluorine-containing block copolymer can be obtained with good soil effect.

In other words, in the second step, when the peroxy bond-containing copolymer or azo bond-containing copolymer obtained in the first step is a fluorine-free copolymer, the fluorine-containing polymer portion is removed in the second step. The fluorine-containing vinyl monomers to be formed are block copolymerized. Further, when the copolymer obtained in the first step is a fluorine-containing copolymer, it is necessary to block copolymerize a fluorine-free vinyl monomer in the second step.

Polymeric peroxides used in the synthesis of fluorine-containing block copolymers include those having the following structures represented by general formulas (I) to (■).

[In the formula, R represents an alkylene group having 1 to 18 carbon atoms, a substituted alkylene group, a cycloalkylene group having 3 to 15 carbon atoms, a substituted cycloalkylene group, a phenylene group, or a substituted phenylene group, and R3 is an alkylene group having 2 to 10 carbon atoms or a substituted alkyref group, -e-aH-aH2o -q R,- (wherein, R8 is a hydrogen atom or a methyl group, and R
6 is an alkylene group or substituted alkylene group having 2 to 10 carbon atoms. It also represents m=1 to 13), or. Further, n = Z~80. ] [In the formula, R
□ is the same group as R in the general L(I) above. R3 represents an ethylene group, a phenylene group, or an acetylene group. Further, n = Z~30. ] [In the formula, R is the same group as R in the general formula (4). Further, n=2 to 30. ] [In the formula, R is the same group as R in the general formula (I). Further, n = 2 to 30. ] [In the formula, R is the same group as Ro in the general formula (I). Also, n=2~
It is 30. ] [In the formula, X represents a hydrogen atom, a methyl group, or a chlorine atom.

Further, n=2 to 30. ] ・・・・・・・・・・・・(■) [In the formula, R is the same group as R in the above general formula (I). R8 represents an ethylene group, an acetylene group, or a phenylene group, and R6 and R6 represent a hydrogen atom or a methyl group. Moreover, n=2-30, m21-100.

] This is a compound represented by

The polyazo compound used in the present invention has the following structure represented by the general formula (C).

(VW) [In the formula, R represents the same group as R in the general formula (I), and R7 represents a methyl group or a cyan group. Also m
−0 to 1, n = 2 to 30. ] This is a compound represented by

Specific examples of the polymeric peroxide of the general formula (I) include (n2-3o in all formulas).

Further, specific examples of the polymeric peroxide of the general formula (II) include: h2+, ;a3 Uli3 UIi
3 (n=2 to 30 in all formulas).

Further, specific examples of the polymeric peroxide of the general formula (III) include the following: G)i30H3 (n22-3o in all formulas).

Further, specific examples of the polymeric peroxide of the general formula (IV) include (n=2 to 30 in all formulas).

Further, specific examples of the polymeric peroxide of the general formula (V) include (n=2 to 30 in all formulas).

Specific examples of the polymeric peroxide of the general formula (■) include Boshin, m=1 to 100, and n=2 to 3G. )
There's somewhere.

Examples of the polyazo compound of the general formula (vI) include (wherein m = 1 to 100 and n = 2 to 30).

Further, as the fluorine-containing vinyl monomer used in the present invention, there are, for example, those having the following structural formulas represented by general formulas ＠) to (XV).

