JPS62290768A - Antifouling paint composition - Google Patents

Abstract

PURPOSE:To provide an antifouling paint compsn. which is nontoxic and has an excellent antifouling performance, containing a copolymer composed of a polymerizable unsaturated polysiloxane, a polymerizable unsaturated alkoxysilane and a polymerizable unsaturated vinyl monomer as a film-forming component. CONSTITUTION:1-50wt% polymerizable unsaturated polysiloxane (A) of formula I (wherein X1 is a group of formula II or III; R6 is H or methyl; R1, R2, R3, R4 and R5 are each a member selected from the group consisting of a 1-4C alkyl, etc.; a is 0 or a number of 1-5; and b is a number of 3-1,000) (e.g., a compd. of formula IV) is copolymerized with 0-30wt% polymerizable unsaturated alkoxysilane (B) of formula V (wherein X2 is a group of formula VI or VII; R8 is H or methyl; R7 is a 1-4C alkyl; and d is 0 or a number of 1-5) (e.g., vinyltrimethoxysilane) and 99-20wt% polymerizable unsaturated vinyl monomer (C) (e.g., methyl acrylate) other than the components A and B. The resulting copolymer is incorporated as a film-forming component to obtain the desired antifouling paint compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an antifouling paint composition, and more particularly to a nontoxic antifouling paint composition for preventing aquatic organisms from adhering to submerged parts of ships and marine relics.

Conventionally, submerged parts of ships and offshore structures have been painted with paints containing cuprous oxide and organic tin compounds, which have been highly effective in preventing aquatic organisms from adhering to them. There is a problem of environmental pollution due to the elution of toxic substances such as tin compounds from paint films, and therefore there is a demand for the development of non-toxic antifouling paints that do not contain toxic substances such as copper compounds and organic tin compounds.

However, in the past, non-toxic antifouling paints have also been proposed.
nd Its Prevention
olis, Maryland: U,S,Nava
RlE, Baler et al. (1952) suggests that paraffin and wax may be used as non-toxic antifouling paints.
Announcement [ProSpect for N onto
xic Fouling Resistant Pa
1ntsJProc.

Annu, Conf, Mar, Techno
gy Sac, (1973) suggests that antifouling properties can be imparted to the surface of a substrate by providing a coating surface containing a mixture of methyl groups and hydroxyl groups.

Additionally, U.S. Patent No. 3,702.778, 4°09
Non-toxic antifouling paints are also disclosed in No. 8.925 and No. 4.234, 340, but both have antifouling performance that is inferior to conventional antifouling paints containing cuprous oxide or organic tin compounds. The reality is that there is still room for improvement.

Therefore, the present inventors developed a non-toxic type antifouling paint that does not contain toxic substances such as metal compounds and organic metals that cause R environment pollution, and whose antifouling performance is comparable to conventional antifouling paints containing toxic substances. As a result of intensive research to develop antifouling paints, we found that the tendency of aquatic organisms to adhere to paint films is that the lower the surface energy of the paint film, and the less polar components there are in the paint film, the more likely water droplets will form on the paint film surface. We discovered that the surface of the paint film, where water droplets tend to fall when dropped, is difficult for organisms to adhere to, and even if organisms do adhere to it, the adhesion force is weak, and we developed a specific paint film-forming component that meets this purpose. This led to the completion of the present invention.

Thus, according to the invention: (A) in the general formula, Xl is a group of the formula CH2=C- or CH2=C-COO-;
Here, R6 represents a hydrogen atom or a methyl group); R,, R2, R1 and R1 are the same or different and each represents an alkyl group, an aryl group or a 7-ralkyl group having 1 to 4 carbon atoms; Rs represents a furkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 6 carbon atoms having 1 to 3 hydroxyl groups; O when representing a group of
R1 is a polymerizable unsaturated polyester represented by A'), X is an integer of 1 to 5; Siloxane compound 1 to 50% by weight ([3) In the general formula, R, R.

X 2 C-formula CH2= C-also 1i CI! 2 = C
-Coo-(7) J&(Co'::-te, R6 represents a hydrogen atom or a methyl group); R7 represents an alkyl group having 1 to 4 carbon atoms; d represents X2 with the formula CH, =OR to express the likelihood of C-.

and when X2 represents a group of the formula CIl□=C-COO-, the number of grams is from 1 to 5.
Forming a film with a vinyl copolymer obtained by copolymerizing 0 weight percent and (C) 20 to 99 weight percent of a polymerizable unsaturated vinyl monomer other than the compounds of (A) and (B) above. Provided is an antifouling paint composition containing the following components.

