JPH0472316A - Production of graft copolymer, slightly water-soluble resin composition and paint containing the same - Google Patents

Abstract

PURPOSE:To obtain the subject copolymer having slight water-solubility and high coating film strength, slowly hydrolyzing in sea water and suitable for antifouling agent for ship's bottom by polymerizing a specific copolymer having reactive double bond with an ethylenically unsaturated monomer. CONSTITUTION:The objective copolymer can be produced by polymerizing (A) 5-95 wt.% of a copolymer produced by reacting (i) a copolymer polyol of formula (R1 and R1' are 3-5C alkylene; R2 is 2-5C alkylene; R3 is 1-8C alkylene; m, m' and n are positive numbers) obtained by reacting an aliphatic dicarboxylic acid with a dialcohol and bonding an aliphatic polyether to both terminals of the reaction product and (ii) a compound having a group reactive with hydroxyl group and a reactive double bond (e.g. maleic anhydride) and (B) 95-5wt.% of an ethylenically unsaturated monomer (e.g. methyl acrylate).

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is a method for producing a graft copolymer that is useful as an antifouling paint, etc., and has moderate water solubility and sufficient coating strength. The present invention relates to a water-bathable resin composition and a paint made using the same.

(Conventional Technique? rJ) Conventionally, submerged parts of ships and offshore structures have been treated with `` -! In order to prevent the death of fish and shellfish due to the adhesion of marine organisms to aquaculture nets and wire meshes, antifouling paints made by blending antifouling agents with vehicle components such as toughner rosin and plasticizers, or
As shown in Japanese Patent Publication No. 21426 and Japanese Patent Publication No. 12049/1984, antifouling paints using polymers or copolymers of organotin-containing unsaturated monomers are applied, and the coating film is continuous in seawater. by gradual elution.

It shows antifouling effect.

(Problem to be Solved by the Invention) The former type of paint exhibits an antifouling effect by the elution of cosine and antifouling agent components contained in the coating film obtained from it, but the coating film does not last for a long time. When immersed in seawater, the amount of insoluble components increases and the coated surface becomes uneven, making it less effective in preventing the adhesion of marine organisms. In addition, in the latter coating, a coating film containing an organotin compound introduced into the 9-polymer via an ester bond is immersed in seawater, and the organotin compound is separated by hydrolysis of the ester bond.
A polymer containing carboxyl groups is produced.

This polymer dissolves in seawater, always exposing a fresh coating.
It maintains stain resistance. However, in order to effectively exhibit the antifouling properties of the coating film, many toxic organic tin compounds are generally introduced, which has the disadvantage of having an adverse effect on seafood.

The present invention was achieved as a result of intensive studies in view of the existence of various shortcomings in these conventional techniques, and the coating is hydrolyzed in seawater and becomes slightly water-soluble even if it does not contain an organic tin compound. The present invention provides a method for producing a graft copolymer, a slightly water-soluble resin composition, and a paint, which can continuously form a fresh coating film.

(Means for Solving Problem H) That is, the present invention solves the following problems: General formula (2); Rtu is an alkylene group having 2 to 5 carbon atoms, FLs is an alkylene group having 1 to 8 carbon atoms, m, m' and Unh
and a copolymer polyol represented by a positive number).

It is obtained by reacting a compound having a group capable of reacting with the hydroxyl group of the copolymer polyol and a reactive double bond.

In the presence of 5 to 95% by weight of a copolymer (A) having a reactive double bond, 95 to 5% by weight of an ethylenically unsaturated monomer (B) copolymerizable with the copolymer (A) %, a slightly water-soluble resin composition containing the graft copolymer obtained by the manufacturing method, and a slightly water-soluble resin composition using the slightly water-soluble resin composition. Regarding paint.

The copolymer polyol represented by the general formula fl) used in the present invention is a polyester polyol obtained from an aliphatic dicarboxylic acid and an aliphatic dialcohol, with aliphatic polyethers bonded to both ends. be.

