JPS61296076A - Antifouling coating compound composition - Google Patents

Abstract

PURPOSE:The titled composition of nontoxic from preventing marine organisms from attaching themselves to under water parts of ships and marine structures, comprising a vinyl copolymer containing a specific polymerizable alkoxy-silane and acrylate compound and hydroxyl group-containing silicon compound. CONSTITUTION:The aimed composition comprising (A) a vinyl copolymer containing (i) 1-50wt%, preferably 5-30wt% (meth)acryloxyalkyltrialkoxysilane compound and/or vinyltrialkoxysilane compound and (ii) 0-50wt%, preferably 5-30wt% perfluoroalkyl group-containing (meth)acrylate compound and (B) a hydroxyl group-containing silicone compound shown by the formula (R is 1-4C alkyl or aryl; a is 1-6 integer; b is 3-200).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an antifouling paint composition, and more particularly to a non-toxic antifouling paint composition for preventing the adhesion of marine organisms to sunken parts of ships and offshore structures. .

Although it is highly effective in preventing the adhesion of marine organisms, there is the problem of environmental pollution caused by steel and organic tin compounds, and the development of non-toxic antifouling paints that do not contain organic metals such as copper and tin compounds is needed. It is requested.

Therefore, the present inventors conducted extensive research to develop a non-toxic antifouling paint that does not contain metal compounds or organic metals that cause environmental pollution. found that the lower the surface energy of the paint film, and the less polar components there are in the paint film, the easier it is for water droplets to fall on the paint film surface. The invention has been completed by developing specific binder components that meet the objectives.

Therefore, according to the present invention, (4) 1 to 50% by weight of a (meth)acrylooxyalkyltrialkoxysilane compound and/or a vinyltrialkoxysilane compound and 0 to 50% by weight of a (meth)acrylate compound containing a perfluoroalkyl group. A vinyl-based copolymer containing % as an essential monomer component, and
aryl ) group, a represents an integer from 1 to 6, and b represents a numerical value from 3 to 200) An antifouling paint composition characterized by containing a hydroxyl group-containing silicon compound represented by .

According to the antifouling coating composition of the present invention, the coating film formed therefrom has low surface energy, and has excellent antifouling properties because water droplets easily fall on the surface of the coating film. It is possible to remove it. Hereinafter, two main components constituting the antifouling paint composition of the present invention will be specifically explained.
The (meth)acryloxyalkyltrialkoxysilane compound which is a constituent component of 4) has the following general formula % formula % (1) (where R1 represents a hydrogen atom or a methyl group, and R2 represents a carbon number of 1 to 4). represents an alkyl group, and represents an integer from 1 to 5) Compounds represented by the following can be advantageously used, specific examples of which include (meth)acryloxymethyltrimethoxysilane, (meth)acryloxyethyltrimethoxysilane ,(
Examples include meth)acryloxypropyltrimethoxysilane, (meth)acryloxypropyltriethoxysilane, (meth)acryloxyethyltriethoxysilane, and (meth)acryloxypropyltriptoxysilane. Among these compounds, when R2 in the formula (1>) becomes an alkyl group having 3 or more carbon atoms, the reactivity between alkoxy and a hydroxyl group-containing silicon compound (Mari's hydroxyl group decreases, so R2 is more preferably a methyl group or a hydroxyl group). l is an ethyl group.

-1, in the above formula (1)! When , is 0, the stability of the compound is poor, while when it is 6 or more, the reactivity of the alkoxy group decreases, so it is usually an integer of 1 to 5, preferably 1.
It is an integer of ~3.

Next, as vinyltrialkoxysilane compounds, there are compounds represented by the following general formula % (in the formula, R2 represents the above-mentioned meaning). Examples include vinyltripropoxysilane and vinyltriptoxysilane. R2 in the above formula (iris) is the above formula (1)
As in the case of the compound, it is preferred that = 5- methyl group and ethyl group.

Mata, perfluoroalkyl group-containing (meth)acrylate
The B1 compound can be represented by the following general formula % formula % (1) (wherein R1 represents the above meaning, m represents an integer from 1 to 5, and n represents an integer from 1 to 21). Example A - B2-Perfluorobutylethyl methacrylate C)13 CH2=C-COO-CH2CH2-C4F B2-Perfluorobutylethyl acrylate CH2=C-C0
O-CH2CH2-C4F82-perfluorooctylethyl acrylate CH2=CH-C0O-CH2CH
2-C8F172-Perfluorooctyl ethyl methacrylate H3 CH2=C-C0O-CH2CH2-C8F172-perfluorooctyl methacrylate CH3 CH2=CCoOCH2CH2-C3F172-perfluorononylethyl methacrylate H3 CH2=C-Con-CH2CH2-(CF2)8
CF 32-Perfluoroisononylethyl methacrylate CF3 2-Perfluoroisononylethyl acrylate F3 CH2-CT(-COO-CH2CH2-(CF2)
6CFCF3 2-perfluorodecylethyl methacrylate H3 CH2=C-COO-CH2CT (2-C10F21, etc.).