The antifouling coating composition of the present invention does not elute toxic substances into water, the coating film formed from it has low surface energy, and water droplets easily fall on the coating surface, so it has excellent antifouling properties. Even if it adheres, it can be easily removed, and it exhibits antifouling performance comparable to conventional antifouling paints that elute toxic substances such as metal compounds and organic metals.

In the present specification, the "alkyl group" may be either linear or so-branched, such as methyl, ethyl, n-propyl, 1so-propyl, n-butyl, 5ee-butyl. , 1so-butyl, ters-butyl, n-pentyl, n-hexyl, and the like.

Further, the "aryl group" includes a phenyl group, tolyl group, xylyl group, naphthyl group, etc., and the [-aralkyl group] includes pennol group, 7enethyl group, etc.

Hereinafter, the main components constituting the antifouling paint composition of the present invention will be specifically explained.

(8) The polymerizable unsaturated polysiloxane compound (△) which is a constituent component of the vinyl polymer in the antifouling paint composition of the present invention is represented by the following general formula, X4, R1 , R2, R3, R4, R5, a and b
has the meaning of 11; I, and has a polymerizable vinyl group at the end of the terminal.

It is a polysiloxane compound having (CI+,=C-).

In the above formula (1), ■ri1, R2, [ri, and Rt
are the same or different, and each carbon atom I! 1.1
~4 alkyl groups, 7-aryl groups, or aralkyl groups, but alkyl groups, especially methyl groups, are preferred because they minimize the surface energy of the coating film formed from the vinyl copolymer.

R5 is an alkyl group having 1 to 4 carbon atoms or 1 hydroxyl group
It represents a hydroxyalkyl group having 1 to 6 carbon atoms, and the latter hydroxyalkyl group is more preferred. The reason for this is that in the case where R3 represents the hydroxyalkyl group, the coating composition of the present invention has the above-mentioned R, E, B
Coating B with a mixture of methyl and hydroxyl groups proposed by a1er! ,! This is because it provides a surface. Such hydroxyalkyl groups include, for example, hydroxymethyl,
2-hydroxyethyl, 1-hydroxyethyl, 1゜2
-hydroxyethyl, 3-hydroxypropyl, 2.
3-nohydroxypropyl, 1,2,3-trihydroxypropyl, 4-hydroxybutyl, 3,4-dihydroxybutyl, 5-hydroxypentyl, 11,5-nohydroxybentyl, 4,5-dihydro-4 -methyl-pentyl, 4,4.5-)lyhydroxybentyl, and the like.

H6 Furthermore, when Xl represents a group of the formula CH2=C-, a
is 0, i.e. the group is bonded directly to Si without -(-CH, ←-), while Xl is preferably an integer from 2 to 4.

Furthermore, in the above formula (1), the siloxane unit is 0001
Preferably 30-500, more preferably 50-30
It is a number within the range of 0, and is a value determined by delper minision chromatography.

Therefore, specific examples of compounds suitable as the polymerizable unsaturated siloxane compound (A) include the following: In view of their ease of availability, compounds ① and ① are particularly preferred. be.

(B) u -ζ Alkoxysilane A In the present invention, the polymerizable unsaturated alkoxysilane compound (B) which can be a synthetic compound of the vinyl copolymer is the following general formula, where X2, R7 and d are the above-mentioned It is a flukoxysilane compound containing a polymerizable vinyl group (C11□=C-) represented by R1.

In the above formula (n), among the alkyl groups having 1 to 4 carbon atoms represented by R, a methyl group is most preferable, and when X2 represents a group of the formula Cl2=C-, d is 0. i.e., the group is directly bonded to the Si atom in the formula, while when X2 represents a group of the formula CH,=C-COO-, d is an integer from 1 to 5, preferably from 2 to 4.

Therefore, specific examples of the polymerizable unsaturated alkoxysilane compound (B) of the above formula (II) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriethoxysilane, (meth)acryloxysilane, Methyltrimethoxysilane, (meth)acryloxyethyltrimethoxysilane, (meth)acryloxypropyltrimethoxysilane, (meth)7cryloxyprobyltriethoxysilane, (meth)acryloxyethyltriethoxysilane, (meth) Examples include acryloxypropyltriptoxysilane. Particularly preferred among these is (meth)acryloxypropyltrimethoxysilane.