Here, as R1 in general formula (2).

(CL)3, (CH2)4, ~(CH2)5-
etc.

R2ke-(CH2)z, (CH2)3 (
CHs)a --(CH2)5-, etc., and R3b,
CR2, (CH2)2.

(C)(z)s (CL)4. (CHHz)s
, (CHz)g.

= (σ city) y, (C) (2) 8-, etc. a
-(cH2)4- is preferred as X, and R
Cut 4 is preferred because it exhibits particularly good slight water solubility.

Further, in the copolymer polyol, the polyester portion preferably has a number average molecular weight of about 300 to 5,000, and the polyether portions at both ends preferably have a number average molecular weight of about 100 to 3,000. If the molecular weight is outside this range, it becomes difficult to obtain an appropriate level of water solubility.

The copolymer polyol represented by general formula [1] can be produced by a known method. For example, as described in JP-A-63-105030, polyester polyol,
A method of adding tetrahydrofuran in the presence of a Lewis acid and a 3- to 4-membered cyclic ether, and JP-A-60-19
As described in Japanese Patent No. 7726, it can be produced by adding a 3- to 5-membered cyclic ether to a polyester polyol using lithium hexafluorophosphate as a catalyst.

The copolymer polyol represented by the general formula (I) is reacted with a compound having a group capable of reacting with the hydroxyl group of the copolymer polyol and a reactive double bond to form 9 reactive double bonds. A copolymer corporation with

As the compound, α, β-unsaturated carboxylic acids such as maleic anhydride/acid, acrylic acid, methacrylic acid, acrylic anhydride, methacrylic anhydride, acid chlorides thereof, or derivatives thereof reactive with hydroxyl groups are used. be able to.

Further, as the compound, a compound having an isocyanate group and a reactive double bond can also be used. In this case, a reaction product obtained by reacting a polyvalent isocyanate having two or more isocyanate groups with a hydroxyl group-containing ethylenically unsaturated monomer is used, and an isocyanate group-containing ethylenically unsaturated monomer is used. be.

In the former case, the polyvalent isocyanate includes hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, diphenylmethane diisocyanate, and z24-trimethylhexamethylene diisocyanate.

Cyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, impropylidene bis(4
-cyclohexyl isocyanate).

Billet form of hexamethylene diisocyanate.

A compound having two or more isocyanate groups, such as a trimer of inphorone diisocyanate containing an incyanurate ring, preferably a reaction compound such as 2,2,4-trimethylhexamethylene diisocyanate, tolylene diisocyanate, etc. It is a diisocyanate compound having isocyanate groups with different properties.

Moreover, as the hydroxyl group-containing ethylenically unsaturated monomer, one having one hydroxyl group is preferable, such as hydroxyalkyl acrylates such as 2- and droxyethyl acrylate, 2-hydroxyalkyl acrylate, and 2-hydroxybutyl acrylate.

Hydroxy alkyl methacrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, N-
Methylol acrylamide.

Examples include N-methylol methacrylamide.

The polyvalent isocyanate compound and the hydroxyl group-containing ethylenically unsaturated monomer have an equivalent ratio of isocyanate group of the former to hydroxyl group of the latter of 1.0/0.5 to 1. It is preferable to mix them so that olo is 7 and carry out one reaction. There may be unreacted hydroxyl group-containing unsaturated monomers. The reaction temperature is usually 0 to 150°C, preferably 40 to 100°C, and a urethane reaction catalyst such as dibutyltin dilaurate may be used for one reaction. Further, during the 9 reaction, a polymerization inhibitor such as bis(2-hydroxy-3-tert-butyl-5-ethylphenyl)methane or hydroquinone may be present. Preferably, the reaction is carried out in a suitable organic solvent.

Examples of the organic solvent include methyl ethyl getone, methyl isobutyl ketone, and ethyl acetate.

Examples include butyl acetate and cellosolve acetate.