Among the compounds represented by the formula (1), compounds with an m value of 0 are unstable and easily hydrolyzed, and compounds with a value of 6 or more have a small effect of lowering the surface tension of the coating film, so they are preferred. Compounds Nos. 1 to 5 are listed below.

Ota n no Yuke 1 to 21 can be used, but n
Even when the number is 10 or more, there is no difference in the effect of lowering the surface tension of the coating film, and from the viewpoint of cost, compounds with n of 1 to 9 are preferred.

The vinyl polymer (A) used in the present invention contains the above-described (meth)acrylooxyalkyltrialkoxysilane compound and/or vinyltrialkoxysilane compound in an amount of 1 to 50% by weight, preferably 5 to 30% by weight, and A conventionally known method is carried out by adding a polymerizable unsaturated vinyl monomer as necessary to a mixture consisting of 0 to 50% by weight of a perfluoroalkyl group-containing (meth)acrylate compound and preferably 5 to 30% by weight. It is produced by copolymerizing with.

Examples of the above-mentioned polymerizable unsaturated vinyl monomers include:
Methyl (meth)acrylate, Ethyl (meth)acrylate, Propyl (meth)acrylate, Isopropyl (meth)acrylate, Butyl (meth)acrylate, Hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate , (meth)acrylic acid alkyl esters such as octyl (meth)acrylate and acrylic (meth)acrylate;
Acrylic unsaturated monomers such as glycidyl (meth)acrylate; (meth)acrylic acid; allyl (meth)acrylate; unsaturated monomers other than those listed above; tristyrene, a
-Methyphrestyrene, vinyl) luene, acrylonitrile, methacrylaterile, acrolein, methacrolein, butadiene, isoprene, and the like.

However, monomers containing hydroxyl groups as polymerizable unsaturated vinyl monomers cannot be used because they will react with the alkoxy groups of (meth)acryloxyalkyltrialkoxysilane compounds and vinyltrialkoxysilane compounds. .

The vinyl polymer used in the present invention has a number average molecular weight of about 3.000 to about 1,000, preferably about 5.000 to about 50,000, and has a glass transition temperature. In the present invention, the temperature is in the range of -1()°C to 100°C, preferably -9°C to 30°C. The hydroxyl group-containing silico compound used (■, the following general formula % formula % (where R represents an alkyl group having 1 to 4 carbon atoms or an aryl group [7, a 1 to 6) Represents an integer, h is 3~
200) having primary hydroxyl groups at both ends, examples of which include C11s CHa -10 -.

In the hydroxyl group-containing silicon compound (B), if R in the general formula is an alkyl group having 5 or more carbon atoms, the stability of the compound is poor, and R is more preferably an alkyl group having 1 to 2 carbon atoms. If the value of t*, a is an integer of 7 or more, the reactivity with the vinyl polymer prisoner will be poor, and the value of t* and a is more preferably 1 to 1.
It is an integer of 3. Furthermore, the value of l) representing the number of repetitions of siloxane bonds is 3 to 20(), preferably 20 to 100.
If it is less than 3, the surface tension of the coating film will be lowered, and wI
The effect of lowering t friction is poor, and on the other hand, when it exceeds 200, the stability of the compound decreases.

The antifouling coating composition of the present invention comprises the above-mentioned vinyl polymer (
It is a combination of A) and a hydroxyl group-containing silicon compound (B), and the blending ratio is (0.5 to 140 PHR of component (B) to the λ component, preferably 5 to 50 PHR).
It is. (If the Bll component 1 ratio is less than 0.5 PHR, the surface energy effect of the coating film and the sliding effect of water droplets will be small. On the other hand, if it exceeds 140 PHR, the stability of the mixture will be poor.

The antifouling paint composition of the present invention improves the physical properties of the paint film due to the curing reaction of the (Anti) component < (A) Iff, the component itself, and the curing reaction of the recovered component with the (B ly2. component). The surface energy of the coating film is lowered by the optionally introduced perfluoroalkyl group.On the other hand, (1 component has primary hydroxyl groups at both ends, [if1 acts as a crosslinker with the alkoxy group, and the crosslinking reaction may proceed during film formation, but if necessary, it is also possible to crosslink the (A component and (l component) in advance by hot blending t7). This does not interfere with the effects of the present invention.The surface energy of the coating film formed from the resin component obtained by the crosslinking reaction of (A)[min and (l)component is greater than the surface energy of the coating film formed by (4)relative 1min only. Even if it becomes somewhat higher, it makes it easier for water droplets to fall on the membrane surface, thereby achieving both the antifouling property and the effect of reducing the adhesion of living organisms, which are the objectives of the present invention.

In addition to the composition of the present invention, the recovered material and (814), coloring pigments, anticorrosive pigments, plasticizers, anti-sagging agents, etc. can also be blended.

The present invention will be explained below with reference to Examples, but the present invention is not limited only to the Examples. Note that the numbers in Examples and Comparative Examples indicate parts by weight unless otherwise specified.