(C) Mu・Japanese vinyl, 1 As the polymerizable unsaturated vinyl monomer (C) other than the above-mentioned compounds (A) and (B), which are the constituent components of the vinyl copolymer in the present invention, There is no particular restriction as long as it radically polymerizes with the compound (A) and/or (8) above to give a film-forming polymeric substance, but in general, radically polymerizable a, β-ethylene is used. Compounds containing one or two, preferably one, sexually unsaturated bond are suitable.

Specific representative examples of such polymerizable unsaturated vinyl monomers (C) include the following: (a) (meth)
Methyl acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, impropyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ( (meth)acrylic acid C1~+□ alkyl ester such as octyl meth)acrylate, lauryl (meth)acrylate; (b) 2-hydroxyethyl (meth)acrylate, (
(meth) aphryl C2-B hydroxyalkyl esters such as 2-hydroxypropyl acrylate; (C) glycidyl-containing vinyl monomers such as glycitul (meth) 7 acrylate, allyl glycitulu ether; (d) (meth) ) Carboxyl-containing vinyl monomers such as acrylic acid, itaconic acid, and crotonic acid; (e) (meth)acrylic acids C2~ such as allyl (meth)acrylate;
, alkenyl esters; (r) Vinyl aromatic compounds such as styrene, α-methylstyrene, and vinyltoluene; <iz> Others: (meth)acrylonitrile, (meth)acrolein, butadiene, isoprene, etc.

These polymerizable unsaturated vinyl monomers can be used individually, or two or more kinds can be used in combination. Among the above vinyl monomers, particularly preferred ones include ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and styrene.

The above-mentioned polymerizable unsaturated polysiloxane compound (A), polymerizable unsaturated alkoxysilane compound (B) and polymerizable unsaturated vinyl monomer (0 represents the present invention by copolymerizing with each other) A vinyl copolymer is used.The proportions of each of the components (A), (B), and (C) mentioned above can be as follows.

(8) 1-50 5-30
8-20 (B) 0-30 3-15
5-10 (C) 20-9955-9270-8
7% by weight is a weight percentage based on the total amount of the three components (A), (B), and (Q).

The above copolymerization can be carried out in an inert organic solvent according to radical polymerization methods known per se. Examples of Aiso solvents that can be used in copolymerization include ethyl acetate,
Esters such as butyl acetate; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; alcohol solvents such as isopropyl alcohol and butamele; or two or more of these solvents. Mixtures of the above may be mentioned. In addition, as a radical polymerization initiator,
Examples include polymerization initiators commonly used in radical polymerization, such as benzoyl peroxide, azobisisobutyronitrile, lauroyl peroxide, and cumene hydroperoxide.

The above copolymerization reaction is usually carried out over a period of about 80 to about 200' (:,
Preferably, it can be carried out at a temperature of about 100 to about 120 DEG C., and can be allowed to stand for about 2 to 20 hours, preferably 5 to 10 hours, under harsh conditions.

The vinyl-based copolymer thus left behind generally has a gJ of about 3,000 to about 200,000. Weight M'l/- preferably within the range of about 5,000 to about 100,000
It has a uniform molecular fit (Mw) and also -30-1
It is preferable to have a glass transition temperature (Tg) in the range of 00°C1, preferably -10 to 30°C.

Sky 1 Ju branch first! The coating composition of the present invention can be prepared by dissolving or dispersing the vinyl copolymer produced as described above in an appropriate solvent.

Solvents that can be used to prepare the coating composition include those that are relatively volatile at room temperature, such as ketone solvents such as acetone and methyl ethyl ketone; ester magents such as ethyl acetate and butyl acetate; Aromatic hydrocarbon solvents such as benzene, toluene, and silene; Alcohol solvents such as isopropyl alcohol and butyl alcohol;
Examples include petroleum solvents such as mineral spirit and aromatic petroleum naphtha; or mixed solvents of two or more of these solvents.

In addition to the above-mentioned vinyl copolymer, the coating composition of the present invention further contains an alkyl group having 1 to 4 carbon atoms, in which R2°, R11%, R2 and R13 are the same or different, and each has 1 to 4 carbon atoms. represents a group, an aryl group, or an aralkyl group; p is an integer of 1 to 5; q is a number of 3 to 1, OOO; This can further improve the antifouling performance of the coating composition.