OH= 0RICOOR2Rf ・−・・
( [ represents an alkyl group, and p is a positive number of 1 to 1O.) Ro represents a hydrogen atom or a methyl group, n is a positive integer of 1 to 16, and m k'il -10. ]
CH,=0RICOOR2(OF2),OR8...
...(X) [wherein, R3 is CmH2mCJF2A+1
group, or -CmH2mCA! F2JH group, R2 is an alkylene group represented by 10pH2p-, -CHOH
0-1R□ represents a methyl group, or a hydrogen atom, m is a positive integer of 0-10, and l is 0
~16 positive integer, p is a positive integer from 1 to IO, q is 1-
It is a positive integer of 10. ]OH= ORGOOR(OF
) H・・・・・・(Xl)2 1
2 2n [wherein, R2 is an alkylene group represented by -CrnH2rn-, 10R8H-, -CH2CR2H- (wherein, R3 is an alkyl group represented by CpH2p+, and p is a positive integer from 1 to 1O) ) Ro represents a hydrogen atom or a methyl group, n is a positive integer of 1 to 16, and m is a positive integer of 1 to 1O. ]0H=0RIC
OOR2NCORf =・−・(X[[)
[In the formula, Rf is a perfluoron represented by OF
Zn+10 alkyl group, R2 is an alkylene group represented by -CmH2m-, -0R3H--0H20R8H- (wherein, R8 is an alkyl group represented by CpH2p+1, and p is a positive integer from 1 to 10). , R is CH
an alkyl group represented by, R6 is water 4 q2q+
1 elementary atom represents a methyl group, n is a positive integer of 1 to 16, m is a positive integer of 1 to 10, and q is a positive integer of 1 to 10. ] CH2=CRICoOR2NSO2Rf...Song (XIl
[) [In the formula, Rf is a perfluoronn2n+10 alkyl group represented by OF; R2 is an alkylene group represented by -CmH2m-;
2p+1, where p is a positive integer from 1 to 10. ) R is an alkyl group represented by OH, R□ is water 4 q 2q
+1 represents an elementary atom or a methyl group, n is a positive integer of 1 to 16, m is a positive integer of 1 to 10, and q is a positive integer of 1 to IO. ) CH2-ORICoOR2R8...Song (X■) [In the formula,
R□ is a fluorine atom, CHF2 group, 0H2F group, CF, group, 0COCR2F group, or 0OOCHF 2 group, R2
is an alkylene group represented by -CInH2n1-, -0
R8H--0H2CRH- (wherein, R is an alkyl group 3 p
2p+1, where p is a positive integer of 1-10. ), R is OH
an alkyl group represented by or a perfluoroalkyl group represented by a q 2q+1 CrF2r+1,
or -(OF, ), H, where m is a positive integer from 1 to 10, q is a positive integer from 0 to 16, r is a positive integer from 1 to 16, and l is a positive integer from 1 to 16. It is. ]0RIR2= 0
R8R, ... song (xv) [in the formula, R engineering, R2, R8,
R is a hydrogen atom, a chlorine atom, a fluorine atom, a phenyl group,
It represents a substituted phenyl group, i or a perfluoroalkyl n 2n+1 group represented by cF 2 , and at least one of R to R2 is a fluorine-containing substituent. Moreover, n is a positive integer of 1 to 5. ] Specifically, the fluorine-containing vinyl monomer of the general formula (IX) is, for example, 0F3(CF, )70H20H20COCH=0H2
0F3(OF2), (EH20H2QC; 0C(OH3
) = 0H2CF30H2QC; OCH= CH2, etc.

Further, specific examples of the fluorine-containing vinyl monomer of the general formula (X) include 0F30H20CH20H20COCH= CH2HC
F20F20CR, 0H20 (30CH=OH.

02F5(OH20H20)20H20COCH=0
H208F□7ocn, aH,ococ(an3)=
0H2CF8(OF2), 0CH20H2QCOC(O
H8) = OH2, etc.

Further, specific examples of the fluorine-containing vinyl monomer of the general formula (XI) include H(OF,)80H20COOH= 0H2H(OF2
), CH20COCH= 0H2H(OF2)60H
2000G(OH8) =CH20F8(OF2) 3
There are 0FHOF20H, OCH=CH2, etc.

Further, specific examples of the fluorine-containing vinyl monomer of the general formula (XI[) include, for example, C9F,,GON(C2H,)CI(2000G(OH
a) = CH.

(32F5CON(G,H,)OH20COCH=C
H20F8(OF!S) 2GON(OH8)OH(C
:H,)OH20COCH= 0H2CH, (OF2)
7CON(OH2C)i20H8)OH20H20CO
Examples include C(OH3)20H2.

Further, specific examples of the fluorine-containing vinyl monomer of the general formula (XI) include OF, (OF, )7802N(OH8)OH20H20
00G(OH3) =CH.

CF3(OH2')7So2NCCH3)CH2CH2
0COCH=CH208F, 5o2N(OH3)(O
H2). 0COCH= CH2OF So N(CH
)OHOH000G(OH3) =OH2c8r, 7s
o□N(OH8)(OH2), CIC0CR=CH20
2F, 802N (C8H7) OH20H2000C (O
H8') = CH202F, So, N(02H,)C
(02H,)HGH20COCH=CH2, etc.

Further, the fluorine-containing vinyl monomer of the general formula (XIV) is specifically, for example, 0H30COCF = CH2 F0H20H20COF2CH2 C2H,0000(CiH,F) = 0H20H,0
000(OHF,) = CH2C3H70COC(C
F8) = CH2 CH80COC (OCOCiH2F) = 0H2C2
Sweet, 0OOC (OCOCH2F) = OH208F, 70
000 (CF8) 20H2O8F, 0000 (OCOC
H2F) = CH2He, F6000CF = OH
2 etc.

Further, specific examples of the fluorine-containing vinyl monomer of the general formula (XV) include OCl=CFGl, C,FQl=GFC1,
0F2=GC12゜CCIF=CF, C, F2=
OF3.0HC6=CFO1.

