# US 9,752,036 B2 · Curable organopolysiloxane antifouling composite coating film, and antifouling substrate coated with the same

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- Number: US 9,752,036 B2
- Document ID: US9752036B2
- Status: Granted
- Kind: B2
- Application number: 14/439,110
- Filed: 2013-11-08
- Published: 2015-10-15
- Granted: 2017-09-05
- Earliest claimed: 2012-11-13
- Assignees: Chugoku Marine Paints, Ltd.
- Applicants: Chugoku Marine Paints, Ltd.
- Inventors: Masaaki Oya; Kiwamu Yamane; Shinichi Tashiro
- Web page: https://patentgrep.com/patent/US9752036B2

## CPC

- C09D 5/1693: {as part of a multilayer system}
- B32B 15/095: comprising polyurethanes
- C08G 18/61: Polysiloxanes
- C09D 5/08: Anti-corrosive paints
- C09D 5/082: {characterised by the anti-corrosive pigment}
- C09D 5/16: Antifouling paints; Underwater paints
- C09D 5/1637: {Macromolecular compounds}
- C09D 5/165: {containing hydrolysable groups (C09D5/1643 takes precedence)}
- C09D 5/1675: {Polyorganosiloxane-containing compositions}
- C09D 7/65: macromolecular (C09D7/41-C09D7/48 take precedence)
- C09D 175/04: Polyurethanes
- C09D 183/08: containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
- B32B 2255/10: on synthetic resin layer or on natural or synthetic rubber layer
- B32B 2255/26: Polymeric coating
- B32B 2307/752: Corrosion inhibitor
- B32B 2307/754: Self-cleaning
- B32B 2605/12: Ships
- C08G 77/16: to hydroxy groups
- C08G 77/26: nitrogen-containing groups
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

## Abstract

[Problem] To provide a curable organopolysiloxane antifouling composite coating film obtained by using a urethane resin anticorrosive coating film excellent in curability instead of one or two organopolysiloxane intermediate coating film layers (Tie Coats) to layer an organopolysiloxane antifouling coating film excellent in both interlayer adhesiveness with the anticorrosive coating film and antifouling performance; and an antifouling substrate coated with the composite coating film. [Solution] An antifouling composite coating film, comprising a laminated urethane resin anticorrosive coating film and antifouling coating film, (I) the urethane resin anticorrosive coating film being formed from an anticorrosive paint composition comprising a main agent selected from the group consisting of polyols and glycidyl ethers, and an isocyanate curing agent, (II) the antifouling coating film being formed from a curable polysiloxane composition comprising specific components (a), (b), and (c).

## Claims

### Claim 1

An antifouling composite coating film, comprising:
(I) a urethane resin anticorrosive coating film formed from an anticorrosive paint composition comprising a main agent selected from the group consisting of a polyol and a glycidyl ether, and said composition further comprises an isocyanate curing agent and a tertiary amine compound as a catalyst for accelerating curing, and
(II) an antifouling coating film formed from a curable polysiloxane composition comprising components (a), (b), (c), and (f) below,
the urethane resin anticorrosive coating film (I) and the antifouling coating film (II) being laminated,
(a) a diorganopolysiloxane having at least two functional groups in one molecule,
(b) an organosilane having at least two hydroxyl groups or hydrolyzable groups in one molecule represented by formula (2) and/or a partial hydrolysis-condensate thereof:
R8dSiY4-d (2)
wherein
R8 represents a hydrocarbon group having 1 to 6 carbon atoms selected from the group consisting of a straight-chain alkyl group, a branched alkyl group, a cyclic alkyl group, and a phenyl group;
Y represents a hydroxyl group or a hydrolyzable group selected from the group consisting of a an iminoxy group, an acetyloxy group, an alkoxy group, an acyloxy group, an amino group, an amide group, and an aminoxy group; and
d is an integer of 0 to 2,
(c) an amino group-containing alkoxysilane represented by formula (1) and/or a reaction product thereof:
X—R1—SiR2n(OR3)3-n (1)
wherein
R1 represents an alkylene group having 1 to 10 carbon atoms;
R2 represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms;
R3 represents an alkyl group having 1 to 10 carbon atoms;
X is a group represented by R4R5N— or R6R7C═N—, wherein R4 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or H2N(CH2)p(NH(CH2)q)r—, wherein p and q are integers of 2 to 5, and r is an integer of 0 to 5; R5 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms; and R6 and R7 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms; and
n is an integer of 0 to 2, and
(f) a color pigment.

### Claim 2 (depends on 1)

The antifouling composite coating film according to claim 1, wherein the functional groups of the diorganopolysiloxane (a) are selected from the group consisting of a hydroxyl group, an iminoxy group, an amino group, an acetyloxy group, and an alkoxy group.

### Claim 3 (depends on 1)

The antifouling composite coating film according to claim 1, wherein Y in the general formula (2) is selected from the group consisting of a hydroxyl group, an iminoxy group, an acetyloxy group, and an alkoxy group.

### Claim 4 (depends on 1)

The antifouling composite coating film according to claim 1, wherein the amino group-containing alkoxysilane (c) is γ-aminopropyltrimethoxysilane.

### Claim 5 (depends on 1)

The antifouling composite coating film according to claim 1, wherein 0.001 to 5 parts by weight of (c) the amino group-containing alkoxysilane is contained based on 100 parts by weight of the solid contents of the curable polysiloxane composition.

### Claim 6 (depends on 1)

The antifouling composite coating film according to claim 1, wherein the main agent is a polyol and the isocyanate curing agent is a polyisocyanate.

### Claim 7 (depends on 6)

The antifouling composite coating film according to claim 6, wherein the anticorrosive paint composition has a ratio of the equivalent of an isocyanate group contained in the polyisocyanate to the equivalent of a hydroxyl group contained in the polyol [NCO group/OH group] is 0.3/1.0 to 2.0/1.0.

### Claim 8 (depends on 1)

An antifouling substrate comprising a substrate and the antifouling composite coating film according to claim 1 laminated on a surface of the substrate in order of substrate/coating film (I)/coating film (II).

### Claim 9 (depends on 8)

The antifouling substrate according to claim 8, wherein the substrate is an underwater structure or a ship.

### Claim 10 (depends on 1)

A method for producing an antifouling substrate, comprising laminating the antifouling composite coating film according to claim 1 on a surface of a substrate in order of substrate/coating film (I)/coating film (II).