JP2002327064A - Organopolysiloxanethioblock vinyl copolymer and antifouling paint composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organopolysiloxanethioblock vinyl copolymer for an antifouling paint, capable of forming an antifouling coating giving less load to environment and influence to human body, also excellent in antifouling property and its sustainability and excellent in mechanical strength, if it is blended in the antifouling paint. SOLUTION: An organopolysiloxanethioblock vinyl copolymer is formed from [A] a vinyl copolymer block having a polyoxyalkylene group and [B] a specific organopolysiloxanethioblock. The above vinyl copolymer block [A] is formed from (a1) a component unit derived from a polyoxyalkylene polymerizable unsaturated caboxylate shown by general formula [1]: R<4> [OR<1> ]m [OR<2> ]n -OCOR<3> (in general formula [1], R<1> and R<2> denote divalent hydrocarbon group, R<3> denotes a polymerizable nusaturated hydrocarbon containing group, and R<4> denotes a hydrogen atom, a hydrocarbon group or an organic carboxylic acid residual group, etc.), (a2) a component unit derived from a polymerizable unsaturated carboxylic acid or its ester, and (a3) a component unit derived from a crosslinkable polymerizable unsaturated monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organopolysiloxane thioblock vinyl copolymer suitably used as a resin for an antifouling paint and an antifouling paint composition containing the copolymer. The present invention relates to an organopolysiloxane thioblock vinyl copolymer which is suitable for use as an antifouling paint and has a low impact on the human body and a small effect on the human body, and an antifouling paint composition containing the copolymer.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Ship bottoms, fishing nets, seawater plumbing pipes, underwater structures, etc. are exposed to water for a long time,
When animals such as oysters, mussels and barnacles, plants such as laver (seaweed), and various aquatic organisms such as bacteria adhere and propagate on the surface, their appearance may be impaired and their functions may be impaired. .

[0003] In particular, when such aquatic organisms attach to and propagate on the bottom of the ship, the surface roughness of the bottom of the ship increases, which may cause a decrease in ship speed, an increase in fuel efficiency, and the like. Also, removing such aquatic organisms from the ship bottom requires a great deal of labor and work time. In addition, when aquatic organisms adhere to and grow on fish nets such as aquaculture nets and fixed nets, serious problems may occur, such as the lack of oxygen by the fish caught due to the obstruction of the mesh.

In addition, if aquatic organisms adhere to and breed in seawater supply / drainage pipes of thermal power plants, nuclear power plants, etc., the supply / discharge circulation of cooling water may be hindered. Conventionally, in order to prevent such damage, antifouling paints having excellent antifouling properties such as a copolymer of tributyltin methacrylate and methyl methacrylate, and a cuprous oxide (Cu
Those containing ₂ O) and have been applied. The copolymer in this antifouling paint is hydrolyzed in sea water to form bistributyltin oxide (tributyltin ether, Bu ₃ S
n-O-SnBu ₃ : Bu is a butyl group) or tributyltin halide (Bu ₃ SnX: X is a halogen atom)
Since it is an `` hydrolysable self-polishing paint '' that releases organic tin compounds such as etc. and exhibits an antifouling effect, and the hydrolyzed copolymer itself becomes water-soluble and dissolves in seawater, The bottom surface of the hull can be kept active without any resin residue.

However, such organotin compounds are highly toxic, and there are concerns about marine pollution, occurrence of malformed fish and malformed shellfish, and adverse effects on the ecosystem due to the food chain.
There has been a demand for the development of an antifouling paint having good antifouling properties without containing tin which can be used instead. Various studies and proposals have been made to solve such problems.

Further, without using a poison such as an organotin compound,
To prevent the adhesion of marine organisms, for example,
Japanese Patent No. 2995 discloses a non-toxic antifouling paint composition obtained by mixing a chemical reaction type silicone rubber, a petrolactam or liquid paraffin mixture, and a low-viscosity silicone oil, and JP-A-10-316933. Contains (a) a room-temperature-curable silicone rubber having a number-average molecular weight of 20,000 to 100,000, (b) a room-temperature-curable silicone rubber having a number-average molecular weight of 500 to 20,000, and (c) a silicone oil as main components. Coating compositions are disclosed.

However, so far, no harmful poisons have been used, the antifouling property and its durability have been excellent, the coating film strength has been excellent, and even if various additives have been blended, they do not become brittle, No resin for antifouling paint capable of forming an antifouling coating film having good physical properties such as adhesion has been found. JP-A-2-41307 discloses that one or more ethylenically unsaturated monomers and 100 parts by weight of an organopolysiloxane compound containing at least one thiol group are used. A method for producing an organopolysiloxane-modified copolymer, which is polymerized in the presence of 0.01 to 50 parts by weight per unit, is disclosed. It is described that it is used as a water repellent, an adhesion-imparting agent, icing prevention, paper sticking prevention, a base resin for weather-resistant paints, and the like.

In this publication, examples of the ethylenically unsaturated monomer include (meth) acrylic acid alkyl esters, alkoxyalkyl esters, alkenyl esters, and hydroxyalkyl esters. Examples of the organopolysiloxane compound containing at least one kind include 1 to n thiol groups (-SH
Group), or an organopolysiloxane having thiol groups at both ends of the main chain.

[0009] JP-A-3-88815 and corresponding Japanese Patent No. 2939309 disclose a free radical polymerizable monomer (1) and a specific formula:

[0010]

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(Wherein R ₁ , R ₃ , R ₅ , R ₆ : alkyl,
Aryl, alkoxy, OH, H, etc., R ₂ , R ₄ : divalent bonding group, x, q: integer of 0 to 3, y: integer of 10 or more, and the like. )) Represented by a mercapto-functional silicone compound (2)
And a free-radical-forming initiator (3) to perform a free-radical polymerization to obtain a vinyl-silicone copolymer. It is described that it can be used for agents, selectively permeable membranes, release coatings and the like.

The above-mentioned free radical polymerizable monomer
As (1), styrene, (meth) acrylic acid, (meth) acrylate, and the like are mentioned. JP-A-9-100445 discloses a coating composition comprising a copolymer having a polydimethylsiloxane block in a polymer chain and / or a copolymer having a polydimethylsiloxane chain grafted on the polymer chain. It describes that if the coating composition is applied to a building, the lubricity of the composition can prevent sticking paper and graffiti and maintain the landscape.

The above-mentioned polydimethylsiloxane block copolymer is obtained by polymerizing a polymerizable vinyl monomer using a polydimethylsiloxane compound having a group capable of generating a radical such as an azo group or a peroxy group. thing,
Examples thereof include those obtained by polymerizing a polymerizable vinyl monomer using a polydimethylsiloxane compound having an SH group introduced at a terminal, and a polydimethylsiloxane compound having an SH group introduced at the terminal. A polydimethylsiloxane compound having an epoxy group at a terminal is added to HS-CH ₂ CO
OH, it is described that obtained by adding the HS-CH ₂ CH ₂ COOH.

Further, the polymerizable vinyl monomer includes:
Examples thereof include aliphatic or cyclic (meth) acrylates such as methyl acrylate and ethyl acrylate, vinyl ethers, styrenes, nitriles, and vinyl chloride. However, these publications disclose an organopolysiloxane having, as polymerizable vinyl monomers, a copolymer block containing a component unit using a polyoxyalkylene polymerizable unsaturated carboxylate, and an organopolysiloxane thioblock vinyl. The siloxane thio block vinyl copolymer is not described or suggested at all, much less
There is no description or suggestion that the organopolysiloxane thioblock vinyl copolymer can be used for antifouling paint applications.

[0015] JP-A-9-157551 discloses that
A vinyl copolymer as a main chain, containing a graft copolymer having an organopolysiloxane unit and an organopolyoxyalkylene unit as a side chain bonded to the main chain, and an organic compound having an antifouling property. Underwater antifouling agent is described, and it is described that a coating film made of the underwater antifouling agent can prevent adhesion of marine organisms to a substrate.

Further, the graft copolymer comprises an organopolysiloxane compound having a radically polymerizable group such as (meth) acryloyloxy, a polyoxyalkylene compound having a radically polymerizable group, and a vinyl monomer. It is described that it can be obtained by copolymerization.
In the graft copolymer described in this publication, instead of having an organopolysiloxane unit and an organopolyoxyalkylene unit in the vinyl-based copolymer main chain, as a side chain from the vinyl-based copolymer main chain, Since the organopolysiloxane unit and the organopolyoxyalkylene unit are bonded, the resulting antifouling coating film is insufficient in mechanical strength and antifouling property.

Japanese Patent No. 2863562 discloses that the following formula (1):

[0018]

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(M: positive integer, X: divalent hydrocarbon group, etc.)
_{R 1, R 2, R 3} : C1~4 alkyl group, an alkoxy group, a phenyl group, Y, Z: same groups or the formula and the like R ₁ (2):

[0020]

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Represents an organosiloxane group represented by ) As a chain transfer agent, and a block copolymer of a polysiloxane-vinyl polymer obtained by polymerizing a radical polymerizable vinyl monomer in the presence of a radical initiator as a film-forming component. An antifouling coating composition containing a water-repellent substance is disclosed. The publication states that the antifouling coating composition can form a coating film that is nontoxic and has excellent antifouling performance. Examples of the radical polymerizable vinyl-based monomer include (meth) acrylates such as methyl (meth) acrylate, styrenes, and vinyl esters.

However, the coating film made of the antifouling coating composition described in the publication has poor antifouling properties and poor mechanical strength. The publication also discloses, as a polymerizable vinyl monomer,
A copolymer block containing a component unit using a polyoxyalkylene polymerizable unsaturated carboxylate, and an organopolysiloxane thioblock vinyl copolymer having an organopolysiloxane thioblock vinyl are not described or suggested at all. Furthermore, there is no description or suggestion that the organopolysiloxane thioblock vinyl copolymer can be used for antifouling paint applications.

Japanese Patent Application Laid-Open No. 9-216922 discloses that
Polyorgano obtained by polymerizing a hydrophilic ethylenically unsaturated monomer and a hydrophobic ethylenically unsaturated monomer, or an amphiphilic ethylenically unsaturated monomer in the presence of a polyorganosiloxane having a mercapto group-containing organic group. Disclosed is a water resistance imparting agent comprising a siloxane-modified amphiphilic polymer. The water resistance imparting agent can improve the water resistance of a formed film by being added to an emulsion resin, and can be added to an ink composition. Describes that the water resistance (waterproofness) of the formed coating is significantly improved.

The publication also discloses (meth) acrylamide, maleic acid and the like as the hydrophilic ethylenically unsaturated monomers, and methoxypolyethylene glycol monomethacrylate and polypropylene glycol as the amphiphilic ethylenically unsaturated monomers. Monomethacrylate, polyethylene glycol polypropylene glycol monomethacrylate and the like are mentioned, and as the hydrophobic ethylenically unsaturated monomer, (meth) acrylates such as methyl (meth) acrylate and styrenes are mentioned.

Further, among the polyorganosiloxanes having a mercapto group-containing organic group, those having a main chain skeleton of polydialkylsiloxane include polydialkylsiloxanes at the side chain, at both ends, at one end, or at the side chain. And those having an SH group introduced at both ends. However, in this publication, a water-resistance imparting agent, which is a polyorganosiloxane-modified amphiphilic polymer,
It can be added as a film-forming component for an antifouling paint, and if the water-resistance imparting agent, which is an amphiphilic polymer, is added to the antifouling paint composition, the antifouling property and its durability are excellent, and the mechanical strength is high. There is no description or suggestion that a good antifouling coating film can be formed.