Production Example 1 of Production Examples MMA (methyl methacrylate) 60fSn to butyl methacrylate 20r and methacryloxypropifretrimethoxysilane 2 (1f was dissolved in xylene 67f, benzoyl peroxide 1.OV was added, and heated to 90 to 100°C with stirring. The reaction was completed by holding for 6 hours.

Example 1 80 parts of the vinyl copolymer solution obtained in Production Example 1 (solid content 6
0%), 4.8 parts of silicon compound represented by CH3CH3, Erosyl≠200
(manufactured by Degussa AG, West Germany) and 14.7 parts of xylene were mixed and dispersed using a paint conditioner to obtain an antifouling paint composition of the present invention. The results of the coating film performance test are shown in Hikari-2 below.

Examples 2 to 8 Antifouling paint compositions were prepared in the same manner as in Example 1 using the blending ratios shown in Table 1. The coating film performance test results are shown in Table 2 below.

Comparative Examples 1 to 4 Antifouling paint compositions were prepared in the same manner as in Example 1 with the following formulations. The coating film performance #t and test results are shown in Table 2 below.

Comparative Example 1 Vinyl chloride resin 10.0 (parts)
Rosin
10.0 Tricresyl phosphate 4.0 Triphenyltin fluoride 10.0 Talli

5.0 Bengara 5.0 Kijiroru 28.0 Methyl Reisoptil Gtone 28.0 Total 1 0
0.0 (parts) Comparative Example 2 Chlorinated rubber resin 5.0 (parts) Rosin
15. (1 tricresyl phosphate 4.0 cuprous oxide
3 (1,0 tarri)

5.0 (Part) Pari Ta

3.0 valve handle
4.0 total t o o, o (parts) Production example 2 of vinyl valve type &[ containing trialkoxysilane 40f styrene, 30% t-butyl methacrylate, 209731 perfluoropropylethyl methacrylate
and acryloxypropyltriethoxysilane 10f were dissolved in a mixed solvent of xylene 3397 and butyl acetate 341, azobisisobutyronitrile 0.7F was added, and the temperature was maintained at 100 to 110°C for 6 hours with stirring, and the fermentation period was completed 17 Just in case.

Production Example 3 Vinyl acetate 30F, vinyl chloride 20V, vinyltrimethoxysilane 107'El, and perfluorooctylethyl methacrylate 40F were dissolved in a mixed solvent of xylene 20V and butyl acetate 47F, and 12 and benzoyl peroxide 0.52 were added and stirred. The reaction was then maintained at 90°C to 100°C for 6 hours to complete the reaction.

Production Example 4 10f of t-butyl methacrylate, 20t1 of 1-butyl methacrylate, 30f of vinyltriethoxysila and 40f of perfluoromethylethyl acrylate were kept for 2Or of xylene and 47f of butyl acetate to complete the reaction.

The above copolymer was a pale yellow liquid and formed a good coating film upon evaporation of the solvent.

Comparative Example 3 Vinyl chloride resin 5.5 (Tokyo) Rosin
5.5 Tricresyl Phosphate 2.0 Cuprous Oxide
30.0 Triphenyltin hydroxide 10.0 Paricum sulfate
4.0 tal
1 1.0 (part)
Red Garla 10.0 Kijiroll
11.0 total 1 0 0.
0 (parts) Comparative Example 4 Room temperature hardening type silicone resin 50 (parts) Total 100 (parts) The paints obtained in Examples 1 to 8 and Comparative Examples 1 to 3 were treated with size 10 (IX3 (10 x 2 m sandblasting Zinc epoxy shop brimer (dry P) on steel plate
Jq 15 a) and epoxy anti-rust paint (Jq 15 a)
0μ) was applied to a coated board in advance so that the soft bullet thickness was 50μ, and the test board was dried for 7 days.

(1) Water droplet slipping test A 0.03 mt water droplet was placed on the coating film-H, and 1@ was gradually lifted to indicate the angle of the coated plate at which the water droplet would begin to slide.

(2) Critical surface tension side fixation W Measure the contact angle with #drops of wood and paraffin and measure the critical surface tension of the painted surface 17 lbs.

(3) Anti-fouling condition, 1 results The test board was immersed in Toba Bay, Sankyo Prefecture for 12 months, and the state of the needles of living things was investigated. Values are % adhesion.

Table-2 As is clear from Table-2, the antifouling paint according to the present invention is
It showed performance comparable to conventional paints using cuprous oxide and organic tin.

Claims (1)

Scope of Claims: (A) 1 to 50% by weight of (meth)acrylooxyalkyltrialkoxysilane compound and/or vinyltrialkoxysilane compound and perfluoroalkyl group-containing (
A vinyl copolymer containing 0 to 50% by weight of a meth)acrylate compound as an essential monomer component and (B) the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R has 1 to 1 carbon atoms) 4 alkyl group or aryl (
aryl) group, a represents an integer of 1 to 6, and b
represents a numerical value of 3 to 200) An antifouling paint composition characterized by containing a hydroxyl group-containing silicone compound.