CHF=CHF, 0HCIl=OF2. CH
F=CHF.

CTiF=CF, CHF=(3HC1,0H2=
OOlF.

CHF=CHF, OH,=(3F, 2.0H2=C
FH.

CF2=G(CF3), , OF, -CF=OF,
, 0F8-GH=CHF.

CF-CH=CH2,03F7(C)18)CH2CH
2゜0F OF CF=CCC,F ), (CF
8) 20FCF=CF-OF.

3 2 3g and so on.

Specific examples of the fluorine-containing vinyl monomer forming the fluorine-containing polymer portion are as shown above, and one or more of these are used as the main component of the fluorine-containing vinyl monomer, Fluorine-containing vinyl monomers or vinyl monomers other than the above-mentioned main components can also be added within the range in which the characteristics of the fluororesin antifouling paint can be exhibited.

Examples of the vinyl monomer used in the present invention include methyl (meth)acrylate [methyl (meth)acrylate refers to methyl methacrylate or methyl acrylate. Same below. ], lower alkyl (meth)acrylates such as ethyl (meth)acrylate, n-furovir (meth)acrylate, isopropyl (meth)acrylate, and glycidyl (meth)acrylate; n-butyl (meth)acrylate; Isobutyl (meth)acrylate, tert-butyl (meth)acrylate, (meth)a') '
) Higher alkyls such as n-hexyl, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate (
meth)acrylate; lower fatty acid vinyl esters such as vinyl acetate and vinyl propionate; higher fatty acid vinyl esters such as vinyl butyrate, vinyl caproate, vinyl 2-ethylhexanoate, vinyl laurate, and vinyl stearate; styrene, vinyl toluene, Aromatic vinyl type monomers such as vinylpyrrolidone; Vinyl type monomers containing amide groups such as (meth)acrylamide, N-methylol (meth)acrylamide, N-methoxymethyl (meth)acrylamide; (meth)acrylic acid hydroxy ethyl,
Hydroxyl group-containing vinyl monomers such as hydroxypropyl (meth)acrylate and allyl alcohol; Carboxylic acid group-containing vinyl monomers such as (meth)acrylic acid, itaconic acid, crotonic acid, fumaric acid, and maleic acid; butadiene ;
Vinyl chloride; vinylidene chloride; (meth)acrylonitrile; dibutyl fumarate; maleic anhydride; dodecyl succinic anhydride; (meth)allyl glycidyl ether; radically polymerizable unsaturated carboxylic acid such as itaconic acid, (meth)acrylic acid, crotonic acid, etc. Alkali metal salts, ammonium salts, and organic amine salts of acids; radically polymerizable unsaturated monomers having sulfonic acid groups such as styrene sulfonic acid, and their alkali metal salts, ammonium salts, and organic amine salts; 2-hydroxy - Quaternary ammonium salts derived from (meth)acrylic acid, such as 8-methacryloxibu alpha pyrutrimethylammonium chloride; (meth)
Examples include (meth)acrylate esters of alcohols having a tertiary amine group, such as diethylamine acrylate ester, and quaternary ammonium salts thereof.

One or more of these vinyl monomers are used as the main component of the vinyl monomer.

Furthermore, in order to improve the compatibility, miscibility and crosslinking reactivity between the fluorine-containing block copolymer and the coating resin, vinyl monomers other than those mentioned above may be added.

The peroxy bond-containing copolymer or polyazo bond-containing gold copolymer used in the present invention is a polymeric peroxide represented by the general formulas (I) to (■) or the general formula (■).
It can be easily obtained by polymerizing a vinyl monomer or a fluorine-containing vinyl monomer using a polyazo compound represented by the formula by ordinary solution polymerization or non-aqueous polymerization.

In this case, the amount of the polymeric peroxide or polyazo compound used is 0.5 to zO parts by weight per 100 parts by weight of the vinyl monomer or fluorine-containing vinyl monomer, and the polymerization temperature is 60 to 130" C1 polymerization. Time is 2-10
It takes about an hour. In this case, the polymeric peroxide or polyazo compound used is one or two of them.
A mixture of more than one species can be used.

In addition, the polymerization temperature of block copolymerization reaction is 60~140''
C. The polymerization time is about 3 to 15 hours, and the fluorine-containing block copolymer is obtained as a solution or a non-aqueous liquid.

Further, a preferable weight ratio of the fluorine-free polymer portion and the fluorine-containing polymer portion in the fluorine-containing block copolymer is 1/19 to 19/1.

If the fluorine-containing polymer portion is less than 1/19, the antifouling effect of the fluorine-containing resin antifouling paint containing this fluorine-containing block copolymer will not be sufficiently expressed, and if it exceeds 19/1, it will not contain fluorine. Too little polymer moiety reduces compatibility or miscibility with coating resins.

(Effects of the Invention) The fluorine-containing resin antifouling paint of the present invention can be used on seawater contact surfaces of structures and equipment that come into contact with seawater, such as ships, marine structures, power plant cooling water systems, etc. Also air spray painting, airless spray painting, dipping painting,
Commonly used methods such as brush painting can be used, and no special coating method is required. The objects to be coated include iron, zinc, aluminum, brass, titanium, ceramic, concrete,
Can be painted on all kinds of materials including slate and plastic.

Hereinafter, the present invention will be explained in more detail with reference to production examples, examples, and comparative examples. In the text, unless otherwise specified, "parts" indicate parts by weight, and "%" indicates weight %.

(Example) Production Example 1 50 parts of methyl methacrylate and 125 parts of methyl ethyl ketone were charged into a reactor equipped with a thermometer, a stirrer, and a reflux condenser, heated to 70°C while blowing nitrogen gas, and polymerized for 3 hours. A clear solution of the peroxy bond-containing copolymer was obtained. Next, a mixture of 08F, 0H2CiH, 0GOCH=CH250 parts and 30 parts of methyl ethyl ketone was added dropwise to this solution at 70°C while blowing nitrogen gas over 0.5 hours, and a polymerization reaction was further carried out at 70°C for 5 hours. Solid content 40.2%, viscosity (25°C) 2.
A 5 poise white polymer dispersion (A) was obtained.

Production Example 2 Into the same reactor as Production Example 1, 42 parts of methyl methacrylate, 8 parts of 2-hydroxyethyl methacrylate, 8 parts of Φ part, 125 parts of methyl ethyl ketone were charged, heated to 70''C while blowing nitrogen gas, and polymerized for 3 hours. The reaction was carried out to obtain a transparent solution of the peroxy bond-containing copolymer.Next, at 70°C while blowing nitrogen gas,
To this solution was added a mixture of 250 parts of 08F, 0H2CH2000C:H-CH and 15 parts of methyl ethyl ketone.
．． It was added dropwise over 5 hours, and the polymerization reaction was further carried out at 70°C for 5 hours, resulting in a solid content of 42.6% and a viscosity (at 25°C) of 3.3.
A white polymer dispersion (B) was obtained.

Furthermore, a fluorine-containing block copolymer dispersion C-H having the composition shown in Table 1 was obtained by the same manufacturing method.

Examples 1-51. Comparative Examples 1 to 6 The obtained fluorine-containing block copolymer dispersions A to H were added to commercially available paints in the formulations shown in Table 2, and the resulting fluorine-containing resin paints were mixed using a stirrer. Comparative Example 1 A commercially available paint containing no fluorine-containing block copolymer dispersion
~6. The same commercially available paint used in the actual Mfflj and comparative example was pre-applied as an anti-corrosion paint.
The coating was applied to a X20α mild steel plate using a brush to a coating thickness of 50 μm, and after drying, it was immersed 1.5 dips below the water surface from a raft in Yura Bay, Shumoto City, Hyogo Prefecture, to remove fouling organisms. The state of adhesion was observed.

The immersion test results are shown in Table 3.

Table 8 As is clear from the immersion results shown in Table 8, Example 1
-51 showed no deposits at all even after one year, whereas in Comparative Examples 1 to 6, half had deposits of 50% or more after one month, and all of them had deposits on the entire surface after nine months.

Therefore, the fluorine-containing resin antifouling paint of the present invention has an antifouling effect of 1.
It should be 00% complete. What's more, it was possible to prevent marine life from getting stuck without using any harmful substances. This can be said to be an innovative antifouling paint that does not cause environmental pollution. −

Claims (1)

[Claims] 1. Copolymerizing a polymeric peroxide or a polyazo compound with a fluorine-containing vinyl monomer or a fluorine-free vinyl monomer forming a fluorine-containing polymer portion to form a peroxy bond. Alternatively, the first step is to obtain an azo bond-containing copolymer, and then the peroxy bond- or azo bond-containing copolymer obtained in the first step, and when a fluorine-containing vinyl monomer is used in the first step, a fluorine-containing copolymer is used. If a vinyl monomer that does not contain fluorine is used in the first step, or a vinyl monomer that does not contain fluorine is used in the first step, a fluorine-containing vinyl monomer that forms a fluorine-containing polymer portion is used, and the first step to be copolymerized is 2
A fluorine-containing resin antifouling paint containing a fluorine-containing block copolymer obtained in the step.