JPS58108264A - Submarine antistaining composition - Google Patents

Abstract

PURPOSE:The titled composition, prepared by adding a thermoplastic elastomer in a specific amount to a copolymer consisting of a polymerizable unsaturated carboxylic acid, an acrylic compound, etc. and containing a triorganotin compound in a low tin concentration, having improved dissolving property and solubility and flexural properties, and suitable for ship bottom coating materials, etc. CONSTITUTION:A composition obtained by adding (B) 3-40pts.wt. thermoplastic elastomer to (A) 100pts.wt. copolymer, containing (i) 40-80wt% triorganotin salt units of a monobasic or (and) dibasic polymerizable unsaturated carboxylic acid, e.g. tributyltin methacrylate, and (ii) 20-60wt% polymerizable unsaturated compound, e.g. methyl methacrylate, selected from the group consisting of acrylic compounds, vinyl compounds having functional groups and vinyl hydrocarbons. EFFECT:Improved physical properties of antistaining films, e.g. tensile strength, adhesive properties, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an underwater antifouling composition containing a triorganotin-containing copolymer having a low tin concentration.

Currently, it is obtained by copolymerizing a triorganotin salt of a polymerizable unsaturated carboxylic acid and other polymerizable monomers. Tri-organotin-containing copolymers, which have a linear polymer skeleton and a tri-organotin ester bond in the side chain, are used as the most excellent underwater antifouling agents in fields such as ship bottom paints.

These tri-organotin-containing copolymers undergo gradual hydrolysis in seawater, and the tri-organotin group, which is an antifouling component, is eluted from the tin ester bond in the side chain, and the remainder is eluted from the carboxyl group in the side chain. Because it has a straight chain polymer skeleton that becomes water-soluble and dissolves in seawater, a new antifouling surface is constantly exposed and it is said to exhibit excellent antifouling effects.

However, in order to exert this antifouling mechanism, it is actually necessary to have at least 57% by weight of triorganotin salt in the solid content of the resin, and below this, the solubility of the linear chain skeleton of the polymer is greatly reduced. Since the antifouling surface is not renewed, the elution of tri-organotin groups is inhibited, and a long-term antifouling effect cannot be expected.

Therefore, at present, triorganotin salts are contained in high concentrations, but this is economically disadvantageous.

Therefore, as a method for lowering the tin concentration, for example, (1) a triorganic-tin-containing copolymer having a high tin concentration is mixed with another resin (for example, an acrylic resin) that is compatible with the triorganic-tin-containing copolymer. ■Choose a water-soluble compound as a comonomer component with triorganotin salt of polymerizable unsaturated carboxylic acid.

(2) A second method has been proposed in which a triorganotin-containing polymer is graft-polymerized onto polyvinyl chloride. However, in all of these methods, insoluble polymeric substances remain on the surface of the coating film, inhibiting the elution of antifouling components and the solubility of the antifouling coating film, and making it impossible to prevent long-term adhesion of marine organisms.
□ As a result of extensive research, the present inventors added a specific amount of thermoplastic elastomer to a tri-organotin-containing copolymer, thereby increasing the tri-organotin salt content in the resin solid content from 40 to 65.
We succeeded in obtaining an underwater antifouling agent of a triorganotin-containing copolymer that has excellent dissolution and solubility even in terms of weight percentage.

That is, 1 the present invention comprises (a) 40 to 80% by weight of units of a triorganotin salt of a basic or (and) dibasic polymerizable unsaturated carboxylic acid and (b) an acrylic compound.

20 units of a polymerizable unsaturated compound selected from the group consisting of a vinyl compound having a functional group and a vinyl hydrocarbon.
100 of triorganotin-containing copolymer containing ~60% by weight
This is an underwater antifouling composition characterized by adding 3 to 40 parts by weight of a thermoplastic elastomer.

The thermoplastic elastomer used in the present invention is 2
Normally, it consists of a polymeric molecule/group (hard segment) whose glass transition point is higher than room temperature and a polymeric molecular group (soft segment) whose glass transition point is lower than room temperature. The soft segment becomes a bridge point and exhibits rubber elasticity, and when heated,
- As a result of fluidization in the de-segment portions, the entire polymer becomes more fluid.

It is a polymer with a structure and physical properties that allow it to be easily molded. Here are some representative examples.

(1) Styrene-butadiene (or imprene) block polymer Living polymerization of styrene is performed under an anionic catalyst, followed by block polymerization of butadiene (or isoprene), or a polyfunctional initiator is used.

Create chain- or star-shaped living soft polymers.

It is obtained by block polymerization of a node polymer of K styrene. Such polymers.

For example, Shell Chemical Company's Cauliflex (Ca
riflex) TR, Phillips Petroleum's Norprene-T+ Anitsx (7) Yaw 0 Knob V 7 (Europrene
) It is sold under the trademark 5QL-T. Moreover, the weight ratio of styrene/phridien (or isoprene) of the block polymer is about 25-50/75-50.

(2) Obtained by thermoplastic polyester elastomer polycondensation. One example has the following structure.

0 0 0 II II II4+0-(
CH2)4”)qO−C−o+−m+0−(CH2)4
-0-(, @-C+n (q is an integer from 2 to 14) Such polymers include 9, for example, Toyobo's Kuiron,
It is sold under the trade names of Hurbon by Norbon Company and Hytrel by II DuPont.

(3) Thermoplastic polyurethane di-stomer is obtained by polyaddition reaction of an aromatic diisocyanate (for example, 4,4'-diphenylmethane diiso/anate, etc.) and a short-chain nol based on one type of polyether or polyester. Such polymers include American/Anamide's Cyanaprene (polyester based) and Uniroyal's Roylar (polyester based).
77 Pellethane from Pujillon.

It is marketed under the trademark Polyester and Polyether Base).

(4) Trans-1,4-Polyisoprene Trans-1,4i-polyinoprene with trans content of 9 and 5%, molecules of 14×10 and crystals, and degree of conversion of 30%. Such polymers are sold under the trademark Trans-Pip by Polysar Corporation.

(5) Polyethylene-Butyl Rubber Graft Polymers Such polymers are sold under the trademark ET by Allied Chemical Company.

A triorganotin salt of a monobasic or dibasic polymerizable unsaturated carboxylic acid, an acrylic compound, a vinyl compound having a functional group' and a vinyl hydrocarbon constituting the triorganotin-containing copolymer of the present invention Examples of copolymers with other polymerizable unsaturated compounds such as
No. 9, Special Publication No. 13392-1970, Special Publication No. 49-204
No. 91 and Japanese Patent Publication No. 52-48170.

- A triorganotin-containing copolymer obtained by copolymerizing a triorganotin salt of a basic or dibasic polymerizable unsaturated carboxylic acid with another polymerizable unsaturated compound.

- A triorganic compound obtained by reacting a triorganotin compound with a high acid value vinyl resin obtained by copolymerizing a basic or dibasic polymerizable unsaturated carboxylic acid with another polymerizable unsaturated compound. Examples include tin-containing copolymers.

Here, in the triorganotin group in the triorganotin-containing copolymer of the present invention, the organic group is an alkyl group having 3 to 10 carbon atoms,
/chloroalkyl group, phenyl group is an aralkyl group, that is, tri-alkyltin group, tricycloalkyltin4. )177-nyltin group and triallkyltin group. -1 The monobasic and dibasic unsaturated carboxylic acids used in the above methods 1 to 2 include acrylic acid, methacrylic acid, and α-cyanoacrylic acid.

Examples include crotonic acid, vinylbenzoic acid, maleinoic acid, fumaric acid, itaconic acid, anthraconic acid, or their acid anhydrides.

Typical examples of triorganotin salts of monobasic polymerizable unsaturated carboxylic acids of the present invention include tributyltin methacrylate and tributyltin acrylate.

tricyclohexyltin methacrylate, trinochlorohexyltin acrylate, triphenyltin methacrylate,
Examples include triphenyltin acrylate. Typical examples of triorganotin salts of polymerizable unsaturated carboxylic acids that are still dibasic include 9 such as bis(tributyltin)malate, bis(triamyltin)malate, bis()IJcyclohexyltin)malate, and bis(tributyltin)malate. phenyltin) malate, tributyltin butylmalate, triphenyltin dodecyl/l/-7r) r monotricyclohexyltin maleate.

Bis(tributyltin) fumarate, bis(triphenyltin) fumarate, tributyltin butyl fumarate, triphenyltin ethyl fumarate, bis(tributyltin) citraconate, bis(tributyltin) itaconate, bis(triphenyltin) itaconate, Bis(tricyclohexyltin) itaconate, α-tributyltin butyl itaconate, α-tributyltin benzyl itaconate,
Examples include monotributyltin itaconate.

These compounds may be used alone or in combination of two or more.

Examples of other polymerizable unsaturated compounds to be copolymerized with the triorganotin salts of these unsaturated carboxylic acids include methyl methacrylate and butyl methacrylate.

/ Acrylic compounds such as chlorohexyl methacrylate, phenyl methacrylate, ethyl acrylate, butyl acrylate, octyl acrylate, dodecyl acrylate, cyclohexyl acrylate, phenyl acrylate, hydroxyethyl acrylate, acrylic acid, methacrylic acid.

Vinyl chloride, vinylidene chloride, acrylonitrile.

Methacrylic nitrile, acrylamide, vinyl acetate, vinyl phthylate, methyl vinyl ether.

Vinyl compounds with functional groups such as octyl vinyl ether and dodenruvinyl ether, and styrene.

These other polymerizable unsaturated compounds, including vinyl hydrocarbons such as α-methylstyrene, phtageno, and vinyltoluene, may be used alone or in combination of two or more.

In the underwater antifouling composition of the present invention, the thermoplastic elastomer contains the thermal ET911u elastomer in a ratio of 3 to 40 parts by weight to 100 parts by weight of the triorganotin-containing copolymer, so that the thermoplastic elastomer exhibits its characteristics. requires an amount of at least 3 by weight in the total polymer solids (total of the triorganotin-containing copolymer and thermoplastic nidistomer) and that the triorganotin salt units of the polymerizable unsaturated carboxylic acid are It is necessary to contain it in an amount of 40 to 65% by weight in the total polymer solid content. If it is less than 40% by weight, the solubility and dissolution of the copolymer coating will decrease, and if it exceeds 65% by weight, the solubility will increase and it will be uneconomical due to wasteful elution.0 Thermal i=J Plasticity The elastomer may be added and dissolved after producing the tri-organotin-containing copolymer solution, or it may be added together with the tri-organotin-containing copolymer at the time of forming the coating.

The underwater antifouling composition of the present invention thus obtained can be used as is.
Dissolved in organic solvents or copper compounds.

It is used in ship bottom antifouling paints and fishing net antifouling agents together with pigments, carriers, plasticizers, paint conditioners, toxic substance elution control agents, and if necessary, tri-organotin compounds and diluents.

The underwater antifouling composition of the present invention has the following features.

In other words, even though a polymer with a low tin concentration is used, it is possible to maintain an effective amount of tin leached into the sea, and the entire antifouling coating exhibits homogeneous solubility, as well as a moderate solubility. have. Furthermore, the physical properties of the antifouling coating film include improved flexibility, tensile strength, and adhesion. In particular, with respect to bending, no peeling or cracking occurs even if the film is bent 180 degrees at room temperature.

Next, the present invention will be explained with reference to Examples and Test Examples. In Examples and Test Examples, ``chi'' and ``part'' indicate weight % and weight part, respectively.

Example 1 Tributyltin methacrylate 195f was added to an 11-quart Kolbe equipped with a condenser, stirrer and thermometer.

Add 105 f of methyl methacrylate, 1.5 g of benzoyl peroxide and 300 g of xylene, 1o
(Polymerization was carried out at 1 to 105°C for 8 hours. After the completion of the reaction, the internal temperature was lowered to 60°C, and a styrene-inobrene block compound (manufactured by Shell Chemical Company, CALIFLEX TR-1) was added.
107) 251 and 25f/xylene were added and stirred and dissolved to obtain a solution of a bipolymer composition. The viscosity of this solution (
25°C) is 690 cps, and the solid content concentration is 50 cm, so it can be used as an antifouling agent.

The proportions of each compound used in the silkworm production of the polymer composition are as follows.

Example 2 Tributyltin methacrylate 19 was added to the reaction vessel of Example 1.
5F, methyl methacrylate 105F, pen, 1.5 g of silver bar oxide, and 300 f of xylene were added, and polymerization was carried out at 100 to 105°C for 8 hours. After the reaction, the internal temperature was lowered to 60°C, and a styrene-butadiene block polymer (Califlex TR-1 manufactured by Shell Chemical Co., Ltd.
102) 90f, butyl acetate 40F and xylene 50
Add 9 and stir until dissolved.

A solution of the polymer composition was obtained. The viscosity of this solution (25”C
) is 720 cps, and the solid content concentration is 50 g, so it can be used as an antifouling agent. The proportions of each compound used in the production of the polymer composition are as follows.

Example 3 Tributyltin methacrylate 15 was added to the reaction vessel of Example 1.
0f, methyl methacrylate 150F, benzoyl peroxide 1.5g and xylene 300g,
Polymerization was carried out at 00-105°C for 8 hours. After that, the internal temperature was lowered to 60°C and the thermoplastic polyester elastomer (
30chi solution, manufactured by Toyobo Co., Ltd., Byron: 30S) 250
f was added and dissolved with stirring to obtain a solution of the bipolymer composition.

This solution has a viscosity (25°C) of 580 Cps and a solids concentration of 44.1%, and can be used as an antifouling agent. The proportions of each compound used in the production of the polymer composition are as follows.

Example 4 26.3 f of maleic anhydride was added to the reaction vessel of Example 1.

103 M of methyl methacrylate, 9 g of octyl acrylate, 0.49 g of benzoyl peroxide and 140.3 g of xylene were added and polymerized at 100 to 105°C for 4 hours.Next, the solution was once cooled to 80°C, and 0.4 g of benzoyl peroxide was added. Add 39 and then 100 to 10
Polymerization was carried out at 5°C for 4 hours. After that, lower the internal temperature to 90℃,
159.79 F of bis(tributyltin) oxide and 159.7 F of xylene were added, and the mixture was heated and stirred at 90'C for 2 hours to react. After the reaction, the internal temperature was lowered to 50'C, and polyethylene-butyl rubber graft polymer (manufactured by Allied Chemical Co., Ltd., ET-1100) 3B, 2f and butyl acetate 38. :1 was added and dissolved with stirring to obtain a solution of the 9 polymer composition. The viscosity of this solution (25°C) is 270 cps
The solid content concentration is 50%, and it can be used as is as an antifouling agent. The proportions of each compound used in the production of the polymer composition are as follows.

Comparative example 1 Add 180 f of tributyltin methacrylate to the reaction vessel.

Add 120 g of methyl methacrylate, 1.5 g of benzoyl peroxide and 300 g of xylene,
Polymerize for 8 hours at 05 °C. A polymer solution layer was obtained.

The viscosity (at 25° C.) of this solution was 810 cps, the solid content concentration was 50 cps, and the proportions of each compound used to produce the copolymer were as follows.

Comparative Example 2 Tributyltin methacrylate) 15 (1!
-'.

105 f of methyl methacrylate, 45 g of octyl acrylate, 1.59 g of benzoyl peroxide and 300 g of xylene were added and polymerized at 100 to 105°C for 8 hours to obtain a copolymer solution. Viscosity of this solution (25°C)
is 960 cps and the solids concentration is 50%.

The proportions of each compound used to produce the copolymer are as follows.

Comparative Example 3 Trimethyltin methacrylate 1201i' in the reaction vessel
Add 120F/1 methyl methacrylate, 30g butyl acrylate, 3of octyl acrylate, 1.5f/benzoyl peroxide, and 300g xylene.

Polymerization was carried out at 100-105°C for 8 hours to obtain a copolymer solution. The viscosity of this solution (25°C) is 1100 cps
in.

The solid content concentration was 50%, and the proportions of each compound used to produce the copolymer were as follows.

Comparative Example 4 In Example 1, 25 g of styrene-isoprene block polymer and 25 g of xylene were substituted for nib f/L/methacrylate polymer (40% solution, manufactured by Rohm & Haas, Acryloid F-10) 62.5F. A solution of the polymer composition was obtained in exactly the same manner as in Example 1 except for the addition of the following. The viscosity (25°C) of this solution was 650 cps, the solid content concentration was 49.1%, and the proportions of each compound used in the production of the bipolymer composition were as follows.

Comparative Example 5 A solution of the polymer composition was obtained in the same manner as in Comparative Example 4 except that 225 f was added in place of the butyl methacrylate polymer (40 T solution>62.51. The viscosity of this solution (25°C
) was 580 cps, the solid content concentration was 47.3%, and the proportions of each compound used in the production of 1 polymer were as follows.

Comparative Example 6 In Example 4, 95.5 g of butyl methacrylate polymer (40% solution, manufactured by Rohm & Haas, Acryloite F-10) was used instead of 38.29 g of polyethylene-butyl rubber graft polymer and 38.2 f of butyl acetate. A solution of the -C polymer composition was obtained in exactly the same manner as in Example 4 except that . The viscosity of this solution (at 25°C) is 260 c
ps, and the solid content concentration was 48.6%.

The proportions of each compound used in the production of the polymer composition are as follows.

The solutions or copolymer solutions of the polymer compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 6 were added to 13aRX7.7cIRX0
．． It was coated on both sides of a 3cIR glass plate to a dry film thickness of about 200μ. Each coated glass plate is immersed in artificial seawater for a certain period of time, for one week or one month.

Why not raise it after 3 months, 6 months and 12 months?

Tin eluted from the coating film was measured in the following manner.

The pulled-up coated glass plate was immersed in 1 liter of natural seawater whose liquid temperature was adjusted to 20°C, and the organic tin content was extracted for 2 hours while bubbling at a rate of +500 + W7/min. A portion of this seawater was taken for quantitative analysis of eluted tin. Results first
Shown in the table.

Table 1 (Note) The unit of numerical values in the table is pf Sn /d/day
.

Here, eluted tin (Sn) indicates the weight as bis(tributyltin) oxide.

■ Antifouling Test Using the polymer composition solutions or copolymer solutions obtained in Test Examples 1 to 4 and Comparative Examples 1 to 6, a 9th order ship bottom paint formulation was attempted.

Copolymer composition or copolymer (as solid content) 20 parts subdued acid
Chemical Copper 40 parts Benga
La 5
Part number
12 Part 1
Appropriate amounts of each paint were applied to both sides of a 17αX 9crrIX 0.3m hard vinyl chloride resin board to a dry film thickness of approximately 200μ, and a raft penetration test was conducted at Mie System 9 Owase Bay. I observed it. The results are shown in Table 2.

Table 2 (Note) The symbols in the table indicate the following.

○: No marine fauna or flora attached △: Attachment, less than 5% ×
Adhesive, 5-20% XX mark; Adhesive, 20 cm or more in the center of the aquarium with a diameter of 318 mm and a height of 44 mm
I installed a rotating drum in 0 order and made it possible to rotate it with a motor. Seawater was constantly pumped up to fill the aquarium, and an overflow port was installed so that fresh seawater constantly came into contact with the surface of the rotating drum.

The solutions of each polymer composition or copolymer solution obtained in Examples 1 to 4 and Comparative Examples 1 to 6 were applied to a galvanized iron plate coated with a rust-preventing primer to a dry film thickness of 150. It was applied so that it became u. Each coated galvanized iron plate was wrapped around the rotating drum of the above device and fixed in contact with seawater.

It was rotated in seawater at a speed of 37 h/hr for 90 days, and the initial film thickness on the galvanized iron plate and the remaining film thickness after 90 days were measured using a microscope, and the dissolved film thickness was calculated from the difference.

The results are shown in Table 3.

Table 3 Examples 5 to 1O Put the monomer compounds in the amounts listed in Table 4 and the same value of xylene into a reaction vessel, add 1.5 f of pe/zoylno z-oxide, and heat at 100 to 105°C for 8 hours. Polymerization was performed. To the obtained copolymer solution, a thermoplastic elastomer with a self-loading amount of H as shown in Table 4 and the same amount of solvent were added.

Stir and dissolve well to obtain a polymer composition. 0 Types of monomer compounds used and amount of inertia 0 Types of thermoplastic elastomer and amount of calories added 9 Ratio of each compound in the polymer composition (
h) is shown in Table 4.0 Examples 5 to 1 obtained in Table 4
Each polymer composition of O was also subjected to a tin elution test from a transparent coating film, an antifouling test, and a coating film solubility test.
Similar trends and good results were obtained when using polymer compositions 4 to 4.

Patent applicant Nitto Kasei Co., Ltd. Agent Patent Attorney Tetsuya Matsu

Claims (1)

[Claims] 1', (a) - 40 to 80 units of triorganotin salt of basic or (and) dibasic polymerizable unsaturated carboxylic acid
and (b) a triorganotin-containing copolymer containing 20 to 60% by weight of units of a polymerizable unsaturated compound selected from the group consisting of an acrylic compound, a vinyl compound having a functional group, and a vinyl hydrocarbon. An underwater antifouling composition characterized in that 3 to 40 parts by weight of a thermoplastic elastomer is added to 100 parts by weight of the composition.