In the latter case, the isocyanate group-containing polymerizable monomers include incyanoalkyl acrylates such as isocyanomethyl acrylate, isocyanoethyl acrylate, and incyanobutyl acrylate, isocyanomethyl methacrylate, iso/anobutyl methacrylate, and / incyanoalkyl acrylate such as abutyl methacrylate, etc. can be used.

These compounds contain 0.01 to 0.55 mol of 2-reactive double bonds per 100 g of the resulting copolymer (A).

In particular, it is preferable to carry out the reaction so that the amount is 0.1 to 0.4 mol. If the amount is less than 0.01 mol, graft polymerization tends to be difficult during the subsequent copolymerization with the ethylenically unsaturated monomer CB+, whereas if it exceeds 0.55 mol, gelation may occur during polymerization. more likely to occur.

Note that the two reactions can be carried out by known methods.

As the ethylenically unsaturated monomer polymerized in the presence of the resulting copolymer CAI, for example, the following can be used.

(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, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate, etc.

(b) Vinyl aromatic compounds; e.g. styrene, α-
Methylstyrene, vinyltoluene, p-O-rustyrene, etc.

(c) Hydroxyl group-containing monomer; for example, hydroxyethyl acrylate, hydroxyethyl methacrylate.

Hydroxy alkyl esters of acrylic acid or methacrylic acid such as hydroxypropyl acrylate and hydroxypropyl methacrylate.

(d) Sono et al.; acrylonitrile, methacrylonitrile, vinyl acetate, etc.

These unsaturated monomers can be used alone or in combination of two or more. The above unsaturated monomer CB+
Alkyl esters of acrylic acid or methacrylic acid are used because of their excellent coating properties such as coating strength and salt water resistance.
It is preferable to mainly use styrene or the like.

The graft copolymer of the present invention can be obtained by polymerizing component (B) in the presence of component) described above. Here, the amount of each compounded component (A) is 5 to 95% by weight, preferably 5 to 50% by weight.
9% by weight, preferably 10 to 40% by weight, and one component (B) is 95 to 5% by weight, preferably 95 to 50% by weight.
% by weight, particularly preferably from 90 to 60% by weight.

If the ratio of component (included here) and component (Bl) is 1+/IB+ (weight ratio) less than 5/95, in terms of slight water solubility.

The elution rate is low both initially and over a long period, and there is almost no antifouling effect. On the other hand, if it exceeds 9515.

The initial elution rate is too high to maintain the antifouling effect, and the adhesiveness of the coating film is too thick to obtain a good coating film. From these aspects, the range of 5/95 to 50150 is the most excellent in terms of antifouling effect, and the most excellent is the range of 10/90 to 40/60.

[A) Polymerization of Bl component in the presence of It component (polymerization of Bl component is performed using xylene, toluene, methyl isobutyl ketone as necessary).

Organic solvents that do not contain hydroxyl groups, such as butyl acetate and cellosolve acetate, can be used as the reaction solvent or diluent solvent. As polymerization catalysts, peroxide-based radical initiators such as benzoyl peroxide and ditertiary-butyl peroxide, and azo-based radical initiators such as azobisisobuticonitrile and azobisvaleronitrile are used. Although solution polymerization is simple and preferable, suspension polymerization,
Bulk polymerization, ionic polymerization, photopolymerization, radiation polymerization, etc. can also be used. The number average molecular weight of the resulting graft copolymer is preferably 3,000 to 100,000, particularly s,
o o o to 30,000 is preferred.

If the number average molecular weight is smaller than a or ooo, the water resistance of the coating film will be poor and phenomena such as whitening will easily occur;
If the amount exceeds 100%, the solubility in water tends to be poor.

In addition, the glass transition temperature of the obtained graft copolymer is
The temperature is preferably -60°C to 80°C, particularly preferably -30°C to 40°C. Copolymers with a low glass transition temperature are advantageous for police nets that require flexibility, while copolymers with a high glass transition temperature are advantageous for use in areas with high water resistance such as ships. It is.

The graft copolymer thus obtained is:

It is contained as a main component in the slightly water-soluble resin composition of the present invention. The slightly water-soluble resin composition of the present invention can also contain other known resins to the extent that the good slightly water-soluble resin composition of the graft copolymer is not impaired.

The slightly water-soluble resin composition of the present invention can be made into an antifouling paint by adding known antifouling agents, pigments, etc., if necessary.

Typical antifouling agents include zinc oxide, zinc chromate,
Strontium chromate, cupric chromate, cupric citrate, cupric ferrocyanate, quinoline steel, cupric δ-hydroquinone, cupric oleate, cupric nitrate,
Cupric phosphorus, cupric tartrate, cuprous oxide, iodide
Copper or cuprous sulfite.

On the other hand, typical pigments include inorganic pigments such as titanium oxide (titanium white), iron oxide, and carbon black;
Although organic pigments such as azo, cyanine, and quinacridine pigments can be used, inorganic pigments are usually used.

In addition, organic tin compounds, triazine compounds,
There is no hindrance to the combined use of organic sulfur compounds and the like.

Furthermore, it is also possible to use rosin, gum rosin, wood rosin, tall oil rosin, etc. as an elution aid. The paint of the present invention thus obtained is useful as a ship bottom paint, a paint for fishing nets, and the like.

(Example) Next, an example of the present invention will be shown. Hereinafter, "part" means "part by weight"
, "%" means "% by weight".

Synthesis Example 1 (Production of Copolymer (A)-■) A copolymer polyol (trade name: PTG-E,
300 parts of Odougaya Chemical Co., Ltd., hydroxyl value 82.6°, number average molecular weight 1400) were placed in a four-lobe flask equipped with a thermometer, reflux condenser, stirrer and nitrogen gas inlet, and 400 parts of xylene, m water male rain II! 0.75
Copolymer (3)-■ having about 0.123 mol of reactive double bonds per 1009 of the resin was synthesized by further charging and reacting at 130°C for 2 hours, and a resin solution containing it (solid content 70% ) was obtained.

Synthesis Example 2 (Synthesis of the reaction product of trimethylene diisocyanate and 2-hydroxyethyl acrylate) Tolylene diisocyanate (TMD2) 63.3 ml was placed in a four-bottle flask equipped with a thermometer, reflux condenser, stirrer, and nitrogen gas inlet.
parts, methyl ethyl ketone 29.3 parts 1 polymerization inhibitor AW-
500 (manufactured by Kawaguchi Chemical Co., Ltd., trade name, 0.1 part of methylene bis(2-ethyl-4-t-butylphenol), 0.05 part of dibutyltin dilaure) was added, and while keeping the temperature at 60°C, 2-hydroxy acrylic acid was added. ethyl 36.7m 1
After dropping over a period of time, the mixture was reacted at the same temperature for 1 hour to obtain a grafting agent. A solvent (methyl ethyl ketone) was added to the obtained grafting agent so that the solid content was about 70%. The obtained grafting agent had a heating residue of 70.6% and a viscosity (
Gardner/25°C) and color number (Gardner) was 1 or less.

Synthesis Example 3 (Production of Copolymer (A)-〇) Copolymer polyol PTG-E used in Synthesis Example 1 (Hodogaya Chemical Industry ■
300 parts of xylene and 400 parts of
Prepare the department.

The temperature was raised to 130°C. Next, 50 parts of the reactant obtained in Synthesis Example 2 was added and reacted for 2 hours to obtain a copolymer (50 parts) having about 0.37 moles of reactive double bonds per 100 g of resin.
)-〇 synthesized and a resin solution containing it (solid content 50%)
I got it.

Synthesis Example 4 (Formation of Graft Copolymer) For 100 parts of the formulation shown in Table 1 (mixture of methyl methacrylate and butyl acrylate as copolymer (5), monomer ■), azobisisobutyl Lonitrile 0.
A graft copolymer was prepared in the following manner using 5 parts and 0.2 parts of di-t-butyl peroxide.

That is, the polyol solution obtained in Synthesis Example 1 was charged into a flask so that the solid content was as shown in Table 1.

Next, n-butanol was charged into the flask so that the amount of n-butanol was 30% based on the solid content of the polyol solution. Then 110℃
Methyl methacrylate, butyl acrylate, azobisisobutyronitrile and di-t-
After adding the butyl peroxide mixture dropwise over 2 hours, the mixture was further kept at the same temperature for 1 hour, and then heated to 130°C and reacted for 3 hours to obtain a graft copolymer.

A solvent (xylene) was added to the obtained graft copolymer so that the solid content was about 50X. Table 1 shows the solid content, viscosity, and theoretical glass transition point of the obtained graft copolymer solution.

Coating film evaluation Each graft copolymer shown in Table 1 was
It was applied to a single-sided ground glass plate measuring m x 3 mm to a dry film thickness of 50 μm, dried at 100°C for 4 hours, then immersed in 1 knot of flowing seawater (20°C), and the change in the coating film overlapping was measured to determine the wear rate. (%) was calculated.

The weight of the test piece after immersion was measured after drying at 110°C for 1 hour.

The test results are summarized in Table 2.

(Effects of the Invention) The graft copolymer obtained by the production method of the present invention and the slightly water-soluble resin composition containing the same are gradually hydrolyzed in seawater, and are strong and have appropriate paint film wear resistance. Therefore, when used in an antifouling paint, it is easy to select an antifouling agent, and the antifouling agent can be stably eluted over a long period of time. Therefore, surface coating of ship bottoms, underwater structures, etc.
It is extremely useful for coating fish farming nets, etc.

Agent Patent Attorney Kuni Wakabayashi V, 4'-1+

Claims (1)

[Claims] 1. General formula (I); ▲Mathematical formulas, chemical formulas, tables, etc.▼…………(I) (However, R_1 and R_1' are alkylene groups having 3 to 5 carbon atoms, and R_2 is Alkylene group having 2 to 5 carbon atoms, R_3
is an alkylene group having 1 to 8 carbon atoms, m, m' and n are positive numbers), a group that can react with the hydroxyl group of the copolymer polyol, and a reactive double In the presence of 5 to 95% by weight of a reactive double bond-containing copolymer (A) obtained by reacting a bond-containing compound, an ethylenic polymer copolymerizable with the copolymer (A) is added. A method for producing a graft copolymer, which comprises polymerizing 95 to 5% by weight of a saturated monomer (B). 2. The method for producing a graft copolymer according to claim 1, wherein 95 to 50% by weight of the ethylenically unsaturated monomer (B) is polymerized in the presence of 5 to 50% by weight of the copolymer (A). . 3. The copolymer (A) binds the reactive double bonds to 100% of the resin.
Claim 1 or 2 having 0.01 to 0.55 mol per g.
Method for producing the described graft copolymer. 4. The method for producing a graft copolymer according to claim 1, 2 or 3, wherein R_3 in general formula (I) is -(CH_2)_4-. 5. R_1 and R_1' in general formula (I) are -(CH
_2)_4- The method for producing a graft copolymer according to any one of claims 1 to 4. 6. The method for producing a graft copolymer according to any one of claims 1 to 5, wherein the compound having a group capable of reacting with the hydroxyl group of the copolymer polyol and a reactive double bond has an isocyanate group. . 7. Any one of claims 1 to 5, wherein the compound having a group capable of reacting with the hydroxyl group of the copolymer polyol and a reactive double bond is an α,β-unsaturated carboxylic acid or an anhydride thereof. A method for producing a graft copolymer. 8. A slightly water-soluble resin composition comprising a graft copolymer obtained by the production method according to any one of claims 1 to 7. 9. A paint comprising the slightly water-soluble resin composition according to claim 8.