In Japanese Patent Publication No. 54-28438,
(i) In a matrix of a thermoplastic vinyl polymer, (ii) a graft copolymer obtained by dispersing gel particles of a rubber-like organopolysiloxane, wherein component (i) is polymethyl methacrylate and styrene. Component (ii) is selected from the group consisting of copolymers of a series monomer and a small amount of an acrylonitrile monomer, and the component (ii) has the formula: HSRSi (R ′) O [R: a divalent saturated hydrocarbon group of C1-8, R ′: C1-8, a monovalent hydrocarbon group containing no aliphatic unsaturation]
It is described that dimethylsiloxane units are the main component (ie, essentially all), and the graft copolymer is obtained by dispersing the component (ii) in at least one monomer of the component (i). , Are prepared by bulk or suspension polymerization in the presence of free radical generators.

However, this publication discloses that as a polymerizable vinyl monomer, a copolymer block containing a component unit using a polyoxyalkylene polymerizable unsaturated carboxylate and an organopolysiloxane thioblock vinyl are used. There is no description or suggestion of the organopolysiloxane thioblock vinyl copolymer, and moreover, there is no description or suggestion that the organopolysiloxane thioblock vinyl copolymer can be used for antifouling paint applications. Not.

[0028]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems associated with the prior art as described above, and when incorporated into an antifouling paint, has less impact on the environment and the effect on the human body. Organopolysiloxane thioblock vinyl copolymer for antifouling paint capable of forming an antifouling coating film having excellent antifouling property and its durability and excellent mechanical strength, and antifouling containing the copolymer It is intended to provide a coating composition.

In particular, according to the present invention, even when silicone oil, paraffin wax and the like are blended, the above-mentioned characteristics are exhibited and a coating film capable of effectively suppressing the brittleness of the coating film can be formed. An object of the present invention is to provide an organopolysiloxane thioblock vinyl copolymer for an antifouling paint and an antifouling paint composition containing the copolymer.

[0030]

SUMMARY OF THE INVENTION The organopolysiloxane thioblock vinyl copolymer of the present invention has the following formula (A) (a1):
Is represented by [I], the polyoxyalkylene compound is at least its one end with the heavy polymerizable unsaturated carboxylic acid ester to form formed by polyoxyalkylene polymers unsaturated carboxylates: general formula [I]: R ⁴ [ OR ^l ] _m [OR ² ] _n -OCOR ³ ... [I] In the formula [I], R ¹ and R ² represent a divalent hydrocarbon group which may be the same or different from each other. , R ³ represents a polymerizable unsaturated hydrocarbon group-containing group, and R ⁴ represents a hydrogen atom, a monovalent hydrocarbon group which may have a polymerizable unsaturated bond, or a polymerizable unsaturated bond. A monobasic or dibasic organic carboxylic acid residue which may have: “R ⁵ CO— (R
⁵ represents an organic group which may contain a polymerizable unsaturated bond. ) ", And m and n are positive numbers. (A2) at least one non-crosslinkable polymerizable unsaturated carboxylic acid other than the component (a1) or an ester thereof, and (a3) a crosslinkable polymerizable unit. A component unit derived from an unsaturated monomer,
(A4) If necessary, a polyoxyalkylene group-containing vinyl copolymer block formed from a component unit derived from another polymerizable unsaturated monomer, and [B] a general formula [II]:

[0031]

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In the formula [II], R ⁶ represents 1 to 10 carbon atoms.
Of a hydrocarbon group, R ^7, R ⁸ and R ⁹ are each independently a number of carbon atoms a divalent organic machine 20 a (preferably thio organic group or a similar group as the R ⁶⁾ And n and m are positive numbers. Having an average molecular weight (Mw) of 1,000 to 200,000 as measured by GPC.
Preferably, it is 2,000 to 100,000.

In the present invention, the component unit (a) derived from the above polymerizable unsaturated carboxylic acid or its ester
2) is preferably a component unit derived from (meth) acrylic acid or an ester thereof. In the present invention, the component unit (a1) derived from the polyoxyalkylene polymerizable unsaturated carboxylate [I] is preferably a component unit derived from polyoxyalkylene (meth) acrylate.

In the present invention, the component unit (a3) derived from the cross-linkable polymerizable unsaturated monomer is a cross-linkable group having a hydroxyl group, an alkoxysilyl group, an aryloxysilyl group, an epoxy group, an isocyanate group, It is desirable to be derived from an unsaturated monomer containing at least one of a carboxyl group, a (meth) acryloxy group, a vinyl group, a silanol group, and an amino group.

In the present invention, styrenes, vinyl esters, (meth) acrylamides, vinyl ethers, itaconic acid, maleic acid, fumaric acid, citraconic acid may be used as other component units (a4) if necessary. And derivatives thereof, and those derived from at least one of acrylonitrile.

The antifouling coating composition according to the present invention is characterized by containing any of the above-mentioned organopolysiloxane thioblock vinyl copolymers as a vehicle component. The organopolysiloxane thioblock vinyl copolymer composition and the antifouling coating composition according to the present invention,
It is characterized by containing the organopolysiloxane thioblock vinyl copolymer [I] described in any one of the above and a water repellent component [II] (preferably silicone oils and / or paraffins).

The antifouling coating composition according to the present invention may further contain an antifouling agent. The antifouling coating film according to the present invention is characterized by being formed from the organopolysiloxane thioblock vinyl copolymer composition or the antifouling coating composition described in any of the above.

The substrate according to the present invention is characterized in that the substrate is covered with an antifouling coating film formed from the organopolysiloxane thioblock vinyl copolymer composition or the antifouling coating composition described above. And In the underwater structure according to the present invention, the surface of the substrate is coated with an antifouling coating film formed from the organopolysiloxane thioblock vinyl copolymer composition or the antifouling coating composition according to any of the above. It is characterized by having.

In the ship according to the present invention, the surface of the ship base material is
It is characterized by being coated with an antifouling coating film formed from the organopolysiloxane thioblock vinyl copolymer composition or the antifouling coating composition according to any of the above. The antifouling method for a substrate according to the present invention, the surface of the substrate, an antifouling coating film formed from the organopolysiloxane thioblock vinyl copolymer composition or the antifouling coating composition according to any of the above. It is characterized by coating.

According to the present invention, when incorporated into an antifouling paint,
An organopolysiloxane thioblock vinyl copolymer which has a low impact on the environment and the effect on the human body, and which is excellent in antifouling property and its durability and capable of forming an antifouling coating film having excellent mechanical strength; and A paint represented by an antifouling paint containing the copolymer is provided. In particular, according to the present invention, even when silicone oils, paraffins, and the like are blended, the above-mentioned properties are exhibited, and further, a coating film capable of effectively suppressing the brittleness of the coating film can be formed. Provided are an organopolysiloxane thioblock vinyl copolymer and a paint containing the copolymer, such as an antifouling paint.

[0041]

DETAILED DESCRIPTION OF THE INVENTION The organopolysiloxane thioblock vinyl copolymer preferably used as an antifouling paint according to the present invention and an antifouling paint composition containing the copolymer are specifically described below. Will be described. [Organopolysiloxane thioblock vinyl copolymerization
The organopolysiloxane thioblock vinyl copolymer according to the present invention is composed of the following polyoxyalkylene group-containing vinyl copolymer block [A] and organopolysiloxane thioblock [B]. .

The weight average molecular weight (Mw) of such an organopolysiloxane thioblock vinyl copolymer measured by GPC is usually from 1,000 to 200,000, preferably from 2,000 to 100,000. Desirably. When the molecular weight is in such a range, the obtained copolymer has a viscosity suitable for handling at an appropriate concentration as a solution or an antifouling coating composition, and the antifouling coating composition containing the copolymer has The viscosity becomes suitable for coating, and the resulting coating film (especially antifouling coating film) has appropriate strength and tends to have excellent antifouling durability. <Polyoxyalkylene group-containing vinyl copolymer block
[A]> The polyoxyalkylene group-containing vinyl copolymer block [A] is, (a1) represented by the following formula [I], and weight polymerizable unsaturated carboxylic acid polyoxyalkylene compound at least at its one end A component unit derived from a polyoxyalkylene polymerizable unsaturated carboxylate that forms an ester (hereinafter, also referred to as a “polyoxyalkylene polymerizable unsaturated carboxylate component unit”); and (a)
2) a component unit derived from at least one non-crosslinkable polymerizable unsaturated carboxylic acid or an ester thereof other than the component (a1) (non-crosslinkable polymerizable unsaturated carboxylic acid-based component unit); and (a3) Component units derived from cross-linked polymerizable unsaturated monomers (cross-linked polymerizable unsaturated monomer component units)
And (a4) a component unit derived from another polymerizable unsaturated monomer, if necessary.

First, the polyoxyalkylene polymerizable unsaturated carboxylate component unit (a1) will be described. <Polyoxyalkylene polymerizable unsaturated carboxylate
Component unit (a1)> Polyoxyalkylene polymerizable unsaturated carboxylate Component unit (a1) is a component unit derived from polyoxyalkylene polymerizable unsaturated carboxylate [I] represented by the following formula [I]. is there.

[I]: R ⁴ [OR ¹ ] _m [OR ² ] _n -OCOR ³ ... [I] In the formula [I], R ¹ and R ² may be the same or different from each other. It shows a good divalent hydrocarbon group, and includes an aliphatic group, an alicyclic group, and an aromatic group, and an aliphatic group is preferable. Specifically, for example, a methylene group, an ethylene group, a propylene group (trimethylene: -(CH ₂ ) _3- , methyl dimethylene:-
_{CH 2 CH (CH 3) -} ), butylene group (tetramethylene), 1 to 10 carbon atoms, preferably 1 to 5 poly (methylene) group.

R ³ represents a group containing a polymerizable unsaturated hydrocarbon group, for example, a vinyl group (CH ₂ ＣＨCH—), CH ₂ ＣC
_{(CH 3) -, CH 3} -CH = CH-, CH 3 -CH = C
_{(CH 3) -, HOCOCH =} CH-, CH 3 OCOCH =
Total carbon number of 2 to 15, preferably 2 to 10
And an unsaturated hydrocarbon group-containing group which may have a substituent.

That is, as the formula “R ³ COO-”,
R ³ COO— represents a polymerizable unsaturated carboxylic acid residue, for example, a (meth) acryloyloxy group [CH ₂
= C (H or CH ₃₎ COO-] other, dibasic polymerizable maleinoyloxy group derived from an unsaturated carboxylic acid (HOOCCH = CHCOO-, sis), fumaroyloxy group (HOOCCH = CHCOO-, trans) Groups such as
And their esters, the total carbon number of which is 2 to 16,
Preferably it is 2 to 11, and a substituent (eg, -COO
And H) a polymerizable unsaturated carboxylic acid residue (polymerizable unsaturated group-containing carbonyloxy group).

R ⁴ is a hydrogen atom (a), a monovalent hydrocarbon group optionally having a polymerizable unsaturated bond (b), or an organic carboxylic acid optionally having a polymerizable unsaturated bond. The residue “R ⁵ C
O-(R ⁵ represents an organic group which may contain a polymerizable unsaturated bond.) "Indicating the (c). This organic carboxylic acid residue
(C) may be monobasic or dibasic.

When R ⁴ is a monovalent hydrocarbon group (II) which may have a polymerizable unsaturated bond, examples of such a hydrocarbon group (II) include the aforementioned R ³ and Similar groups, CH ₂ ＣＨCH—, CH ₂ ＣC (CH ₃ ) —, CH ₃ —CH
_{= CH-, CH 3 -CH = C} (CH 3) - in addition to such, CH
_{3 -, C 2 H 5 -} , C 3 H 7 -, C 4 H 9 - carbon atoms such as 1 to 1
0, preferably an alkyl group having 1 to 5; an aryl group having 6 to 20 carbon atoms which may have a substituent; CH ₃ CO—,
_{C 2 H 5 CO-, C 3} H 7 CO-, 1~10 carbon atoms such as C ₄ H ₉ CO-, preferably 1-5 alkylcarbonyl group;
Among them, a hydrogen atom and the above-mentioned alkyl group are preferable.

The alkyl group contained in the above alkyl group or alkylcarbonyl group may be any of linear, branched, alicyclic and the like. In the above formula [I], m and n each represent a positive number, preferably a number of 1 to 50, respectively. Examples of the polyoxyalkylene polymerizable unsaturated carboxylate [I] from which the polyoxyalkylene polymerizable unsaturated carboxylate component unit (a1) can be derived include those described in JP-A-9-216922, paragraph [0009]. And the like, specifically, for example, polyethylene glycol monomethacrylate (eg:
Nippon Oil & Fats Co., Ltd. Blenmer PE series, PE-90, PE-2
00, PE-350), methoxypolyethylene glycol monomethacrylate (eg, Blemmer PME series, PME-100, PME-200, PME-400, manufactured by NOF Corporation), polypropylene glycol monomethacrylate (eg, NOF Corporation) Blemmer PP series, PP-1000, PP-500, PP
-800), polyethylene glycol polypropylene glycol monomethacrylate (eg, Blemmer PEP series, 70PEP-370B, manufactured by NOF Corporation), polyethylene glycol polytetramethylene glycol monomethacrylate (eg, Blemmer 55PET-800, manufactured by NOF Corporation) , Polypropylene glycol polytetramethylene glycol monomethacrylate (eg, Blemmer NK manufactured by NOF Corporation)
H-5050), polypropylene glycol monoacrylate (eg, Blemmer AP-400 manufactured by NOF Corporation), polyethylene glycol monoacrylate (eg, NOF Corporation)
Ltd. Blemmer AE-350), further, methoxy polyethylene glycol _{monoacrylate: [H 3 C- (OC 2} H 4) m + n -OCO (CH) = CH
_2], ethoxy polyethylene glycol _{monomethacrylate: [H 5 C 2 - (} OC 2 H 4) m + n -OCOC (CH 3) = CH 2
], Methyl carboxymethyl polyethylene glycol _{monomethacrylate: [H 3 C-CO- (} OC 2 H 4) m + n -OCOC (CH 3) =
CH ₂ ], methyl carboxy polypropylene glycol monomethacrylate: [H ₃ C—CO— (OC ₃ H ₆ ) _{m + n} —OCORC (CH ₃ )
= CH ₂ ], methoxypolyethylene glycol polypropylene glycol monomethacrylate: [H ₃ C- (OC ₂ H ₄ ) _m (O
_{C 3 H 6) n -OCORC (} CH 3) = CH 2], carboxymethylene carboxymethyl polyethylene glycol _{monomethacrylate: [HOCO-CH 2 -CO (} OC 2 H 4) m + n -OCOC (C
H ₃₎ = CH _2], hydroxy maleic oil polyethylene glycol _{monomethacrylate: [HOOCCH = CHCO (OC 2} H 4) m + n -OCOC
_{(CH 3) = CH 2]} , polyethylene glycol _{dimethacrylate: [CH 2 = CHCO- (OC} 2 H 4) m + n -OCOC (C
H ₃₎ = CH _2], polyethylene glycol _{dimethacrylate: [CH 2 = C (CH} 3) CO- (OC 2 H 4) m + n -OCOC
(CH ₃ ) = CH ₂ ], phenoxy polyethylene glycol monomethacrylate:

[0050]

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And the like. These are one or two
Used in combination of more than one species. Among these polyoxyalkylene polymerizable unsaturated carboxylates [I], polyoxyalkylene (meth) acrylates [the number of carbon atoms of the oxyalkylene group: 1 to 10] are preferable, and methoxypolyethylene glycol mono (meta) is more preferable. )
Acrylate [number of repeating ethylene glycol: 2
100] is desirable. <Non-crosslinkable polymerizable unsaturated carboxylic acid component unit (a2)
> Non-crosslinkable polymerizable unsaturated carboxylic acid component unit (a2)
Is derived from “at least one non-crosslinkable (non-crosslinkable) polymerizable unsaturated carboxylic acid or ester thereof” other than the above-mentioned component polyoxyalkylene polymerizable unsaturated carboxylate component unit (a1). Is a component unit.

Such a (non-crosslinked) polymerizable unsaturated carboxylic acid or ester thereof is disclosed in Japanese Patent No. 29393.
For example, polymerizable vinyl monomers described in JP-A-09-2009, page 13, right column, lower stage to page 14, left column upper column, or JP-A No. 9-100455, page 3, left column to right column [0007] column can be used. Specifically, for example, α, β-unsaturated carboxylic acids such as (meth) acrylic acid, itaconic acid, maleic acid, crotonic acid, citraconic acid, and maleic anhydride, and acid anhydrides thereof; methyl (meth) acrylate , Ethyl (meth)
Acrylate, n-propyl (meth) acrylate, i
So-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl ( (Meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, N-
(1,1-dimethyl-3-oxobutyl) (meth) acrylate, isobornyl (meth) acrylate, methoxyethyl (meth) acrylate, etc., which have about 1 to 30 carbon atoms and are aliphatic, alicyclic or aromatic. (Meth) acrylic acid esters; amino group-containing unsaturated carboxylic acid esters such as dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate and diethylaminoethyl (meth) acrylate; (meth) acryloxypropyl polydimethylsiloxane And unsaturated fluorine-containing carboxylic acid esters such as 2,2,2-trifluoroethyl (meth) acrylate and 1H, 1H, 2H, 2H-heptadecafluorodecyl (meth) acrylate. Is mentioned.

These polymerizable unsaturated carboxylic acids, acid anhydrides and polymerizable unsaturated carboxylic esters can be used alone or in combination of two or more. Among these polymerizable unsaturated carboxylic acids, acid anhydrides and polymerizable unsaturated carboxylic acid esters, the above-mentioned (meth) acrylic acid and esters thereof are preferable, and furthermore, those having 1 carbon atom
The above (meth) acrylic acid and its alkyl ester of 30 to 30 aliphatic and alicyclic groups are preferable. <Cross-Linking Polymerizable Unsaturated Monomer Component Unit (a3)> Examples of the cross-linking polymerizable unsaturated monomer component unit (a3) include the cross-linking polymerizable unsaturated monomer other than (a1) and (a2). A component unit derived from a monomer ".

Examples of the crosslinkable polymerizable unsaturated monomer capable of deriving the polymerizable unsaturated monomer component unit (a3) having a crosslinkable group (also referred to as a crosslinkable group) include, for example, if necessary. As a polymerizable unsaturated monomer having an OH group capable of reacting with a crosslinking agent used, hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate, (poly) caprolactone (meth) acrylaten, 2-hydroxybutyl (meth) acrylate and the like,
As self-crosslinkable hydrolyzable silyl group-containing polymerizable unsaturated monomers, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxy Propylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropylmethoxyethoxysilane, vinyltriacetoxysilane, p-trimethoxysilylstyrene, p-triethoxysilylstyrene, p -Trimethoxysilyl-
α-methylstyrene, p-triethoxysilyl-α-methylstyrene, vinyltrimethoxysilane, vinyltriethoxysilane, N-β (N-vinylbenzylaminoethyl-γ-aminopropyl) trimethoxysilane, hydrochloride, etc. As a polymerizable unsaturated monomer having an epoxy group capable of reacting with a crosslinking agent used as needed,
Glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl (meth) acrylate, etc., are self-crosslinkable or can react with a crosslinking agent used as necessary. (Meth) acryloyl isocyanate as a polymerizable unsaturated monomer having an isocyanate group, 2-
(Meth) acryloxyethyl isocyanate and the like. As a polymerizable unsaturated monomer having a carboxyl group capable of reacting with a crosslinking agent used as necessary, (meth) acrylic acid, maleic acid and derivatives thereof, itaconic acid And its derivatives.

The component unit (a3) derived from the above-mentioned crosslinkable polymerizable unsaturated monomer may be, if necessary, a component unit having a (meth) acryloxy group or a vinyl group which is a crosslinkable group formed by radical polymerization or the like. Derivation to (a3) is possible, and further derivation to a component unit (a3) having a silanol group or an amino group, which is another crosslinking system, is also possible. Among these “crosslinkable polymerizable unsaturated monomers”, from the viewpoints of film forming properties, coating film strength, heat resistance, oil resistance, etc. of the obtained organopolysiloxane thioblock vinyl copolymer,
In a coating film obtained from a paint or the like containing the copolymer, it is desirable that the copolymer forms a crosslinked structure, and the “crosslinkable polymerizable unsaturated monomer” includes a hydroxyl group, an alkoxy group, Silyl group, aryloxysilyl group,
Any one or more functional groups of epoxy group, isocyanate group, carboxyl group, (meth) acryloxy group, vinyl group, silanol group, amino group and the like, preferably hydroxy group, isocyanate group, epoxy group, alkoxysilyl group It is desirable to use a crosslinkable polymerizable unsaturated monomer having at least one of the above functional groups.

These crosslinkable polymerizable unsaturated monomers include 2-hydroxyethyl (meth) acrylate, 3 (or 2) -hydroxypropyl (meth) acrylate,
(Or 2) -hydroxybutyl (meth) acrylate, γ
-(Meth) acryloxypropyltrimethoxysilane,
It is particularly desirable to use γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, and glycidyl (meth) acrylate.

These “crosslinkable polymerizable unsaturated monomers”
Can be used alone or in combination of two or more. <Other polymerizable unsaturated monomer component unit (a4)> As the other polymerizable unsaturated monomer component unit (a4), a unit other than the above (a1), (a2) and (a3) is used as necessary. Component unit derived from the resulting polymerizable unsaturated monomer.

The polymerizable unsaturated monomer capable of deriving the component unit (a4) may be any known radical polymerizable unsaturated monomer capable of forming a vinyl copolymer block component. Monomers can also be used. For example, styrenes such as styrene and α-methylstyrene; vinyl esters such as vinyl acetate and vinyl propionate; acrylamides such as N, N-dimethylacrylamide and dimethylaminoethylacrylamide; vinyl ethers such as ethyl vinyl ether and isobutyl vinyl ether; Examples thereof include dibasic polymerizable monomers such as itaconic acid, maleic acid, fumaric acid, and citraconic acid, and esters thereof; acrylonitrile.

These "other polymerizable unsaturated monomers"
Can be used alone or in combination of two or more as necessary. In the present invention, the polyoxyalkylene group-containing vinyl copolymer block [A] (100% by weight)
In the above, the polyoxyalkylene polymerizable unsaturated carboxylate component unit (a1) is usually 0.1 to 50% by weight, preferably 0.5 to 30% by weight, particularly preferably 1% by weight.
The amount of the polymerizable unsaturated carboxylic acid-based component unit (a2) is usually 1 to 99.9% by weight, preferably 5 to 99.5% by weight, particularly preferably 20 to 99.
In an amount of 0% by weight, the above-mentioned crosslinkable polymerizable unsaturated monomer component unit (a3) is usually 0.1 to 80% by weight, preferably 1 to 70% by weight, particularly preferably 3 to 40% by weight. Is desirably contained in an amount of

The other polymerizable unsaturated monomer component unit (a4) is usually 0 to 80% by weight, preferably 0 to 70% by weight.
%, Particularly preferably from 0 to 50% by weight. With such an amount, each component unit (a1) and (a
2) When (a3) and (a4) are contained in the polyoxyalkylene group-containing vinyl copolymer block [A],
The resulting organopolysiloxane thioblock vinyl copolymer (also referred to as silicone block vinyl copolymer) has an appropriate film-forming property, has a good coating film strength, and tends to have excellent antifouling properties.

The Tg of the above polyoxyalkylene group-containing vinyl copolymer block [A] or the corresponding polyoxyalkylene group-containing vinyl copolymer is usually -7.
The temperature is preferably 5 ° C. or more, more preferably −30 ° C. or more, from the viewpoint of film forming properties. The polyoxyalkylene group-containing vinyl copolymer block [A] 100 contained in 100 parts by weight of the organopolysiloxane thioblock vinyl copolymer is used.
Parts by weight of organopolysiloxane thioblock
[B] is usually 0.01 to 900 parts by weight, preferably 0.1 to 900 parts by weight.
Desirably, it is present in an amount of 1-700 parts by weight.

When each of the blocks [A] and [B] is contained in the organopolysiloxane thioblock vinyl copolymer in such an amount, the organopolysiloxane thioblock vinyl copolymer has poor adhesion. The surface tends to be formed and the antifouling property tends to be good. In the polyoxyalkylene group-containing vinyl copolymer block [A], the polymerizable unsaturated bond (carbon-carbon double bond) in the monomer (polyoxyalkylene polymerizable unsaturated carboxylate [I]) is used.
A component unit (a1) obtained by cleaving, a component unit (a2) obtained by similarly cleaving a polymerizable unsaturated bond contained in a corresponding monomer, and a component unit (a3), if necessary. It is considered that the component unit (a4) used is linked randomly or arranged in blocks to form a copolymer block. <Organopolysiloxane thio block [B]> The organopolysiloxane thio block [B] which forms the organopolysiloxane thio block vinyl copolymer of the present invention together with the polyoxyalkylene group-containing vinyl copolymer block [A]. B] is represented by the following formula [II].

[B] General formula [II]:

[0064]

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In the formula [II], a plurality of R ⁶ are
A hydrocarbon group of 10; R ⁶ is, for example, an alkyl group having 1 to 10, preferably 1 to 5, particularly 1 to 3 carbon atoms such as a methyl group, an ethyl group, or a propyl group; a phenyl group;
Examples thereof include a fluoroalkyl group, and the above-mentioned alkyl group, particularly a methyl group, is preferred. R ⁷ , R ⁸ and R ⁹ are
Each independently represents a divalent organic group having 1 to 20 carbon atoms, preferably a divalent thioorganic group having the same carbon number (eg: thiohydrocarbon group) or a group similar to the aforementioned R ⁶ ; More preferably, the above-mentioned divalent thio organic group is desirable.

The divalent thioorganic group has the formula: “—SX—”
(X: divalent organic group which may have a substituent)
You. The thioorganic group is disclosed in Japanese Patent No. 2863562.
Thiomethylene group (-S-CH)
_Two-), Thiodimethylene group (-S- (CH_Two)_Two-), Thioto
Limethylene group (-S- (CH_Two)_Three-), Thiopropylene group
"-S-CH (CH_Three) CH_Two-", Thiobutylene group" -S-C
H_TwoCH (CH_Three) CH_Two-", Thiodimethylmethylene group"-
SC (CH_Three)_Two-", Thiodimethylethylene group" -S-C
H_TwoC (CH_Three)_Two-", Thiooctamethylene group" -SC (C
H_Three)₈The number of carbon atoms that may have branches, such as "-"
Having 1 to 10 and having a chain divalent hydrocarbon group
Element group; thiophenylene group “—S—C₆H_Four-", Thiopheni
Renethylene group "-S-C₆H _Four-(CH_Two)_Two-"
A thiohydrocarbon group having an aromatic divalent hydrocarbon group;
Further, as described in JP-A-9-100445,
A polydimethylsiloxane compound having an epoxy group at the end
HS-CH_TwoCOOH, HS-CH_TwoCH _TwoCOO
A divalent organic group derived from a structure obtained by adding H
And a thio organic group having the formula:

Among these thio organic groups "-SX-", a thio hydrocarbon group having a chain divalent hydrocarbon group (X) having 1 to 5 carbon atoms such as a thiotrimethylene group is preferable.
The above m indicates the total number (positive number) of the repeating units [SiO (R ⁶ ) ₂ ], and n indicates the repeating unit [Si
O (R ⁶ ) (R ⁹ −)], the total number (positive number) of the repeating units [SiO (R ⁶ ) ₂ ] and [SiO (R ⁶ ) (R ⁹
-)] May be combined in an arbitrary order so that the total number of each repeating unit is m or n. For example, each repeating unit may be alternately arranged one by one and connected, or each may form and arrange an arbitrary number of blocks, and the total number of each repeating unit may be m or n, respectively. Good.

The organopolysiloxane thio block [B] includes the following four types (1) to (4) depending on the types of R ⁷ , R ⁸ and R ^{9 in} the formula [II]. (These formulas [I
In I-1] to [II-4a], R ¹⁰ represents a divalent organic group having 1 to 10, preferably 1 to 5 carbon atoms. R ⁶ is the same as in formula [II]. (1) In the formula [II], one end group R ⁷ of the organopolysiloxane
Or R ⁸ represents a divalent thioorganic group, and R ⁸ and R
Wherein ⁹ represents the same group as R ⁶ (single-terminal type):

[0069]

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Examples of the mercapto-modified polyorganosiloxane [II-1a] from which the organopolysiloxane thioblock [II-1] can be derived include the following.

[0071]

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(In the formulas [II-1] and [II-1a], R ¹⁰ is a propylene group “—CH (CH ₃ ) CH ₂ —” or a trimethylene group “— (CH ₂ ) ₃ —”, and R ⁶ is A methyl group, a phenyl group, or a fluoroalkyl group; m + n = 2 to 1,500.) Such a mercapto-modified polyorganosiloxane [II
[1a], more specifically, α-mercaptopropyl polydimethylsiloxane, epoxy group-containing polydimethylsiloxane (product name: “Silaplane FM-0511, FM-05
21, FM-0525 ", manufactured by Chisso Corporation). (2) In the formula [II], R ⁷ and R ⁸ each represent a divalent thiohydrocarbon group, and R ⁹ represents the same group as R ⁶ (both terminal type):

[0073]

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Examples of the mercapto-modified polyorganosiloxane [II-2a] from which the organopolysiloxane thioblock [II-2] can be derived include the following.

[0075]

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(In the formulas [II-2] and [II-2a], R ¹⁰ is a propylene group “—CH (CH ₃ ) CH ₂ —” or a trimethylene group “— (CH ₂ ) ₃ —”, and R ⁶ is It represents a methyl group, a phenyl group, or a fluoroalkyl group. M + n = 2 to 1500.) Such a mercapto-modified polyorganosiloxane [II
More specifically, "X-22-167B" manufactured by Shin-Etsu Chemical Co., Ltd. and the like can be mentioned as -2a]. (3) In the formula [II], both R ⁷ and R ^8, wherein indicates the same group as R ^6, at least one of R ⁹ of a plurality of (n) (n-p pieces) 2 The remaining R ⁹ (p) represents a group similar to the above R ⁶ , or all of a plurality of R ⁹ (p = 0, n) represent a divalent thiohydrocarbon group; Which shows a thiohydrocarbon group (side chain type):

[0077]

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Examples of the mercapto-modified polyorganosiloxane [II-3a] from which the organopolysiloxane thioblock [II-3] can be derived include the following.

[0079]

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(In the formulas [II-3] and [II-3a], R ¹⁰ represents a propylene group “—CH (CH ₃ ) CH ₂ —” or a trimethylene group “— (CH ₂ ) ₃ —”, and R ⁶ represents Represents a methyl group, m = 1 to 1
500, n = 1 to 100, 0 ≦ p ≦ n (p: integer). ) Such a mercapto-modified polyorganosiloxane [II
-3a], more specifically, manufactured by Shin-Etsu Chemical Co., Ltd.
Product name "KF-2001, KF-2004, KP-35
8 "and the like. (4) In the formula [II], both R ⁷ and R ^{8 represent} a divalent thiohydrocarbon group, and at least one of R ⁹ (np)
Represents a divalent thiohydrocarbon group, and the remainder (p
R ⁹ represents the same group as R ⁶ , or all of R ⁹ (p = 0, n) represent a divalent thiohydrocarbon group (both side chain type):

[0081]

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(In these formulas [II-1] to [II-4], R
¹⁰ represents a divalent hydrocarbon group having 1 to 10, preferably 1 to 5 carbon atoms. R ⁶ is the same as in formula [II]. ) Such an organopolysiloxane thio block [II-
Examples of the mercapto-modified polyorganosiloxane [II-4a] from which [4] can be derived include the following.

[0083]

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(In the formulas [II-4] and [II-4a], R ¹⁰ is a propylene group “—CH (CH ₃ ) CH ₂ —” or a trimethylene group “— (CH ₂ ) ₃ —”, and R ⁶ is Represents a methyl group, m = 1 to 1
500, n = 1 to 100, 0 ≦ p ≦ n (p: integer). ) Such various organopolysiloxane thio blocks
The number of the thioether group “—S—” in [B] or the number of mercapto groups (—SH groups) in the corresponding mercapto-modified polyorganosiloxane is described in, for example,
216922 (Showa Denko KK) page 5 [001
As shown in column [5], it is usually desirable that the average number per block (or one molecule) is 1.0 to 100, preferably 1.0 to 50, and more preferably 1.0 to 30.

The number average molecular weight (Mn) of the organopolysiloxane thioblock [B] or the corresponding mercapto-modified polyorganosiloxane is 300 to 10
It is desirably 0000, preferably 500 to 50,000. The organopolysiloxane thioblock [B] in the organopolysiloxane thioblock vinyl copolymer is derived from a mercapto-modified polyorganosiloxane [II-1a] having one mercapto group at one molecular terminal of the polyorganosiloxane. The one-terminal type [II
-1], a block copolymer ([A]) in which an organopolysiloxane thio block [B] is added to one end of the polyoxyalkylene group-containing vinyl copolymer block [A] (end blocking). ] / [B] type), and the organopolysiloxane thio block [B] is a double-ended [II-2].
In the case of (a), a block copolymer ([A]) in which a polyoxyalkylene group-containing vinyl copolymer block [A] is added to both ends of an organopolysiloxane thio block [B]
[B] / [A] type), and when the organopolysiloxane thio block [B] is the side chain type [II-3], the polyoxyalkylene group-containing vinyl copolymer block [A ] Is an organopolysiloxane thio block [B]
And a graft copolymer (comb-type copolymer) added to the side chain of the above.
When [B] is the side chain double-ended type [II-4], the polyoxyalkylene group-containing vinyl copolymer block is added to both ends and the side chain of the organopolysiloxane thio block [B]. It is thought to be a star copolymer.
However, these reactions can be presumed to have other block structures due to complicated termination reactions of radicals.

The polyoxyalkylene group-containing vinyl copolymer block [A] is contained in 100% by weight of all the component units contained in the organopolysiloxane thioblock vinyl copolymer (solid content) according to the present invention. The polyoxyalkylene polymerizable unsaturated carboxylate component unit (a1) is usually in an amount of 0.01 to 40% by weight, preferably 0.1 to 25% by weight, particularly preferably 0.5 to 20% by weight. In the above, the polymerizable unsaturated carboxylic acid component unit (a
2) is usually 0.5 to 95% by weight, preferably 1 to 9% by weight.
In an amount of 0% by weight, particularly preferably 5 to 80% by weight, the crosslinkable polymerizable unsaturated monomer component unit (a3) is usually
The other polymerizable unsaturated monomer component unit (a4) is contained in an amount of 0.05 to 70% by weight, preferably 0.5 to 60% by weight, particularly preferably 1 to 50% by weight. 0-70%, preferably 0-60%, particularly preferably 0%
It may be contained in an amount of up to 40%.

The organopolysiloxane thioblock [B] is usually contained in an amount of 0.01 to 90% by weight, preferably 0.1 to 70% by weight, particularly preferably 1 to 50% by weight. It is desirable. (The content of block [A] (% by weight) = 100-block [B]
(% By weight) = total (% by weight) of (a1) to (a4)) The component units (a1) and (a) constituting the polyoxyalkylene group-containing vinyl copolymer block [A] in such amounts.
2), (a3), (A4), and the organopolysiloxane thioblock [B] contained in the organopolysiloxane thioblock vinyl copolymer (also referred to as silicone block vinyl copolymer), The resulting organopolysiloxane thioblock vinyl copolymer tends to be excellent in film forming properties, coating strength, and antifouling properties.

When the organopolysiloxane thioblock vinyl copolymer according to the present invention is blended in, for example, an antifouling paint, it has little effect on the environment and the effect on the human body. It is possible to form an antifouling coating film having excellent properties and excellent mechanical strength. In particular, together with the organopolysiloxane thioblock vinyl copolymer of the present invention, a silicone oil or a coating film having excellent properties such as the mechanical strength can be formed even when a paraffin component or the like is blended. It is possible to prepare a paint such as an antifouling paint and a release agent that can form a coating film that can effectively suppress embrittlement.

[Organopolysiloxane Thioblock Bi
Production of Nyl Copolymer] In order to produce such an organopolysiloxane thioblock vinyl copolymer, for example, the above-mentioned (a1) polyoxyalkylene polymerizable unsaturated carboxylate [I] (for example, methoxypolyethylene glycol mono- Methacrylate, in the formula [I], m + n = 2 to 1
00) and (a2) at least one non-crosslinkable polymerizable unsaturated carboxylic acid other than (a1) or an ester thereof (eg, methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, isobornyl (meth) acrylate) and (a3)
Crosslinkable group-containing polymerizable unsaturated monomers (eg, γ-methacryloxypropyltrimethoxysilane, 4-hydroxybutyl acrylate) and (a4) other polymerizable unsaturated monomers used as needed ( Example: styrene, vinyl acetate, acrylonitrile) and the above mercapto-modified polyorganosiloxane [II] (eg, trade names “KF-2001, KP-35”)
8 ", a mercapto-modified silicone manufactured by Shin-Etsu Chemical Co., Ltd.) may be polymerized by heat or light under ordinary reaction conditions in the presence of a radical generation source such as a radical polymerization initiator, if necessary.

At the time of such a polymerization reaction, each of the above-mentioned monomers (including a macromonomer) may be used in an amount corresponding to the amount of each component in the above-mentioned organopolysiloxane thioblock vinyl copolymer. Specifically, the sum of the above monomers (a1), (a2) and (a3) and (a4) ((a1) + (a2) + (a3) + (a
4) The mercapto-modified polyorganosiloxane monomer [II] is usually used in an amount of 0.01 to 9 parts by weight based on 100 parts by weight.
It is used in an amount of 00 parts by weight, preferably 0.1 to 700 parts by weight.

The total of the monomers for forming the polyoxyalkylene group-containing vinyl copolymer block [A] ((a
1) + (a2) + (a3) + (a4)) The monomer (a1) is usually 0.1 to 50 parts by weight based on 100 parts by weight.
The monomer (a2) is usually used in an amount of 1 to 99.9 parts by weight, preferably 5 to 99.5 parts by weight, and the monomer (a3) is used in an amount of 0.5 to 30 parts by weight. )
Is generally used in an amount of 0.1 to 80 parts by weight, preferably 1 to 70 parts by weight, and the monomer (a4) is used in an amount of usually 0 to 80 parts by weight, preferably 0 to 70 parts by weight.

When each monomer is contained in such an amount, the resulting organopolysiloxane thioblock vinyl copolymer tends to be excellent in film-forming properties, coating strength, and antifouling properties. This polymerization includes bulk polymerization, solution polymerization, emulsion polymerization,
It can be carried out by various polymerization methods such as suspension polymerization.

When a radical polymerization initiator is used, the radical polymerization initiator is used based on 100 parts by weight of the total of the above-mentioned unsaturated monomers (a1) to (a4).
Usually, it is used in an amount of 0.005 to 20 parts by weight. As such a radical polymerization initiator, those generally used as a radical polymerization reaction initiator can be widely used, and specifically, for example, 2,2′-azobisisobutyronitrile (AIBN), , 2'-Azobisisovaleronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile) (trade name "ABN-E", Japan Hydrazine, azo compound), polydimethylsiloxane polymer azo polymerization initiator (trade names "VPS-0501, VPS-1")
001 ", an azo compound (manufactured by Wako Pure Chemical Industries, Ltd.); benzoyl peroxide (BPO), hydroperoxide, t-butyl peroxide, lauroyl peroxide, t-butylperoxy 2-ethylhexa. Peroxides such as Eat (trade name “Kayaester O”, manufactured by Kayaku Akzo Co., Ltd.); and the like. These radical polymerization initiators may be used alone or in combination of two or more.

The solvent is not particularly limited as long as it has a moderate volatility at ordinary temperature and can dissolve the used monomer (including the macromonomer) and the obtained organopolysiloxane thioblock vinyl copolymer. But not for example, aromatic hydrocarbons such as toluene, xylene and the like;
Aliphatic hydrocarbons such as hexane and heptane; diethyl ether, di-n-propyl ether, dibutyl ether,
Ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate, propyl acetate, butyl acetate and isobutyl acetate; ketones such as methyl ethyl ketone, methyl isobutyl ketone and acetone; chlorinated hydrocarbons such as dichloromethane, trichloroethylene, tetrachloroethane and chloroform Alcohols such as methanol, ethanol, isopropanol, butanol and isobutanol; and glycol derivative solvents such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether acetate. These solvents (solvents) can be used alone or in appropriate combination of two or more kinds.

These solvents include polymerization monomers (including macromonomers) (a1), (a2), (a3), (a)
4) and mercapto-modified polyorganosiloxane [I
I] can be used in any amount with respect to 100 parts by weight in total, for example, 10 to 1000 parts by weight, preferably 20 to 1000 parts by weight.
Used in an amount of 500 parts by weight. In the present invention, when the solution polymerization is adopted as the polymerization method, the organopolysiloxane thioblock vinyl copolymer obtained by the polymerization reaction can be used without separation and purification without diluting the solvent. ,preferable.

The thus obtained organopolysiloxane thioblock vinyl copolymer has a weight average molecular weight (Mw) measured by GPC of usually 1,000 to 2
00,000, preferably 2,000-100,000, and the viscosity (cps / 25 ° C.) is usually 50-100,000, preferably 100-20,000 in a 50% solution;
The appearance is usually a clear or cloudy solution.

<Applications> The organopolysiloxane thioblock vinyl copolymer (silicone block vinyl copolymer) according to the present invention is, for example, a coating film forming component (vehicle) for paints represented by antifouling paints. Component). Other uses of the organopolysiloxane thioblock vinyl copolymer include, for example, anti-paste paint, anti-stain paint, anti-icing / snow-proof paint, anti-graffiti paint, and release material.

The antifouling paint composition (antifouling paint) containing the organopolysiloxane thioblock vinyl copolymer of the present invention as a resin component can be prepared without blending an antifouling agent unlike the conventional antifouling paint. Sufficient antifouling performance can be exerted, and it is not necessary to add an antifouling agent, but an antifouling agent may be blended if necessary. In addition, paints such as antifouling paints containing the organopolysiloxane thioblock vinyl copolymer include various solvents, water-repellent substances described in Japanese Patent No. 2863562, leveling agents, and ultraviolet absorbers. Agents, extenders, coloring pigments, anti-sagging agents, other vehicle (film-forming components), plasticizers (eg, chlorinated paraffin), etc. Various components may be blended.

The above water repellent substances include petrolatum,
Paraffins such as paraffin wax and liquid paraffin, as well as silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, alkyl-modified silicone oil, fluorosilicone oil, and terminal functional group-containing silicone oil, caprylic acid, capric acid,
Examples include long-chain fatty acids such as lauric acid, palmitic acid, stearic acid, and oleic acid and esters thereof, and natural fats and oils such as beef tallow, lard, cod fat, coconut oil, and palm oil.

The amount of such a water-repellent substance is not particularly limited, but when the water-repellent substance is used, the amount of the water-repellent substance is usually less than that of the present invention in view of the film-forming properties, drying properties and adhesiveness of the resulting coating film. Is usually used in an amount of 1 to 200 parts by weight, preferably 5 to 100 parts by weight, based on 100 parts by weight of the organopolysiloxane thioblock vinyl copolymer (also referred to simply as “copolymer”).

In preparing such an antifouling paint, conventionally known dispersing machines such as a high-speed disperser, a sand grind mill, a basket mill, a three-roll mill, a ball mill, an attritor and the like may be used. it can. Hereinafter, the antifouling coating composition, its coating film, and the antifouling method according to the present invention will be described more specifically.

<Coating composition (paint), antifouling coating composition
(Antifouling paint)> The copolymer composition and the antifouling paint composition according to the present invention contain the above-mentioned organopolysiloxane thioblock vinyl copolymer as a film-forming component or a vehicle. The coating film and the antifouling coating film of the present invention are formed from the organopolysiloxane thioblock vinyl copolymer composition or the antifouling coating composition.

The coating film formed from the organopolysiloxane thioblock vinyl copolymer of the present invention has characteristics such that the polysiloxane chains are strongly oriented on the surface, so that the surface energy is low and the contact angle of water droplet is large. Is done. Due to this property, organisms in water hardly adhere to this coating film, and even if they do, they can be easily removed, and excellent antifouling performance is maintained over a long period of time. In addition, since a vinyl-based monomer containing a polyoxyalkylene group is copolymerized, the development of antifouling properties becomes more remarkable.

The copolymer composition and the paint (including the antifouling paint composition) of the present invention may contain optional components such as those used in ordinary paints and the like. Hereinafter, the antifouling paint composition will be described with specific examples. Examples of optional components that can be blended include antifouling agents, dissolution aids, plasticizers such as chlorinated paraffins, dehydrating agents (stabilizers), anti-sagging / anti-sedimentation agents, pigments, other film-forming components, and solvents. And various other components. If necessary, a curing agent or a curing catalyst for cross-linking can be added at the time of using the paint or at the time of preparing the paint. < Antifouling agent > In the antifouling coating composition of the present invention, as the antifouling agent, metallic copper, cuprous oxide, rodan copper, basic copper sulfate,
Basic copper acetate, copper oxyquinoline, copper naphthenate, copper rosinate, copper pyrithione, zinc pyrithione, tetramethylthiuram disulfide, 2,4,5,6-tetrachloroisophthalonitrile, N, N-dimethyldichlorophenylurea,
2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine, 4,5-dichloro-2-n-octyl-4-
Isothiazolin-3-one, 2,4,6-trichlorophenylmaleimide, pyridine-triphenylborane, amine-triphenylborane and the like. <Elution aid> As the elution aid, various compounds having a surfactant-like action such as to assist the migration of the water repellent to be incorporated to the surface or to allow the antifouling agent to be released slowly and efficiently can be used. Can be used. For example, rosin, monobasic acid such as naphthenic acid,
Various modified polyalkylenes can be used as needed. <Plasticizer> As a plasticizer, it imparts flexibility to the coating film,
Orthophosphate to improve cracking resistance and adhesion,
Plasticizers usually used for paints, such as chlorinated paraffins, phthalates, and adipic esters, may be used.

In the antifouling paint composition according to the present invention,
These plasticizers may be used, if necessary, in an amount of 0 to 100 parts by weight of the silicone block vinyl copolymer (solid content).
It may be contained in an amount of 50 parts by weight. <Dehydrating agent (stabilizer)> The dehydrating agent (stabilizer) is used especially when the component unit (a3) derived from the crosslinkable polymerizable unsaturated monomer contains an alkoxysilyl group or an isocyanate group (protection). The storage stability of the (dirty paint) composition can be further improved.

Specific examples of such a dehydrating agent (stabilizer) include
Specifically, for example, anhydrous gypsum (CaSO _Four), Synthetic Zeoli
Sorbents (trade name: molecular sieve, etc.), ortho
Orthoesters such as methyl formate and methyl orthoacetate;
Orthoborates, silicates and isocyanates
(Trade name: Additive TI) and the like. Departure
In the antifouling paint composition according to the present invention, this dehydrating agent is indispensable.
If necessary, the silicone block vinyl copolymer (solid
Form) 0 to 40 parts by weight per 100 parts by weight
It may be. <Anti-sagging / anti-settling agent (thixotropic agent)> In the present invention, coating
It is used as needed when thick coating and sagging resistance are improved.
Various dripping stops to prevent sedimentation of solvent insolubles (pigments, etc.)
-An anti-settling agent (adhesive) may be added.

Examples of the anti-sagging / anti-settling agents (thixotropic agents) include salts of organoclay-based Al, Ca and Zn such as stearates, lecithins and alkylsulfonates, polyethylene wax, amide wax, hydrogenated castor Examples thereof include an oil wax type, a polyamide wax type and a mixture thereof, a synthetic finely divided silica, a polyethylene oxide type wax, and the like, and preferably, a polyamide wax, a synthetic finely divided silica, a polyethylene oxide type wax, and an organic viscosity type are used. Examples of such anti-sagging and anti-settling agents include “Dispalon 305” and “Dispalon 4” manufactured by Kusumoto Kasei Co., Ltd.
200-20 "and those marketed under the trade name of" Dispalon A630-20X ". Such an anti-sagging / anti-settling agent may be contained in the antifouling coating composition as required, for example, in an amount of 0 to 10% by weight.

<Pigment> As the pigment other than the antifouling agent, various kinds of conventionally known organic or inorganic colored or extender pigments can be used. Examples of the organic pigment include carbon black, phthalocyanine blue, navy blue and the like. Examples of the inorganic pigment include titanium white, red iron oxide, barite powder, silica, calcium carbonate, talc, barium sulfate, zinc white (ZnO, zinc oxide), white lead, lead red, zinc dust and the like. Such various pigments may be incorporated in the antifouling paint composition in a total amount of about 0 to 45% by weight, if necessary.

<Other coating film forming components> The antifouling coating composition of the present invention may contain a resin other than the silicone block vinyl copolymer of the present invention as a coating film forming component. Other coating film forming components include, for example, acrylic resin, acrylic silicone resin, polyester resin, fluororesin, polybutene resin, silicone rubber, urethane resin (rubber), polyamide resin, vinyl chloride copolymer resin, chloride rubber (resin) , Chlorinated olefin resin, styrene-butadiene copolymer resin, ethylene-vinyl acetate copolymer resin, vinyl chloride resin, cumarone resin, trialkylsilyl acrylate (co) polymer (silyl resin), petroleum resin, ketone resin, form Aldehyde resins, polyvinyl alkyl ether resins and the like can be mentioned.

These "other coating film forming components" other than the silicone block vinyl copolymer of the present invention and the like.
May be contained in the antifouling coating composition in an amount of 20% by weight or less. <Solvent> In the antifouling paint of the present invention, the various components as described above are dissolved or dispersed in a solvent. As the solvent used here, for example, various solvents such as an aliphatic type, an aromatic type, a ketone type, an ester type, and an ether type which are usually blended in antifouling paints are used. Examples of the aromatic solvent include xylene and toluene, and examples of the ketone solvent include MIBK and the like.
Examples of the ester solvent include butyl acetate, and examples of the ether solvent include propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate (PMAC).

In the present invention, the amount of these solvents to be added is not particularly limited. <Curing Agent / Curing Catalyst> In the present invention, the organopolysiloxane thioblock copolymer of the present invention is crosslinked by crosslinking the crosslinkable functional group in the component unit (a3) derived from the crosslinkable polymerizable unsaturated monomer. Alternatively, the coating film obtained by applying the coating material containing the copolymer is cured, or a crosslinking reaction including self-crosslinking is promoted to thereby cure the organopolysiloxane thioblock copolymer of the present invention or the coating material containing the copolymer. A known curing agent and a known curing catalyst can be appropriately used in order to cure the coating film formed by applying the composition.

Specifically, when (a3) contains a hydroxyl group, for example, a commercially available isocyanate-based curing agent or melamine-based curing agent can be used, and (a3) contains an alkoxysilyl group. Or an aryloxysilyl group or a silanol group, alkyl silicates can be used as a curing agent, and tin or aluminum is used to further promote self-crosslinking and a crosslinking reaction using the curing agent. , A titanium-based curing catalyst or the like, and when (a3) contains an epoxy group, commercially available amines, thiols, cationic initiators, and epoxy curing agents can be used. When (a3) contains an isocyanate group, a polyol component such as an acrylic polyol or a polyamino compound can be used as a curing agent. Tin order to facilitate self-crosslinking, such as moisture curing, also to promote the cross-linking reaction using a curing agent,
A curing catalyst such as aluminum or titanium can be used, and when (a3) contains a carboxyl group, a polyglycidyl-based compound, a polyvalent metal and a salt thereof can be used as a curing agent, When (meth) acryloxy or vinyl groups are contained in (a3), a radical generator can be used as a curing catalyst, or a polyamine or polymercapto compound can be used as a curing agent.

<Production of antifouling paint composition> The antifouling paint composition of the present invention can be produced by appropriately utilizing a conventionally known method. For example, the silicone block vinyl copolymer solution of the present invention obtained by solution polymerization can be used as it is as an antifouling coating composition. , A dissolution aid, a plasticizer, a dehydrating agent (stabilizer), an anti-sagging / anti-settling agent, a pigment, other components for forming a film, a solvent, etc., in a predetermined ratio once or in any order and stirring and mixing It may be uniformly dissolved and decomposed.

The antifouling paint composition thus obtained may be mixed with a crosslinking agent or a curing catalyst, if necessary, applied to the surface of the substrate to be coated, and then dried. It can be put to practical use at that point. <Use of antifouling paint composition> The antifouling paint composition according to the present invention can form a coating film having stable antifouling performance for a long time,
For example, ships, fishing materials (eg ropes, fishing nets, floats,
Buoys), underwater structures such as water supply / drainage outlets for thermal and nuclear power plants, bay roads, submarine tunnels, port facilities, canals and waterways,
When applied to the surface of various base materials such as a sludge diffusion prevention film for marine civil engineering, a ship or an underwater structure coated with an antifouling coating film having excellent antifouling properties can be obtained.

That is, the antifouling coating film obtained by applying and curing the antifouling coating composition of the present invention on the surface of various substrates has a long adhesion of aquatic organisms such as Aosa, Barnacle, Aonori, Serpula, Oyster, Fusakomushi, etc. It has excellent antifouling properties, such as being able to continuously prevent over a period. In particular, the antifouling coating composition adheres well to the surface of a substrate made of steel, FRP, wood, aluminum alloy, or the like even when the substrate is made of steel, FRP, wood, aluminum alloy, or the like. Further, the antifouling paint composition may be overcoated on the surface of a paint film already applied or on the surface of an existing antifouling paint film.

When the antifouling coating composition of the present invention is applied to the surface of a marine structure, it is possible to prevent the adhesion of marine organisms and to maintain the function of the structure for a long time. I have. In addition, if the antifouling paint composition of the present invention is applied to fishing materials such as fishing nets or fishing gear, it is possible to prevent the fishing net or fishing gear from being stained, and the risk of environmental pollution is extremely low.

The antifouling coating film of the present invention, that is, the coating film applied to the surface of the water-contacting part of a ship or underwater structure is formed from the above-described antifouling coating composition, and has a very low risk of environmental pollution. Excellent long-term antifouling property against organisms attached to ships or underwater structures.

[0118]

When the organopolysiloxane thioblock vinyl copolymer according to the present invention is used in, for example, an antifouling paint, it has little effect on the environment and the effect on the human body. It is possible to form an antifouling coating film having excellent durability and excellent mechanical strength. In particular, the organopolysiloxane thioblock vinyl copolymer of the present invention,
Even when silicone oils, paraffins, and the like are blended, the above properties are exhibited, and a coating film that can effectively suppress the brittleness of the coating film can be formed.

[0119]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. The components used in the following Examples and Comparative Examples, test methods, and the like are as follows.

[0120]

Example 1 75 parts by weight of butyl acetate was charged into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a dropping device, and a reflux condenser, and the temperature was raised to 100 ° C. in a nitrogen gas atmosphere. Then, methyl methacrylate (MMA)
50 parts by weight, 2-ethylhexyl acrylate (2EH
A) 10 parts by weight of methoxypolyethylene glycol methacrylate (trade name “NK Ester M-230G”;
Shin Nakamura Chemical Co., Ltd., n = 23, solid content 100% by weight) 5
Parts by weight, 4-hydroxybutyl acrylate (trade name “4
HBA ", manufactured by Osaka Organic Chemical Industry Co., Ltd.), 10 parts by weight, 2,2'-azobis (2-methylbutyronitrile) as a polymerization initiator
(Trade name "ABN-E", manufactured by Nippon Hydrazine Co., Ltd., azo compound) 2.2 parts by weight of mixture A and mercapto-modified silicone (trade name "KF-2001", Shin-Etsu Chemical Co., Ltd.)
A liquid mixture B of 25 parts by weight of a weight average molecular weight Mw 9200, a solid content of 100% by weight, and the position of the SH group is a side chain type) and 25 parts by weight of butyl acetate manufactured by Co., Ltd. Dropping into the above reaction vessel was started.

The mixture A was dropped in 3 hours, and the mixture B was dropped in 1.5 hours. One hour after the end of the mixture A dropping, A
After adding 0.2 parts by weight of BN-E three times every 45 minutes, 1.5
The mixture was stirred while keeping the temperature for a period of time to obtain a copolymer A-1 solution. The appearance of the obtained A-1 solution was transparent, the NV (residue after drying in a hot air dryer at 105 ° C. for 3 hours) was 49.5%, the viscosity was 340 cps / 25 ° C., and the weight average molecular weight (Mw) )
Was 19,710.

Tables 1 to 3 show the blending composition (parts by weight), the catalyst, the solvent, the reaction temperature and the like in preparing the copolymer A-1, and the properties of the obtained copolymer A-1. Table 4 summarizes the contents of the abbreviations (product names) and manufacturers in the following table. FIG. 1 shows a GPC chromatogram of the obtained copolymer A-1, and FIG. 2 shows a chart of an IR spectrum.

[0123]

Examples 2 to 10 and 13 to 18 Copolymers were synthesized in the same manner as in Example 1 except that the composition was changed as shown in Table 1. The physical properties of the obtained copolymer were evaluated in the same manner as in Example 1 above. Copolymer A-
2 to A-10, A-13 to A-18 Tables 1 to 3 show the composition (parts by weight), the catalyst, the solvent, the reaction temperature, and the like of the obtained copolymers at the time of preparation. .

Further, the obtained copolymers A-2 to A-1
0, GPC chromatograms of copolymers A-13 to A-18 are shown in FIG. 3 (copolymer A-2) and FIG. 5 (copolymer A-
3), FIG. 7 (copolymer A-4), FIG. 9 (copolymer A-
5), FIG. 11 (copolymer A-6), FIG. 13 (copolymer A)
-7), FIG. 15 (copolymer A-8), FIG. 17 (copolymer A-9), FIG. 19 (copolymer A-10), FIG. 25 (copolymer A-13), FIG. (Copolymer A-14), FIG. 29
(Copolymer A-15), FIG. 31 (Copolymer A-16),
FIG. 33 (Copolymer A-17), FIG. 35 (Copolymer A-1)
8).

Further, the obtained copolymers A-2 to A-1
0, the IR spectrum charts of copolymers A-13 to A-18 are shown in FIG. 4 (copolymer A-2) and FIG. 6 (copolymer A-
3), FIG. 8 (copolymer A-4), FIG. 10 (copolymer A-
5), FIG. 12 (copolymer A-6), FIG. 14 (copolymer A)
-7), FIG. 16 (copolymer A-8), FIG. 18 (copolymer A-9), FIG. 20 (copolymer A-10), FIG. 26 (copolymer A-13), FIG. (Copolymer A-14), FIG.
(Copolymer A-15), FIG. 32 (Copolymer A-16),
FIG. 34 (Copolymer A-17), FIG. 36 (Copolymer A-1)
8).

[0126]

EXAMPLE 11 50 parts by weight of butyl acetate and 25 parts by weight of xylene were charged into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a dropping device, and a reflux condenser, and were heated at 90 ° C. in a nitrogen gas atmosphere. Temperature. Subsequently, 30 parts by weight of methyl methacrylate (MMA), 35 parts by weight of n-butyl methacrylate (BMA), and methoxypolyethylene glycol methacrylate (trade name “NK ESTER M-2”)
30G ", manufactured by Shin-Nakamura Chemical Co., Ltd., n = 23, solid content 100
5% by weight), 5 parts by weight of γ-methacryloxypropyltrimethoxysilane (trade name “KBM-503”, manufactured by Shin-Etsu Chemical Co., Ltd.), 2,2′-azobis (2-
Mixture A of 1 part by weight of methylbutyronitrile (trade name “ABN-E”, manufactured by Nippon Hydrazine Co., Ltd., azo compound)
And mercapto-modified silicone (trade name “KF-200
1 ", manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight Mw 920
0, solid content 100% by weight, position of SH group is side chain type) 25
Parts by weight of a mixture B containing 25 parts by weight of butyl acetate
While maintaining the temperature at 0 ° C., dropping into the above reaction vessel was started at the same time.
Both the mixed liquid A and the mixed liquid B were dropped in 2 hours.

One hour after the completion of dropping, ABN-E (0.1,
0.1, 0.2, 0.2 parts by weight) were added four times every 45 minutes. Thereafter, the temperature was raised to 100 ° C., and the mixture was stirred while keeping the temperature for 1.5 hours to obtain a copolymer A-11 solution. The appearance of the obtained copolymer solution A-11 was transparent, the NV was 49.4%, the viscosity was 310 cps / 25 ° C., and the weight average molecular weight (M
w) was 29,030.

Tables 1 to 3 show the blending composition (parts by weight), the catalyst, the solvent, the reaction temperature and the like in preparing the copolymer A-11, as well as the properties of the obtained copolymers. FIG. 21 shows a GPC chromatogram of the obtained copolymer A-11, and FIG. 22 shows a chart of the IR spectrum.

[0129]

Example 12 In Example 11, the composition was changed as shown in Table 1, and the additional catalyst was added 5 times (0.05, 0.
The copolymer was synthesized in the same manner as in Example 11 except that the respective amounts were changed to 0.5, 0.1, 0.1, and 0.2 parts by weight every 45 minutes). The physical properties of the obtained copolymer were evaluated in the same manner as in Example 1 above.

Tables 1 to 3 show the blending composition (parts by weight), the catalyst, the solvent, the reaction temperature and the like in preparing the copolymer A-12, as well as the properties of the obtained copolymer. FIG. 23 shows a GPC chromatogram of the obtained copolymer A-12, and FIG. 24 shows a chart of the IR spectrum.

[0131]

Example 19 42.9 parts by weight of butyl acetate was charged into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a dropping device, and a reflux condenser, and then charged in a nitrogen gas atmosphere.
The temperature was raised to 0 ° C. Then, 50 parts by weight of isobornyl acrylate (IBXA), 10 parts by weight of 2-ethylhexyl acrylate (2EHA), and methoxypolyethylene glycol methacrylate (trade name “NK ESTER M-9”)
0G ", manufactured by Shin-Nakamura Chemical Co., Ltd., n = 9, solid content 100% by weight) 5 parts by weight, 4-hydroxybutyl acrylate (trade name" 4HBA ", manufactured by Osaka Organic Chemical Industry Co., Ltd.) 10 parts by weight, T-butyl peroxy 2-ethylhexaate as a polymerization initiator (trade name “Kayaester O”, manufactured by Kayaku Akzo Co., Ltd.)
Peroxide) 0.8 part by weight of mixture A and mercapto-modified silicone (trade name “KP-358”, Shin-Etsu Chemical Co., Ltd.)
25 wt. Of a mixed solution B (manufactured by Co., Ltd., weight average molecular weight Mw: 4400, solid content: 100 wt%, position of SH group: side chain type) was simultaneously dropped into the reaction vessel while maintaining the internal temperature at 100 ° C. . Both the mixture A and the mixture B were dropped in 3 hours.

1.5 hours after the completion of the dropwise addition, Kayaester O was added three times (0.1, 0.1, 0.1 parts by weight) every 45 minutes, and the mixture was stirred for 1.5 hours while keeping the temperature of the copolymer. A-19 solution was obtained. The appearance of the obtained copolymer solution A-19 was transparent and N
V was 67.3%, the viscosity was 630 cps / 25 ° C., and the weight average molecular weight (Mw) was 20,360.

Tables 1 to 3 show the blending composition (parts by weight), the catalyst, the solvent, the reaction temperature and the like at the time of preparing the copolymer A-19, and the properties of the obtained copolymer. FIG. 37 shows a GPC chromatogram of the obtained copolymer A-19.

[0134]

Examples 20 to 26 In Example 19, except that the composition and the reaction temperature were changed as shown in Table 2,
A copolymer was synthesized in the same manner as in Example 19. The physical properties of the obtained copolymer were evaluated in the same manner as in Example 18 above. Tables 1 to 3 show the composition and the like of the copolymers A-20 to A-26 (parts by weight), the catalyst, the solvent, the reaction temperature, and the properties of the obtained copolymers.

In addition, the obtained copolymers A-20 to A-2
GPC chromatogram of Figure 6 (copolymer A-2)
0), FIG. 39 (copolymer A-21), FIG. 40 (copolymer A-23), FIG. 42 (copolymer A-24), FIG. 44 (copolymer A-25), FIG. Copolymer A-26). In addition, IR of the obtained copolymers A-23 to A-26
The spectrum chart is shown in FIG. 41 (copolymer A-23),
FIG. 43 (Copolymer A-24), FIG. 45 (Copolymer A-2)
5) and FIG. 47 (copolymer A-26).

[0136]

Comparative Example 1 75 parts by weight of butyl acetate was charged into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a dropping device, and a reflux condenser, and heated to 100 ° C. in a nitrogen gas atmosphere. Then, methyl methacrylate (MMA)
60 parts by weight, 2-ethylhexyl acrylate (2EH
A) A mixture of 15 parts by weight and 2.2 parts by weight of a polymerization initiator 2,2′-azobis (2-methylbutyronitrile) (trade name “ABN-E”, manufactured by Nippon Hydrazine Co., Ltd., an azo compound) Liquid A
And mercapto-modified silicone (trade name “KF-200
1 ", manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight Mw 920
0, solid content 100% by weight, position of SH group is side chain type) 25
Parts by weight of a mixed solution B containing 25 parts by weight of butyl acetate
At the same time, the dropwise addition was started to the reaction vessel while maintaining the temperature at 00 ° C. The mixture A was dropped in 3 hours, and the mixture B was dropped in 1.5 hours. One hour after the end of the mixture A dropping, ABN-E
After 0.2 part by weight was added three times every 45 minutes, the mixture was stirred with keeping the temperature for 1.5 hours to obtain a copolymer H-1 solution.

The appearance of the obtained H-1 solution is transparent, NV
(Residue after drying for 3 hours in a hot air dryer at 105 ° C.) was 49.4%, and the viscosity was 440 cps / 25 ° C.
The weight average molecular weight (Mw) was 19,710.

[0138]

Comparative Example 2 75 parts by weight of butyl acetate was charged into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a dropping device, and a reflux condenser, and heated to 100 ° C. in a nitrogen gas atmosphere. Then, methyl methacrylate (MMA)
60 parts by weight, 2-ethylhexyl acrylate (2EH
A) 10 parts by weight of methoxypolyethylene glycol methacrylate (trade name “NK Ester M-230G”;
Shin Nakamura Chemical Co., Ltd., n = 23, solid content 100% by weight) 5
Parts by weight, polymerization initiator 2,2′-azobis (2-methylbutyronitrile) (trade name “ABN-E”, Nippon Hydrazine)
2.2 parts by weight of mixed solution A (manufactured by Azo Compound Co., Ltd.) and mercapto-modified silicone (trade name “KF-2001”, manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight Mw 9200, solid content 100% by weight, A mixture B of 25 parts by weight of the SH group (side chain type) and 25 parts by weight of butyl acetate was simultaneously dropped into the reaction vessel while maintaining the internal temperature at 100 ° C. The mixed solution A was dropped in 3 hours, and the mixed solution B was dropped in 1.5 hours. One hour after the completion of the dropwise addition of the mixed solution A, 0.2 parts by weight of ABN-E was added three times every 45 minutes, and the mixture was stirred while keeping warm for 1.5 hours to obtain a copolymer H-2 solution.

The resulting copolymer H-2 solution was transparent in appearance, had an NV (residue after drying in a hot air dryer at 105 ° C. for 3 hours) of 49.3%, and had a viscosity of 430 cps / 25 ° C.
And the weight average molecular weight (Mw) was 18,090.

[0140]

[Table 1]

[0141]

[Table 2]

[0142]

[Table 3]

[0143]

[Table 4]

[0144]

Examples T-1 to T-28, Comparative Examples HT-1 to HT-
(Production of antifouling paint composition) The following methods were used for producing antifouling paint compositions having the composition shown in Tables 5 to 7. <Composition composed only of liquid components>: Of the components shown in Tables 5 to 7, components other than the curing agent and the catalyst are charged into a container, sufficiently stirred and mixed using a high-speed disper, and then a 120-mesh filter. To obtain a desired antifouling coating composition.

<Composition containing a solid component such as a pigment>: Table 5
The components excluding the curing agent and catalyst among the components shown in Nos. 7 to 7 were charged into a paint shoer using glass beads as a medium, shaken for 2 hours, and then filtered through a 120-mesh filter to obtain a desired antifouling paint composition. I got something. The coating film hardness of the antifouling paint composition was evaluated. <Evaluation of coating film hardness> Tables 5 to 7 show the composition of the antifouling coating composition and the evaluation results of the coating film hardness.

The coating film hardness was evaluated by mixing the antifouling coating composition obtained above immediately before coating with a curing agent or a catalyst in the proportions shown in Tables 5 to 7, and then applying the mixture to a glass plate using an applicator. The coating was applied thereon so as to have a dry film thickness of 30 μm, dried in a room for 2 weeks, and evaluated according to the degree of finger touch. (Evaluation criteria) 5: The formation of a high-hardness coating film that scarcely damages the toe is recognized 4: The formation of a coating film that causes a slight damage to the surface at the toe is recognized 3: The coating film that causes a damage to the surface at the toe 2: The coating film is easily broken at the tip of the toe. 1: The formation of a soft coating that gives a fingerprint when touched with the fingertip is recognized. 0: The coating film is poor in film-forming properties where the coating is easily twisted at the fingertip. <Evaluation of antifouling property> The antifouling property of the antifouling paint composition was evaluated.

The results are shown in Tables 5 to 7. The following method was used to evaluate the antifouling property. 100 mm x 300 mm x 5 mm PVC base plate coated with epoxy undercoat with a dry film thickness of 100
μ using an air spray and drying in a room for 2 weeks. Immediately before coating, the antifouling paint composition obtained above was thoroughly mixed with a curing agent or a catalyst in the proportions shown in Tables 5 to 7. After that, it was applied using an applicator to a dry film thickness of 150μ, dried in a room for one week, immersed in a place 1m below the water surface from a raft installed in Hiroshima Bay, and attached to organisms for 18 months The situation was visually observed.

The evaluation was made based on the area (%) of the macro organism attached. <Measurement conditions of GPC and IR> The measurement conditions of GPC and IR are as follows. [GPC measurement conditions] Apparatus: Tosoh HLC-8120 GPC Column: Tosoh Super H2000 + H4000 6 mm ID, 15 cm Eluent: THF Flow rate: 0.500 ml / min Detector: RI column thermostat temperature: 40 ° C [ IR Measurement Conditions] Apparatus: Hitachi 270-30 Hitachi infrared spectrophotometer Measurement method: KBr cell, coating method

[0149]

[Table 5]

[0150]

[Table 6]

[0151]

[Table 7]

[Brief description of the drawings]

FIG. 1 shows a GPC chromatogram of an organopolysiloxane thio block copolymer A-1.

FIG. 2 shows an IR spectrum chart of organopolysiloxane thioblock copolymer A-1.

FIG. 3 shows a GPC chromatogram of organopolysiloxane thio block copolymer A-2.

FIG. 4 shows a chart of an IR spectrum of organopolysiloxane thio block copolymer A-2.

FIG. 5 shows a GPC chromatogram of organopolysiloxane thioblock copolymer A-3.

FIG. 6 shows a chart of an IR spectrum of organopolysiloxane thio block copolymer A-3.

FIG. 7 shows a GPC chromatogram of organopolysiloxane thioblock copolymer A-4.

FIG. 8 shows a chart of an IR spectrum of organopolysiloxane thio block copolymer A-4.

FIG. 9 shows a GPC chromatogram of organopolysiloxane thioblock copolymer A-5.

FIG. 10 shows a chart of an IR spectrum of organopolysiloxane thio block copolymer A-5.

FIG. 11 shows a GPC chromatogram of organopolysiloxane thioblock copolymer A-6.

FIG. 12 shows a chart of an IR spectrum of organopolysiloxane thio block copolymer A-6.

FIG. 13 shows a GPC chromatogram of organopolysiloxane thioblock copolymer A-7.

FIG. 14 shows a chart of an IR spectrum of organopolysiloxane thio block copolymer A-7.

FIG. 15 shows a GPC chromatogram of organopolysiloxane thioblock copolymer A-8.

FIG. 16 shows a chart of an IR spectrum of organopolysiloxane thioblock copolymer A-8.

FIG. 17 shows a GPC chromatogram of organopolysiloxane thioblock copolymer A-9.

FIG. 18 shows a chart of an IR spectrum of organopolysiloxane thioblock copolymer A-9.

FIG. 19 shows a GPC chromatogram of organopolysiloxane thioblock copolymer A-10.

FIG. 20 shows a chart of an IR spectrum of organopolysiloxane thioblock copolymer A-10.

FIG. 21 shows a GPC chromatogram of organopolysiloxane thioblock copolymer A-11.

FIG. 22 shows a chart of an IR spectrum of organopolysiloxane thioblock copolymer A-11.

FIG. 23 shows a GPC chromatogram of organopolysiloxane thioblock copolymer A-12.

FIG. 24 shows a chart of an IR spectrum of organopolysiloxane thioblock copolymer A-12.

FIG. 25 shows a GPC chromatogram of organopolysiloxane thioblock copolymer A-13.

FIG. 26 shows a chart of an IR spectrum of organopolysiloxane thioblock copolymer A-13.

FIG. 27 shows a GPC chromatogram of organopolysiloxane thioblock copolymer A-14.

FIG. 28 shows a chart of an IR spectrum of organopolysiloxane thioblock copolymer A-14.

FIG. 29 shows a GPC chromatogram of organopolysiloxane thioblock copolymer A-15.

FIG. 30 shows a chart of an IR spectrum of organopolysiloxane thioblock copolymer A-15.

FIG. 31 shows a GPC chromatogram of organopolysiloxane thioblock copolymer A-16.

FIG. 32 shows a chart of an IR spectrum of organopolysiloxane thioblock copolymer A-16.

FIG. 33 shows a GPC chromatogram of organopolysiloxane thioblock copolymer A-17.

FIG. 34 shows a chart of an IR spectrum of organopolysiloxane thioblock copolymer A-17.

FIG. 35 shows a GPC chromatogram of organopolysiloxane thioblock copolymer A-18.

FIG. 36 shows a chart of an IR spectrum of organopolysiloxane thioblock copolymer A-18.

FIG. 37 shows a GPC chromatogram of organopolysiloxane thioblock copolymer A-19.

FIG. 38 shows a GPC chromatogram of organopolysiloxane thioblock copolymer A-20.

FIG. 39 shows a GPC chromatogram of organopolysiloxane thioblock copolymer A-21.

FIG. 40 shows a GPC chromatogram of organopolysiloxane thioblock copolymer A-23.

FIG. 41 shows a chart of an IR spectrum of organopolysiloxane thioblock copolymer A-23.

FIG. 42 shows a GPC chromatogram of an organopolysiloxane thioblock copolymer A-24.

FIG. 43 shows a chart of an IR spectrum of organopolysiloxane thioblock copolymer A-24.

FIG. 44 shows a GPC chromatogram of an organopolysiloxane thioblock copolymer A-25.

FIG. 45 shows a chart of an IR spectrum of organopolysiloxane thio block copolymer A-25.

FIG. 46 shows a GPC chromatogram of organopolysiloxane thioblock copolymer A-26.

FIG. 47 shows a chart of an IR spectrum of organopolysiloxane thioblock copolymer A-26.

Continuation of the front page (72) Inventor Makoto Tsuboi 7-chome, Meiji-Shinkai, Otake City, Hiroshima Prefecture F-Term (reference) 4J031 AA11 AA13 AA17 AA19 AA20 AA22 AA59 AB01 AC11 AD01 AF12 4J038 CQ001 DL131 GA01 GA09 GA13 GA15 MA14 NA05 PB05 PB07 PC02 PC04 PC10

Claims (16)

[Claims] [1] [A] (a1) a polyoxyalkylene compound represented by the following formula [I], wherein the polyoxyalkylene compound forms an ester with a polymerizable unsaturated carboxylic acid at least at one end thereof. Carboxylate: General formula [I]: R ⁴ [OR ^l ] _m [OR ² ] _n -OCOR ³ ... [I] 中 In the formula [I], R ¹ and R ² are the same or different. R ³ represents a group containing a polymerizable unsaturated hydrocarbon group; R ⁴ represents a hydrogen atom or a monovalent group optionally having a polymerizable unsaturated bond; Or a monobasic or dibasic organic carboxylic acid residue which may have a polymerizable unsaturated bond: “R ⁵ CO— (R ⁵ is
It represents an organic group which may contain a polymerizable unsaturated bond. ) ", And m and n are positive numbers. (A2) at least one non-crosslinkable polymerizable unsaturated carboxylic acid other than the component (a1) or an ester thereof, and (a3) a crosslinkable polymerizable unit. A component unit derived from an unsaturated monomer;
4) If necessary, a polyoxyalkylene group-containing vinyl copolymer block formed from a component unit derived from another polymerizable unsaturated monomer, and [B] a general formula [I
I]: ｛In the formula [II], R ⁶ represents a hydrocarbon group having 1 to 10 carbon atoms, and R ⁷ , R ⁸ and R ⁹ each independently represent a divalent thio group having 1 to 20 carbon atoms. It shows an organic group, and n and m show a positive number. And a weight average molecular weight (Mw) measured by GPC of 1,000.
An organopolysiloxane thioblock vinyl copolymer having a molecular weight of 0 to 200,000. 2. The organopoly according to claim 1, wherein the component unit (a2) derived from the polymerizable unsaturated carboxylic acid or its ester is a component unit derived from (meth) acrylic acid or its ester. Siloxane thio block vinyl copolymer. 3. A component unit (a1) derived from the above polyoxyalkylene polymerizable unsaturated carboxylate [I].
Is a component unit derived from a polyoxyalkylene (meth) acrylate. The organopolysiloxane thioblock vinyl copolymer according to any one of claims 1 to 2, wherein 4. The crosslinking group of the component unit (a3) derived from the crosslinking type polymerizable unsaturated monomer is a hydroxyl group,
The compound is any one or more of an alkoxysilyl group, an aryloxysilyl group, an epoxy group, an isocyanate group, a carboxyl group, a (meth) acryloxy group, a vinyl group, a silanol group, and an amino group. 3. The organopolysiloxane thioblock vinyl copolymer according to item 1. 5. Component (a4) derived from the other polymerizable unsaturated monomer is styrenes, vinyl esters, (meth) acrylamides, vinyl ethers,
Any one of itaconic acid, maleic acid, fumaric acid, citraconic acid and derivatives thereof, and acrylonitrile
The organopolysiloxane thioblock vinyl copolymer according to any one of claims 1 to 4, which is derived from at least one species. 6. The weight average molecular weight (Mw) of the organopolysiloxane thioblock vinyl copolymer measured by GPC is from 1,000 to 200,000.
5. The organopolysiloxane thioblock vinyl copolymer according to any one of 5. 7. An antifouling paint composition comprising the organopolysiloxane thioblock vinyl copolymer according to any one of claims 1 to 6 as a vehicle component. 8. [I] The organopolysiloxane thioblock vinyl copolymer according to any one of claims 1 to 7, and [II]
An organopolysiloxane thioblock vinyl copolymer composition comprising a water-repellent component. 9. The method according to claim 8, wherein the water repellent component is a silicone oil and / or paraffin.
3. The organopolysiloxane thioblock vinyl copolymer composition according to item 1. 10. An antifouling paint composition comprising the organopolysiloxane thioblock vinyl copolymer composition according to claim 8. 11. The antifouling coating composition according to claim 7, further comprising an antifouling agent. 12. An antifouling coating film formed from the organopolysiloxane thioblock vinyl copolymer composition or the antifouling coating composition according to any one of claims 7 to 11. 13. A substrate coated with an antifouling coating formed from the organopolysiloxane thioblock vinyl copolymer composition or the antifouling coating composition according to claim 7. 14. The surface of a substrate is coated with an antifouling coating formed from the organopolysiloxane thioblock vinyl copolymer composition or the antifouling coating composition according to any one of claims 7 to 11. Underwater structure. 15. A surface of a marine substrate coated with an antifouling coating film formed from the organopolysiloxane thioblock vinyl copolymer composition or the antifouling coating composition according to any one of claims 7 to 11. Ship. 16. Coating the surface of a substrate with an antifouling coating film formed from the organopolysiloxane thioblock vinyl copolymer composition or the antifouling coating composition according to any one of claims 7 to 11. An antifouling method for a substrate, comprising: