JPH01152170A - Antifouling coating composition - Google Patents

Abstract

PURPOSE:To provide an antifouling coating compsn. having an excellent storage stability, an excellent coating film strength and a suitable water-solubility, by incorporating thereinto specified amts. of rosin and a specific copolymer containing units of an unsatd. monomer having a tertiary amino group. CONSTITUTION:3-80pts.wt. unsatd. monomer having a tertiary amino group (e.g., dimethylaminoethyl acrylate or N,N-dimethylacrylamide) are copolymerized with 97-20pts.wt. unsatd. monomer having no tertiary amino group (e.g., methyl methacrylate or styrene) to prepare a copolymer having a number-average MW of 3,000-200,000 and a glass transition point of -10-200 deg.C. 100pts.wt. said copolymer is blended with 5-100pts.wt. rosin to prepare a vehicle for an antifouling coating compsn., which is then blended with an antifouling agent adapted to the purpose (e.g., copper suboxide or copper thiocyanate), a pigment, etc. to prepare an antifouling coating compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an antifouling paint using a resin composition having sufficient film strength and appropriate water solubility as a vehicle.

[Conventional technology] Conventionally, submerged parts of ships and offshore structures have been used to prevent corrosion due to the adhesion of marine organisms such as barnacles, sea breams, sea squirts, and algae, to prevent a decrease in the navigation speed of ships, and to prevent a decrease in the sailing speed of ships. In order to prevent the death of fish and shellfish due to the adhesion of marine organisms to nets and wire meshes, antifouling paints made by blending antifouling agents with vehicle components such as tougheners, rosin, and plasticizers, or the Special Publication Publication No. 40-21
426 Publication, Special Publication No. 44-9579, Special Publication No. 1977
Antifouling paints using isopolymers or copolymers of organotin-containing unsaturated monomers, as shown in Japanese Patent No. 1-12049, are generally applied.

[Problems to be Solved by the Invention] However, the former paint exhibits an antifouling effect by eluting the rosin and antifouling agent components contained in the coating film obtained from it; When immersed in seawater for a long period of time, as the amount of insoluble components increases, the coated surface becomes uneven and becomes less effective in preventing the adhesion of sea creatures. The latter coating is produced by immersing a coating film containing an organotin compound introduced into the polymer via an ester bond in seawater, and hydrolyzing the ester bond to separate the organotin compound and convert it into a carboxyl group. A polymer containing This polymer dissolves in seawater, constantly exposing a fresh coating film and maintaining antifouling properties. However, in order to effectively exhibit the antifouling properties of the coating film, many organic tin compounds are generally introduced, which has the drawback of having an adverse effect on seafood.

[Means for Solving the Problems] Therefore, the present inventors have developed a new and smooth antifouling coating that can be eroded by seawater (has abrasive properties) even if it does not contain organic tin. As a result of various studies aimed at developing antifouling paints, we have found that synthetic resin compositions with appropriate water solubility include l) those containing quaternary ammonium salts, and (2) those containing primary or secondary ammonium salts. There are those containing 7 groups and 3) those containing carboxylic acid groups and sulfonic acid groups, but 1) and 3) are conventional antifouling agents such as cuprous oxide and zinc ethylene bis(dithiocarbamate). has poor storage stability.

2) If the primary or secondary amine 7 group is used, the water elution property of the copolymerized resin is poor, and when the amount of the functional group is further increased, the water resistance becomes significantly worse, and appropriate water solubility is not achieved. I can't get it.

Due to these problems, none of them could be used in the intended antifouling paint composition, and as a result of further investigation, we found that copolymers with tertiary amine groups were blended with conventionally known antifouling agents. It has good storage stability, and by combining it with rosin, a coating with appropriate water solubility can be obtained. The present invention has been completed by discovering that the above object can be achieved by using a copolymer having a transition temperature as the main vehicle component and adding rosin to improve coating strength and water solubility.

That is, the present invention can be obtained by copolymerizing @3 to 80% by weight of an unsaturated monomer having a tertiary amine group and 20 to 97% by weight of an unsaturated monomer having no tertiary amine group. It is characterized by containing 5 to 100 parts by weight of rosin per 100 parts by weight of a copolymer with a number average molecular weight of 3.000 to 200,000 and a glass transition temperature (hereinafter abbreviated as rTgJ) of -10 to 200°C. The present invention relates to an antifouling paint composition.

The unsaturated monomers having a tertiary amine group used in the present invention include monomers represented by the following formulas (I) and (II) and other water-soluble monomers having a tertiary amine group. Examples include unsaturated monomers (m). ' R2C00R4N \ In the formula, R1, R2+ R3 represents a hydrogen atom or a lower alkyl group, R4 represents an alkylene group having 1 to 4 carbon atoms,
R1 and R6 represent an alkyl group having 1 to 4 carbon atoms.

Typical examples include dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate.

R5 where Rl! R2+ R3 represents a hydrogen atom or a lower alkyl group, and R4, R, represents an alkyl group having 1 to 4 carbon atoms.

Representative examples include N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, and the like. (1) above.

The lower alkyl group represented by R1 and R2*R3 in formula (II) is preferably one having 4 or less carbon atoms, particularly a methyl group.

Furthermore, other water-soluble unsaturated monomers (III) having a tertiary amine group include N-vinylpyrrolidone, N-vinylpyrrolidone,
-vinylcaprolactam, N,N-dimethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, and the like.

These unsaturated monomers having a tertiary amino group can be used alone or in combination of two or more.

The unsaturated monomer having no tertiary amino group 7 used in the present invention is a radically polymerizable unsaturated monomer that can undergo a radical polymerization reaction with the above-mentioned unsaturated monomer having a tertiary amino group. It is the body. Representative examples of such unsaturated monomers are as follows.

(a) Esters of acrylic acid or methacrylic acid; for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, methacrylate 01-18 alkyl esters of acrylic acid or methacrylic acid such as ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate; acrylic acid such as allyl acrylate, allyl methacrylate, or 02-6 alkenyl ester of methacrylic acid; 03-18 alkenyloxyalkyl ester of acrylic acid or methacrylic acid such as allyloxyethyl acrylate and allyloxymethacrylate.

(b) Vinyl aromatic compounds: for example, styrene, α-
Methylstyrene, vinyltoluene, p-chlorostyrene.

(C) Polyolefin compounds: for example, butadiene, isoprene, chlorobrene.

(d) Hydroxyl group-containing monomer: For example, acrylic acid or methacrylic acid such as hydroxyethyl acrylate, hydroxyethyl methacrylenide, hydroxypropyl acrylate, hydroxypropyl methacrylate, etc.
6-hydroxyalkyl ester, etc.

(e) Others: 7 Acrylonitrile, methacrylaterile, methyl isopropenyl ketone, vinyl acetate, Beoba monomer (Shell Chemicals), vinyl propionate, vinyl pivalate, acrolein, methacrylate, etc.

These unsaturated monomers can be used alone or in combination of two or more.

As the unsaturated monomers mentioned above, alkyl esters of acrylic acid or methacrylic acid, styrene, etc. are mainly used because they are easy to undergo radical polymerization reactions and have excellent coating properties such as film strength and salt water resistance. preferable.

In addition, the amount of unsaturated monomer used for copolymer production is
3 to 80% by weight, preferably 20% by weight of unsaturated monomers having 7 tertiary amide groups, based on the weight of all monomers used.
~60% by weight, and 20 to 97% by weight, preferably 40% by weight of unsaturated monomers having no tertiary amino groups.
~80% by weight. If the amount of unsaturated monomer having a tertiary amine group used is 3% by weight, the hydrophilicity of the coating film will be impaired and the antifouling function will not be exhibited. Also, conversely, the third
The amount of unsaturated monomer having a class amine group used is 80% by weight.
If the amount is higher than that, the hydrophilicity becomes too thick, and the abrasion of the coating film increases, resulting in poor long-term stain resistance.

The copolymer used in the present invention can be prepared by adding the above-described unsaturated monomer components in a suitable water-miscible organic solvent in the presence of a radical polymerization catalyst. at a reaction temperature of about 0 to about 180°C, preferably about 40 to about 170°C.
This can be carried out by continuing the reaction for a period of time, preferably about 6 to about 10 hours.

As the water-miscible organic solvent to be used, it is preferable to use a solvent that can dissolve the copolymer produced so as not to cause gelation during the copolymerization reaction and is miscible with water. Examples of such solvents include methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, cyclohexanol, benzyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol. , alcohols such as polypropylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol Ethers such as methyl ether; esters such as ethyl oxate, propyl formate, acetic acid ethylene glycol monoethyl ether, acetic acid diethylene glycol monobutyl ether, and the like. In addition to the water-miscible organic solvents mentioned above, it is also possible to use solvents that are not miscible with water in a range that does not impede the above-mentioned properties.

As the radical polymerization catalyst to be used, for example, radical polymerization initiators that can be used for normal radical polymerization such as azo compounds, peroxide compounds, diazo compounds, nitroso compounds, redox compounds, etc. can be used, and ionizing radiation etc. Can be used to generate radicals.

The copolymer in the present invention has a number average molecular weight of 3.000 to 2.
00.000, preferably in the range of 5.000 to 50.000.

When the average molecular weight is less than 3,00,0, the hydrophilicity becomes large and the long-term stain resistance is poor;
If it is larger than 00,000, the hydrophilic property is lost and the antifouling function is not exhibited.

Further, the copolymer in the present invention has a Tg of 110 to 20.
0°C, preferably in the range of 0-150°C.

When the Tg is less than 110°C, the coating film remains sticky and has poor antifouling properties.On the other hand, when the Tg is greater than 200°C, the coating film becomes brittle and has poor water resistance, salt water resistance, etc.

The copolymer thus obtained can form a coating film exhibiting antifouling properties by itself, but its antifouling properties are insufficient, and furthermore, it increases the strength and water solubility of the coating. In the present invention, it is necessary to contain rosin.

As the rosin used in the present invention, both gum rosin and wood rosin can be used, and modified products thereof can also be used. Among these, rosins containing a high proportion of abietic acid, such as those commercially available as WW rosins, are preferred. Examples of modified products include maleated rosin and phthalated rosin.

In the present invention, the amount of the rosin used is 1 to 1 of the copolymer.
5 to 100 parts by weight, preferably 10 parts by weight
If the amount is less than 5 parts by weight, the strength of the resulting coating film will be low and the water solubility of the coating film will be insufficient. On the other hand, if it exceeds 100 parts by weight, the coating film will become too hard and brittle, making it easy to crack when thickly applied.

The antifouling paint composition of the present invention may contain a mixture of the above-mentioned copolymer and rosin as a paint binder, and a conventionally known antifouling agent depending on the purpose, such as suboxide steel, 1,000 ocyan copper, or triphenyltin. Fluoride, triphenyltin hydroxide, zinc ethylene bis(dithiocarbamate),
Zinc oxide etc. can be blended.

Further, in addition to the above-mentioned antifouling agent, extender pigments, coloring pigments, plasticizers, other resins, and the like may be blended into the antifouling paint composition of the present invention, if necessary.

[Action and Effect of the Invention] The composition of the present invention contains a copolymer having a tertiary amine group and rosin as essential components, but the composition of the present invention also contains an antifouling agent such as cuprous oxide. Even if the copolymer is allowed to dry, the tertiary amine group in the copolymer does not react with the antifouling agent, and the storage stability is good. In addition, by blending rosin with this copolymer, sufficient film strength and appropriate water solubility can be obtained, and since a smooth coating surface is formed even after long-term dissolution, it is possible to prevent corrosion over a long period of time. Shows uncleanness.

Compared to conventional antifouling paints, the composition of the present invention exhibits antifouling properties equivalent to or better than conventional antifouling paints containing organic tin, even when combined with a low-standing antifouling agent that does not contain organic tin. can do.

Next, the present invention will be further explained with reference to Examples, but the present invention is not limited only to the Examples. In Examples and Comparative Examples, "1 part" indicates "part by weight" unless otherwise specified.

1.1 0.5 g of azoisobutyronitrile was added to 70 g of methyl methacrylate, 30 g of dimethylamine ethyl acrylate, and 43 g of ethylene glycol monoethyl ether, and after reacting at 90 to 100°C for 3 hours with stirring, further azoisobutyronitrile was added. Add 107.2g of ethylene glycol monoethyl ether containing 0.2g of lonitrile and bring to a boiling point of 90-100.
The reaction was carried out at ℃ for 2 hours with stirring to obtain a pale yellow viscous liquid with a solid content of about 40%. The copolymer has a number average molecular weight of 45.000.
Tg was 60°C (theoretical value, hereinafter the same meaning).

Ar1 Methyl methacrylate 50g, N-vinylpyrrolidone 2
5 g and 25 g of N,N-dimethylacrylamide were dissolved in 43 g of ethylene glycol monoethyl ether, and 2.0 g of benzoyl peroxide was added thereto and the solution was dissolved under stirring for 90 to 1
After reacting at 00°C for 3 hours, benzoyl peroxide i, og and ethylene glycol monoethyl ether 1
07g was added and reacted for 2 hours under stirring at 90-100'O.
A pale yellow viscous liquid with a solids content of about 40% was obtained. The polymer has a number average molecular weight of 21.000. The Tg was 130'O.

. Part 3: Add 1.0 g of azoisobutyronitrile to 20 g of styrene, 40 g of methyl methacrylate, 40 g of diethylaminoethyl methacrylate, and 43 g of ethylene glycol monoethyl ether, react with stirring at 90 to 100°C for 3 hours, and then add azoisobutyronitrile. Add 0.4g, 107g of ethylene glycol monoethyl ether and 90~
The reaction was carried out at 100'O for 2 hours to obtain a pale yellow viscous liquid with a solid content of about 40%. The copolymer has an average molecular weight of 34.000
．． Tg was 65°C.

Tributary 1" To 50.0 parts of the copolymer solution of Production Example 1, 5.0 parts of WW rosin was added.
0 parts, cuprous oxide 20 parts, saponified zinc 5.0 parts, xylene 2
0 parts were mixed and dispersed with a paint conditioner to obtain an antifouling paint composition.

Subsoil rotation: Example 2 was carried out in the same manner as in Example 1 with the blending ratio shown in Table 1.
-9 antifouling paint compositions were prepared.

An antifouling paint composition was prepared in the same manner as in Example 1 with the following formulation.

Comparative Example 1 (Part) Vinyl chloride resin 10. OWW rosin
10.0 Tricresyl phosphate 4.0 Triphenyltin fluoride 10.0 Talc
5.0 Bengara
5.0 xylene
28.0 Methyl isobutyl ketone 28.
0 total 100.0 (parts) Comparative example 2 (parts) Chlorinated rubber resin 5. OWW rosin
15.0 tricresyl phosphate
4.0 Cuprous oxide 30.
0 Talc 5.0 Barita 3.0 Bengara
4.0 xylene
34.0 total 100.0 (parts) Comparative example 3 (parts) Vinyl chloride resin 5.5 WW rosin
5.5 tricresyl phosphate
2.0 Cuprous oxide 30.0
Triphenyltin hydroxide 10.0 Barium sulfate 4.0 Talc
11.0 Bengala
10.0 xylene 1
1.0 methyl isobutyl ketone 11.0 total
100.0 (parts) The coating film performance test results of Examples 1 to 9 and Comparative Examples 1 to 3 are summarized in Table 2 below.

For the paints obtained in Examples 1 to 9 and Comparative Examples 1 to 3 above, zinc epoxy shop brusher (dry film thickness 15 μm) and epoxy antirust paint were applied to a 10100 x 300 x 20 sandblasted steel plate. (200L) was coated in advance to a dry film thickness of 50JL and dried for 7 days. The results of evaluating the antifouling properties (numbers indicate the area of attached organisms in %) are shown below.

Table 2: Antifouling Performance Test Results As is clear from the test results, the antifouling paint according to the present invention exhibited good antifouling performance.

Claims (1)

[Claims] (1) 3 to 80 parts by weight of an unsaturated monomer having a tertiary amino group and 20 to 80 parts by weight of an unsaturated monomer having no tertiary amino group
Number average molecular weight 3,000 to 200,000 obtained by copolymerizing 97 parts by weight, glass transition temperature -1
An antifouling paint composition comprising 5 to 100 parts by weight of rosin per 100 parts by weight of a copolymer at 0 to 200°C.