In the above formula (III), R1°, R1, R12 and (
/R, co are each preferably a methyl group, p
is preferably in the range of 2 to 4, and q is preferably in the range of 30 to 500, particularly 50 to 300 for the siloxane compound.

Therefore, specific examples of the siloxane compounds of the above formula (III') include those of dogs: q' = 30 to 500 These siloxane compounds of the formula (Ill) can be prepared by adding 100 parts by weight of the above-mentioned vinyl copolymer. generally 1 to 50 parts by weight,
Preferably 5 to 30 parts by weight, more preferably 8 to 20 parts by weight
Conveniently, they are incorporated in parts by weight.

The coating composition of the present invention may further contain conventional coating additives, such as coloring pigments (e.g., benzene, subsynthesis, titanium oxide, yellow lead, etc.), extender pigments (e.g., talc, clay, etc.), as necessary.
Calcium carbonate, etc.), anti-rust pigments (e.g. red lead, zinc chromate, lead chromate, etc.), plasticizers (e.g. tricresyl diphosphate, chlorinated paraffin, heptatarate, etc.)
, an anti-sagging agent (eg, fine silica, aluminum stearate, zinc stearate, etc.) may be added in amounts within commonly used ranges.

31 of the antifouling paint product of the present invention! The preparation can be carried out by mixing and dispersing the above-mentioned components in the above-mentioned solvent using a dispersion device such as a ball mill or attritor.

The amount of the vinyl copolymer according to the present invention in the composition is not strictly limited, and can be varied over a wide range depending on the type and location of the substrate to be coated. , generally speaking, 1 based on the weight of the composition.
It can be in the range of 5 to 70% by weight, preferably 30 to 50% by weight.

#1 Item 1 The antifouling coating composition provided by the present invention has a small sliding friction angle and critical surface tension of the coating film, and has excellent resistance to adhesion of organisms in contact with water, as evidenced by the examples described below. It is resistant to dirt, and its antifouling performance is 8 times higher than that of conventional metal compounds! It is equivalent to or even better than antifouling paints that elute toxic substances such as metals. In addition, the antifouling paint composition of the present invention can be easily removed even if aquatic organisms adhere to it, making it extremely excellent as a non-toxic antifouling paint.

However, the antifouling paint composition of the present invention can be applied to various types of ships, underwater and above-water fJ! It can be used to paint submerged parts of objects (e.g. cutting ribs, floating docks, water gates, buoys, etc.).

The present invention will be further explained below with reference to Examples, but it should be understood that the present invention is not limited only to the Examples, and that various modifications can be made within the scope of the invention. . In addition, parts and % in Examples and Comparative Examples indicate parts by weight and % by weight unless otherwise specified.

Vinyl system - [Production of human body] 1 In a reaction vessel, 40 parts of methacryloxypropyl polymethylsiloxane methyl methacrylate and 40 parts of n-butyl methacrylate were dissolved in 67 parts of a mixed solvent of xylene/butyl acetate = 8/2, Add 1.0 part of benzoyl peroxide and react at 90 to 100°C for 6 hours with stirring.
A vinyl copolymer solution having a weight average molecular weight of 30.0 (60%, O and 1 solids content) was obtained.

Production of vinyl-based A゛12 In a reaction vessel, 20 parts of methacryloquine brobyl 4,5-nohydroxy-4-methylpentylpolydimethylsiloxane, 2 parts of methacryloxypropyltrimethoxysilane
0 parts, 40 parts of inbutyl acrylate and 20 parts of Nested Reno
was dissolved in 67 parts of a mixed solvent of xylene/butyl acetate = 8/2, and 0.5 parts of azobisisobutyronitrile was added thereto and reacted at 90 to 100°C for 6 hours with stirring to obtain Tg-1.
0℃, weight average molecule! i45,000 and solids content 60%
A vinyl copolymer solution was obtained.

Roasted ball clay 1 clear) LIA delivery ↓ Methacryloxypropyl polys J used in Production Example 1
J-11, 30 parts of methacryloxypropyltrimethoxysilane and 40 parts of L-butyl methacrylate were polymerized in the same manner as in Production Example 1 to obtain 7g3
0. Obtain a vinyl copolymer solution with a weight average molecular weight i of 30,000 and a solid content of 60%.

In a reaction vessel, 10 parts of acryloxypropylborinomethylsiloxane, t-
butyl methacrylate) 30 ff1s and butyl methacrylate) 30 parts xylene/butyl acetate -8 parts 2
It was dissolved in 67 parts of a mixed solvent, 1.0 part of azobisisobutyronitrile was added, and the mixture was reacted for 6 hours at 100-110'C.
gl,! °C1l! ! i average molecule f130 , 0()(
) and a solid 'I) 609b vinyl copolymer solution.

Example 1 80 parts of the vinyl copolymer solution obtained in Production Example 1, Elonorl $200 (Crystalline SiO2 fine powder manufactured by Degussa, Germany) 0
．． 5 parts and 19.5 parts of xylene were mixed and dispersed with a paint conditioner to obtain an antifouling paint composition of the present invention. The coating film performance test results are shown in Table 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.
Shown below.

Comparative Examples 1 to 4 Antifouling paint compositions were prepared in the same manner as in Example 1 with the following formulations.
It was manufactured by fIJ4. The coating film performance test results are shown in Table 2 below.

Comparative Example 1> Vinyl chloride resin 10.0 (parts) Rosin 10.0 Triclenorphos 7ate 4.0 Triphenyltin fluoride 10.0 Talc
5.0 Pen handle 5.
0 Kijirol 28.0 Methyl isobutyl ketone 28.0 Total 100.0
(Parts) Comparative Example 2> Chlorinated rubber U4 fat 5.0 (parts) Rosin 15.0 Tricresyl phosphate 7ate 4.0 Cuprous oxide
30.0 talc
5. O (Part) Barita
3.0 Pen handle 4.0 Kijiroll 34.0 Total 100.
0 (#) Comparative Example 3> Vinyl chloride! f-fat 5.5 (parts) Rosin 5.5 Tricresylphos7ate 2.0 Cuprous oxide
30.0 Triphenyltin hydroxide 10.0 Barium sulfate 4.0
Tal 2 11.0 (parts) Red Garla 10.0 Kijiroll
11.0 Methyl isobutyl ketone 11.0 #t 100.0 (parts) Comparative example 4> Room temperature curing silicone resin 50 (parts) N silole 50 total 100
(Part) Evacuation The paints obtained in Examples 1 to 8 and Comparative Examples 1 to 4 above were applied to a sandblasted copper plate measuring 100,100 x 300 x 2 with zinc epoxy shop primer (dry film 115
A test plate was prepared by coating a coated board with epoxy anticorrosion paint (200μ) and epoxy anticorrosion paint (200μ) to give a dry thickness of 50μ, and after drying for 7 days, it was tested.

(1) Water droplet sliding test Place a 0.03 ml water droplet on the coating film, gradually raise it to 1ya, and measure the angle of the coated plate at which the water droplet begins to slide.

(2) Measurement of critical surface tension The contact angle between water and paraffin droplets is measured to determine the critical surface tension of the coated surface.

(3) The antifouling test board was immersed in Toba Bay, Mie Prefecture, for 12 minutes, and the state of adhesion of organisms was sub-inspected. Values are in % of the attached area.

Table 2 As is clear from Table 2, the antifouling paint composition of the present invention exhibits performance comparable to that of conventional paints using suboxide steel and organic tin.

Claims (1)

[Claims] 1. (A) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) In the formula, X_1 is a formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ Numerical formulas, chemical formulas, tables, etc. represents a group ▼ (where R_6 represents a hydrogen atom or a methyl group); R_1, R_2, R_3 and R_4 are the same or different and each represents an alkyl group having 1 to 4 carbon atoms, an aryl group, or represents an aralkyl group; R_5 represents an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 6 carbon atoms containing 1 to 3 hydroxyl groups; , tables, etc. When representing the group ▼, it is 0, and when X_1 represents the group ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, it is an integer from 1 to 5; b is 3 to 1,000. A polymerizable unsaturated polysiloxane compound represented by 1 to 50, which is the number of
Weight% (B) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) In the formula, X_2 is the group of the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. Here, R_6 represents a hydrogen atom or a methyl group; R_7 represents an alkyl group having 1 to 4 carbon atoms; d represents a group where X_2 is the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Sometimes it is 0, and when X_2 represents a group of the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, it is an integer from 1 to 5.
0% by weight and (C) 20 to 99% by weight of a polymerizable unsaturated vinyl monomer other than the compounds (A) and (B) above. An antifouling paint composition characterized by containing: