阅读说明：本技术 涂料组合物及由此形成的涂膜 (Coating composition and the film being consequently formed ) 是由 鹰尾雄祐 辻智广 北村涉 永濑靖久 锻治弘一 于 2018-03-30 设计创作，主要内容包括：提供涂料组合物、由此形成的涂膜以及具有该涂膜的水中结构物及船舶,其中,该涂料组合物为包含含硅原子树脂和消泡剂的涂料组合物,含硅原子树脂包含由单体(a)衍生的结构单元(A),单体(a)具有从由以下述通式(Ⅰ)表示的基团、以下述通式(Ⅱ)表示的基团、以下述通式(Ⅲ)表示的基团及以下述通式(Ⅳ)表示的基团组成的组中选择的至少一种含硅原子基团；单体(a)的分子量为400至2500；消泡剂的含量相对于含硅原子树脂100质量份为0.7质量份至24质量份。(Coating composition, the film being consequently formed and aouatic structure object and ship with the film are provided, wherein, the coating composition is the coating composition comprising silicon atoms resin and defoaming agent, silicon atoms resin includes the structural unit as derived from monomer (a) (A), and monomer (a) has at least one silicon atoms group selected from group, the group indicated with the following general formula (II), the group that indicates with the following general formula (III) and the group formed with the group that the following general formula (IV) indicates by indicating with the following general formula (I)；The molecular weight of monomer (a) is 400 to 2500；The content of defoaming agent is 0.7 mass parts to 24 mass parts relative to 100 mass parts of silicon atoms resin.)

1. coating composition, for the coating composition comprising silicon atoms resin and defoaming agent, the silicon atoms resin includes The structural unit as derived from monomer (a) (A), the monomer (a) have from by being indicated with the following general formula (I) group, with following Group, the group indicated with the following general formula (III) and the group formed with the group that the following general formula (IV) indicates that general formula (II) indicates At least one silicon atoms group of middle selection；

The molecular weight of the monomer (a) is 400 to 2500；

The content of the defoaming agent is 0.7 mass parts to 24 mass parts relative to 100 mass parts of silicon atoms resin；

[chemical formula 1]

In general formula (I), a and b separately indicate 2~5 any integer, and m indicates 0~50 any integer, n indicates 3~ 80 any integer, R¹~R⁵Separately indicate alkyl, alkoxy, phenyl, substituted-phenyl, phenoxy group or substituent phenoxy；

[chemical formula 2]

In general formula (II), c and d separately indicate that 2~5 any integer, p indicate 0~50 any integer, R⁶、R⁷And R⁸ Separately indicate alkyl, R^aOr R^b；

R^aFor

[chemical formula 3]

In general formula, x indicates 0~20 any integer, R²³~R²⁷It is same or different, indicate alkyl；

R^bFor

[chemical formula 4]

In general formula, y indicates 1~20 any integer, R²⁸And R²⁹It is same or different, indicate alkyl；

[chemical formula 5]

In general formula (III), e, f, g and h separately indicate that 2~5 any integer, q and s separately indicate 0~50 Any integer, r indicate 3~80 any integer, R⁹~R¹²Separately indicate alkyl, alkoxy, phenyl, substituted-phenyl, Phenoxy group or substituent phenoxy；

[chemical formula 6]

In general formula (IV), i, j, k and l separately indicate that 2~5 any integer, t and u separately indicate 0~50 Any integer, v and w separately indicate 0~20 any integer, R¹³~R²²It is same or different, indicate alkyl.

2. coating composition according to claim 1, the monomer (a) is from the monomer by being indicated with the following general formula (I ') (a1), the monomer (a2) that is indicated with the following general formula (II '), the monomer (a3) indicated with the following general formula (III ') and with the following general formula (IV ') at least one selected in the group of monomer (a4) composition indicated；

[chemical formula 7]

In general formula (I '), R³¹Indicate hydrogen atom or methyl, a, b, m, n and R¹~R⁵It indicates and above-mentioned identical meaning；

[chemical formula 8]

In general formula (II '), R³²Indicate hydrogen atom or methyl, c, d, p and R⁶~R⁸It indicates and above-mentioned identical meaning；

[chemical formula 9]

In general formula (III '), R³³And R³⁴Separately indicate hydrogen atom or methyl, e, f, g, h, q, r, s and R⁹~R¹²It indicates With above-mentioned identical meaning；

[chemical formula 10]

In general formula (IV '), R³⁵And R³⁶Separately indicate hydrogen atom or methyl, i, j, k, l, t, u, v, w and R¹³~R²²Table Show and above-mentioned identical meaning.

3. coating composition according to claim 1 or 2, the silicon atoms resin further has to be spread out by monomer (b) Raw structural unit (B), the monomer (b) have from the group by being indicated with the following general formula (V) and with the following general formula (VI) table At least one group containing metallic atom selected in the group of the group composition shown；

[chemical formula 11]

In general formula (V), M indicates the metallic atom of divalent, R³⁰Indicate organic acid residue or alcohol residue；

[chemical formula 12]

In general formula (VI), M indicates the metallic atom of divalent.

4. coating composition according to claim 3, the monomer (b) is from the list by being indicated with the following general formula (V ') At least one selected in the group that body (b1) and the monomer (b2) indicated with the following general formula (VI ') form；

[chemical formula 13]

In general formula (V '), R³⁷Indicate hydrogen atom or methyl, M and R³⁰It indicates and above-mentioned identical meaning；

[chemical formula 14]

In general formula (VI '), R³⁸And R³⁹Separately indicate hydrogen atom or methyl, M is indicated and above-mentioned identical meaning.

5. coating composition according to any one of claims 1 to 4, the silicon atoms resin further has by monomer (c) structural unit derived from (C), the monomer (c) have the group indicated with the following general formula (VII)；

[chemical formula 15]

In general formula (VII), R⁴⁰、R⁴¹And R⁴²It is same or different, indicate the hydrocarbon residue of carbon atom number 1~20.

6. coating composition according to claim 5, the monomer (c) is the monomer indicated with the following general formula (VII ') (c1)；

[chemical formula 16]

In general formula (VII '), R⁴³Indicate hydrogen atom or methyl, R⁴⁰~R⁴²It indicates and above-mentioned identical meaning.

7. the defoaming agent includes silicon class defoaming agent according to 1~6 described in any item coating compositions.

8. coating composition according to claim 7, the silicon class defoaming agent is fluorine richness silicon class defoaming agent.

9. film is formed by coating composition according to any one of claims 1 to 8.

10. there is compelx coating the bottom film being made of antirusting paint and lamination to be wanted on the bottom film by right The film for asking 1~8 described in any item coating compositions to be formed.

11. compelx coating according to claim 10 further has between the bottom film and the film The intermediate film that the whole surface or part of the surface of the bottom film are formed.

12. aouatic structure object has film as claimed in claim 9 or the described in any item compound paintings of claim 10~11 Film.

13. ship has film as claimed in claim 9 or the described in any item compelx coatings of claim 10~11.

Technical field

The present invention relates to the coating compositions comprising silicon atoms resin.In addition, the invention further relates to by the Coating material composition The film that object is formed and the compelx coating with the film and the aouatic structure object and ship that have the film or compelx coating Oceangoing ship.

Background technique

On aouatic structure object or ship, the biologies such as barnacle easy to attach, mussel, algae.Such as on ship, due to life The attachment of object, the waste for producing and interfering its efficient operation, lead to fuel.Currently, applying deployment on the surface of ship etc. Dirty coating composition is to prevent biological attachment.

In international publication the 2011/046086th (patent document 1), disclose comprising the silicon atoms tree as carrier The antifouling paint compositions of rouge, thermoplastic resin and/or plasticizer.

On the other hand, as ship in the case where the place for generating friction with liquid (such as seawater) forms film, From the viewpoint of the navigation fuel consumption or energy-saving for reducing ship, it is expected that hindering the friction of itself and liquid using film Power reduces.

As the ability that there is the frictional resistance for making itself and liquid to reduce (hereinafter, also referred to as " low friction performance ".) coating, In international publication the 2005/116155th (patent document 2), disclose comprising vector resin, specific organic polymer grain The coating composition of son.

Summary of the invention

Problems to be solved by the invention

It is a first object of the present invention to provide coating composition, is capable of forming with excellent low friction performance, simultaneously And to the film of substrate (surface being coated with by coating composition) with excellent adaptation.

It is a second object of the invention to provide coating composition, is capable of forming with excellent low friction performance, simultaneously And there is the film of excellent adaptation to substrate, and the coating composition has excellent defoaming.

It is a third object of the invention to provide with the film formed by the coating composition and with the film Compelx coating and the aouatic structure object and ship for having the film or compelx coating.

The means to solve the problem

The present invention provides coating composition, film, compelx coating, aouatic structure object and ship below.

[1] coating composition, for the coating composition comprising silicon atoms resin and defoaming agent, the silicon atoms resin Comprising the structural unit as derived from monomer (a) (A), the monomer (a) have from by being indicated with the following general formula (I) group, with It group that the following general formula (II) indicates, the group that is indicated with the following general formula (III) and is formed with the group that the following general formula (IV) indicates Group at least one silicon atoms group for selecting；

The molecular weight of the monomer (a) is 400 to 2500；

The content of the defoaming agent is 0.7 mass parts to 24 mass relative to 100 mass parts of silicon atoms resin Part；

[chemical formula 1]

In general formula (I), a and b separately indicate that 2~5 any integer, m indicate that 0~50 any integer, n indicate 3~80 any integer, R¹~R⁵Separately indicate alkyl, alkoxy, phenyl, substituted-phenyl, phenoxy group or substituted benzene oxygen Base；

[chemical formula 2]

In general formula (II), c and d separately indicate that 2~5 any integer, p indicate 0~50 any integer, R⁶、R⁷ And R⁸Separately indicate alkyl, R^aOr R^b；

R^aFor

[chemical formula 3]

In general formula, x indicates 0~20 any integer, R²³~R²⁷It is same or different, indicate alkyl；

R^bFor

[chemical formula 4]

In general formula, y indicates 1~20 any integer, R²⁸~R²⁹It is same or different, indicate alkyl；

[chemical formula 5]

In general formula (III), e, f, g and h separately indicate 2~5 any integer, q and s separately indicate 0~ 50 any integer, r indicate 3~80 any integer, R⁹~R¹²Separately indicate alkyl, alkoxy, phenyl, substituted benzene Base, phenoxy group or substituent phenoxy；

[chemical formula 6]

In general formula (IV), i, j, k and l separately indicate 2~5 any integer, t and u separately indicate 0~ 50 any integer, v and w separately indicate 0~20 any integer, R¹³~R²²It is same or different, indicate alkyl.

[2] coating composition according to [1], the monomer (a) are from the monomer by being indicated with the following general formula (I ') (a1), the monomer (a2) that is indicated with the following general formula (II '), the monomer (a3) indicated with the following general formula (III ') and with the following general formula (IV ') at least one selected in the group of monomer (a4) composition indicated；

[chemical formula 7]

In general formula (I '), R³¹Indicate hydrogen atom or methyl, a, b, m, n and R¹~R⁵It indicates and above-mentioned identical meaning；

[chemical formula 8]

In general formula (II '), R³²Indicate hydrogen atom or methyl, c, d, p and R⁶~R⁸It indicates and above-mentioned identical meaning；

[chemical formula 9]

In general formula (III '), R³³And R³⁴Separately indicate hydrogen atom or methyl, e, f, g, h, q, r, s and R⁹~R¹² It indicates and above-mentioned identical meaning；

[chemical formula 10]

In general formula (IV '), R³⁵And R³⁶Separately indicate hydrogen atom or methyl, i, j, k, l, t, u, v, w and R¹³~ R²²It indicates and above-mentioned identical meaning.

[3] coating composition according to [1] or [2], the silicon atoms resin further has to be spread out by monomer (b) Raw structural unit (B), the monomer (b) have from the group by being indicated with the following general formula (V) and with the following general formula (VI) table At least one group containing metallic atom selected in the group of the group composition shown；

[chemical formula 11]

In general formula (V), M indicates the metallic atom of divalent, R³⁰Indicate organic acid residue or alcohol residue；

[chemical formula 12]

In general formula (VI), M indicates the metallic atom of divalent.

[4] coating composition according to [3], the monomer (b) are from the monomer by being indicated with the following general formula (V ') (b1) and with the following general formula (VI ') at least one selected in the group that the monomer (b2) indicated forms；

[chemical formula 13]

In general formula (V '), R³⁷Indicate hydrogen atom or methyl, M and R³⁰It indicates and above-mentioned identical meaning；

[chemical formula 14]

In general formula (VI '), R³⁸And R³⁹Separately indicate hydrogen atom or methyl, M is indicated and above-mentioned identical contained Justice.

[5] according to the described in any item coating compositions in [1]~[4], the silicon atoms resin further has by list Structural unit derived from body (c) (C), the monomer (c) have the group indicated with the following general formula (VII)；

[chemical formula 15]

In general formula (VII), R⁴⁰、R⁴¹And R⁴²It is same or different, indicate the hydrocarbon residue of carbon atom number 1~20.

[6] coating composition according to [5], the monomer (c) are the monomer indicated with the following general formula (VII ') (c1)；

[chemical formula 16]

In general formula (VII '), R⁴³Indicate hydrogen atom or methyl, R⁴⁰~R⁴²It indicates and above-mentioned identical meaning.

[7] according to the described in any item coating compositions in [1]~[6], the defoaming agent includes silicon class defoaming agent.

[8] coating composition according to [7], the silicon class defoaming agent are fluorine richness silicon class defoaming agent.

[9] film is formed by described in any item coating compositions of [1]~[8].

[10] compelx coating, have the bottom film that is made of antirusting paint and lamination on the bottom film by [1] film that the described in any item coating compositions in~[8] are formed.

[11] compelx coating according to [10] further has between the bottom film and the film The intermediate film that the whole surface or part of the surface of the bottom film are formed.

[12] aouatic structure object has the described in any item compelx coatings of film or [10]~[11] described in [9].

[13] ship has the described in any item compelx coatings of film or [10]~[11] described in [9].

The effect of invention

In accordance with the invention it is possible to provide coating composition, it is capable of forming with excellent low friction performance and to base Bottom has the film of excellent adaptation.

In accordance with the invention it is possible to provide coating composition, it is capable of forming with excellent low friction performance and to base Bottom has the film of excellent adaptation, and the coating composition has excellent defoaming.

In accordance with the invention it is possible to provide the compound painting with the film formed by the coating composition and with the film Film and the aouatic structure object and ship for having the film or compelx coating.

Specific embodiment

Coating composition of the invention, comprising as carrier components, aftermentioned specific silicon atoms resin, and defoaming Agent.The content of defoaming agent is 0.7 mass parts to 24 mass parts relative to 100 mass parts of silicon atoms resin.

Coating composition of the invention due to the defoaming agent comprising specified amount, and includes specific silicon atoms resin, Therefore good defoaming can be shown." defoaming " is meant that, can reduce in the film formed by coating composition Bubble property.

Generally, coating composition preferably still shows good defoaming being saved after a certain period of time.This hair Bright coating composition can still show good defoaming saving after a certain period of time.

The present invention is based on unexpected opinions, combine the defoaming agent of specific silicon atoms resin and specific quantity, in addition to Excellent defoaming also brings the excellent low friction performance and film of film to both excellent adaptations of substrate.That is, this Invention passes through combination in the case where using specific silicon atoms resin as carrier components based on unexpected opinion The defoaming agent of appropriate amount not only increases the defoaming generally yielded by the use of defoaming agent, and can be improved painting Adaptation of the low friction performance and film of film to substrate.

In addition, coating composition of the invention, due to including specific silicon atoms resin, energy as carrier components It is enough to form the film for showing soil resistance.Therefore, coating composition of the invention can be suitable as to ship surface, Or aouatic structure object surface or inner surface carry out antifouling antifouling paint compositions and use.

It as aouatic structure object, enumerates: the various fishing nets of cultivation fishnet etc. and other fishing gears；Port equipment；Petroleum Fence；The intake equipment in power station etc.；The piping of cooling aqueduct etc.；Bridge；Buoy；Industrial water system facility；Submarine Basic Ground etc..

Coating composition of the invention being capable of shape due to including specific silicon atoms resin as carrier components The film of good soil resistance is shown in growth time.

<silicon atoms resin>

The silicon atoms resin that antifouling paint compositions of the invention include, comprising structural unit (A).

Structural unit (A) is the structural unit as derived from monomer (a), and monomer (a) has from by being indicated with above-mentioned general formula (I) Group, the group indicated with above-mentioned general formula (II), the group that is indicated with above-mentioned general formula (III) and indicated with above-mentioned general formula (IV) Group composition group at least one silicon atoms group for selecting.

(1) silicon atoms group

Silicon atoms group possessed by monomer (a), for from by being indicated with above-mentioned general formula (I) group, with above-mentioned general formula (II) group that indicates and selects the group indicated with above-mentioned general formula (III) in the group formed with the group that above-mentioned general formula (IV) indicates At least one selected.

In general formula (I), a and b separately indicate that 2~5 any integer, m indicate that 0~50 any integer, n indicate 3~80 any integer.R¹~R⁵Separately indicate alkyl, alkoxy, phenyl, substituted-phenyl, phenoxy group or substituted benzene oxygen Base.

In general formula (II), c and d separately indicate that 2~5 any integer, p indicate 0~50 any integer.R⁶、R⁷ And R⁸Separately indicate alkyl, R^aOr R^b。

In R^aIn, x indicates 0~20 any integer.R²³~R²⁷It is same or different, indicate alkyl.

In R^bIn, y indicates 1~20 any integer.R²⁸And R²⁹It is same or different, indicate alkyl.

In general formula (III), e, f, g and h separately indicate 2~5 any integer, q and s separately indicate 0~ 50 any integer, r indicate 3~80 any integer.R⁹~R¹²Separately indicate alkyl, alkoxy, phenyl, substituted benzene Base, phenoxy group or substituent phenoxy.

In general formula (IV), i, j, k and l separately indicate 2~5 any integer, t and u separately indicate 0~ 50 any integer, v and w separately indicate 0~20 any integer.R¹³~R²²It is same or different, indicate alkyl.

About a~n, p~y and R¹~R²⁹, behind be described in detail.

Silicon atoms resin also can have from by being indicated with above-mentioned general formula (I) group, indicated with above-mentioned general formula (II) Group, the group indicated with above-mentioned general formula (III) and two kinds selected in the group formed with the group that above-mentioned general formula (IV) indicates Above silicon atoms group.In this case, it is possible to have the group indicated with above-mentioned general formula (I) it is two or more, with The two or more of the group that above-mentioned general formula (II) indicates, the group that is indicated with above-mentioned general formula (III) two or more, and/or more than State the two or more of the group of general formula (IV) expression.

A kind of preferred example of silicon atoms resin, for (methyl) acrylic resin with silicon atoms group.

" (methyl) acrylic acid ", which refers to, indicates at least one of of methacrylic acid and acrylic acid.

(2) monomer (a)

Monomer (a) preferably, for from by being indicated with above-mentioned general formula (I ') monomer (a1), indicated with above-mentioned general formula (II ') Monomer (a2), the monomer (a3) indicated with above-mentioned general formula (III ') and the monomer (a4) indicated with above-mentioned general formula (IV ') form At least one selected in group.By the inclusion of the polymerization of the monomer composition of monomer (a) so, (methyl) acrylic compounds are obtained The silicon atoms resin of resin, should (methyl) acrylic resin include by from monomer (a1), monomer (a2), monomer (a3) and single Structural unit (A) derived from the monomer (a) selected in the group of body (a4) composition.This silicon atoms resin has from by with above-mentioned logical Group that formula (I) indicates, the group indicated with above-mentioned general formula (II), the group that is indicated with above-mentioned general formula (III) and with above-mentioned general formula (IV) at least one silicon atoms group selected in the group of the group composition indicated.

Silicon atoms resin also may include the two or more structural units as derived from monomer (a) (A).

In general formula (I '), R³¹Indicate hydrogen atom or methyl, a, b, m, n and R¹~R⁵It indicates and above-mentioned identical meaning.

In general formula (II '), R³²Indicate hydrogen atom or methyl, c, d, p and R⁶~R⁸It indicates and above-mentioned identical meaning.

In general formula (III '), R³³And R³⁴Separately indicate hydrogen atom or methyl, e, f, g, h, q, r, s and R⁹~R¹² It indicates and above-mentioned identical meaning.

In general formula (IV '), R³⁵And R³⁶Separately indicate hydrogen atom or methyl, i, j, k, l, t, u, v, w and R¹³~ R²²It indicates and above-mentioned identical meaning.

The monomer (a1) that is indicated with above-mentioned general formula (I '), the monomer (a2) indicated with above-mentioned general formula (II '), with above-mentioned general formula (III ') monomer (a3) indicated and the monomer (a4) indicated with above-mentioned general formula (IV), respectively having is indicated with above-mentioned general formula (I) Group, the group indicated with above-mentioned general formula (II), the group that is indicated with above-mentioned general formula (III) and indicated with above-mentioned general formula (IV) Group silicon atoms polymerizable monomer.

Monomer (a1) is indicated with above-mentioned general formula (I ').Monomer (a) is used as by using monomer (a1), obtains having on side chain There is the silicon atoms resin of (methyl) acrylic resin of the silicon atoms group indicated with above-mentioned general formula (I).

Silicon atoms resin also may include the structural unit as derived from two or more monomers (a1).

It the use of molecular weight is 400 to 2500 as monomer (a).This is because having with silicon atoms resin defined Silicon atoms group, and premised on making the defoaming agent in coating composition containing specified amount, can be conducive to provide can be formed There is the coating composition of the film of excellent adaptation with excellent low friction performance and to substrate, or can have There is the coating composition of excellent defoaming conducive to offer.

It is being the coating composition of 400 to 2500 monomer (a) to molecular weight has been used, and is using the molecular weight not to be When the coating composition of 400 to 2500 monomer compares, the former in low friction performance, to the adaptation and defoaming of substrate Arbitrary one or more of, the two more than or it is all in, it is more excellent than the latter.

The molecular weight of monomer (a) is preferably 800 to 1500.

Monomer (a) is also possible to belong to the mixture of the two or more monomers of monomer (a), in this case, above-mentioned point Son amount is also possible to the average molecular weight of these monomers.

General formula (I ') is [same for general formula (I).] in a be preferably 2 or 3.

B is preferably 2 or 3.

From the viewpoint of water resistance of the m from film, adaptation to substrate etc., preferably 0 to 25, more preferably 0 to 20.M is either 3 or more perhaps 5 or more are also possible to 10 or less or 8 or less.

From the viewpoint of soil resistance of the n from film and the dissolubility to general organic solvent, preferably 5 to 50, more Preferably 8 to 40, it is also possible to 20 or less or 10 or less.

R¹~R⁵Substituted-phenyl and substituent phenoxy possessed by substituent group, for example, alkyl, halogen atom.

R¹~R⁵The alkyl that preferably alkyl, more preferably carbon atom number are 1~6, further preferably carbon atom number are 1~4 alkyl such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl etc., particularly preferably For methyl, ethyl.

As monomer (a1), " FM-0711 " (trade name), SHIN-ETSU HANTOTAI's chemical industry (strain) system of such as JNC (strain) system are enumerated " X-22-174BX ", " X-22-174ASX ", " X-22-2404 " (the above are trade names) etc..

Monomer (a2) is indicated with above-mentioned general formula (II ').Monomer (a) is used as by using monomer (a2), is obtained on side chain The silicon atoms resin of (methyl) acrylic resin with the silicon atoms group indicated with above-mentioned general formula (II).

Silicon atoms resin also may include the structural unit as derived from two or more monomers (a2).

General formula (II ') is [same for general formula (II).] in c, preferably 2 or 3.

D is preferably 2 or 3.

From the viewpoint of water resistance of the p from film, adaptation to substrate etc., preferably 0 to 25, more preferably 0 to 20.P is either 3 or more perhaps 5 or more are also possible to 10 or less or 8 or less.

X and y is respectively preferably 0 to 10, more preferably 0 from the viewpoint of the dissolubility to general organic solvent To 5.

R⁶~R⁸And R²³~R²⁹Alkyl, preferably carbon atom number be 1~6 alkyl, more preferably carbon atom number be 1 ~4 alkyl such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl etc., further preferably For methyl, ethyl.

R⁶~R⁸Both preferably alkyl.

As monomer (a2), enumerate such as " TM-0701 " (trade name) that JNC (strain) makes.

Monomer (a3) is indicated with above-mentioned general formula (III ').Monomer (a) is used as by using monomer (a3), can be had (this silicon atoms group is the crosslinking group that main polymer chain is cross-linked to each other to the silicon atoms group indicated with above-mentioned general formula (III) Group.) (methyl) acrylic resin silicon atoms resin.

Silicon atoms resin also may include the structural unit as derived from two or more monomers (a3).

General formula (III ') is [same for general formula (III).] in e and h, be respectively preferably 2 or 3.

F and g is respectively preferably 2 or 3.

From the viewpoint of water resistance of the q and s from film, adaptation to substrate etc., it is respectively preferably 0 to 30, it is more excellent It is selected as 0 to 25, further preferably 0 to 20.Q and s respectively either 3 or more perhaps 5 or more be also possible to 10 or less or 8 or less.

From the viewpoint of soil resistance of the r from film, the dissolubility to general organic solvent, preferably 5 to 50, it is more excellent 8 to 40 are selected as, is also possible to 20 or less or 10 or less.

R⁹~R¹²Substituted-phenyl and substituent phenoxy possessed by substituent group, for example, alkyl, halogen atom.

R⁹~R¹²The alkyl that preferably alkyl, more preferably carbon atom number are 1~6, further preferably carbon atom number For 1~4 alkyl such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl etc., particularly preferably Ground is methyl, ethyl.

As monomer (a3), " FM-7711 " (trade name), SHIN-ETSU HANTOTAI's chemical industry (strain) system of such as JNC (strain) system are enumerated " X-22-164A ", " X-22-164AS " (the above are trade names) etc..

Monomer (a4) is indicated with above-mentioned general formula (IV ').By using monomer (a4) be used as monomer (a), had more than Stating the silicon atoms group that general formula (IV) indicates, (this silicon atoms group is the crosslinked group that main polymer chain is cross-linked to each other.) (methyl) acrylic resin silicon atoms resin.

Silicon atoms resin also may include the structural unit as derived from two or more monomers (a4).

General formula (IV ') is [same for general formula (IV).] in i and l be respectively preferably 2 or 3.

J and k is respectively preferably 2 or 3.

From the viewpoint of water resistance of the t and u from film, adaptation to substrate etc., it is respectively preferably 0 to 30, it is more excellent It is selected as 0 to 25, further preferably 0 to 20.Q and s respectively either 3 or more perhaps 5 or more be also possible to 10 or less or 8 or less.

From the viewpoint of soil resistance of the v and w from film, the dissolubility to general organic solvent, preferably 0 to 10, more Add preferably 0 to 5, is also possible to 1 to 3.

R¹³~R²²Alkyl, preferably carbon atom number be 1~6 alkyl, more preferably carbon atom number be 1~4 alkane Base such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl etc. is further preferably methyl, Ethyl.

It as monomer (a4), enumerates for example: the commodity of former Japan Unika (strain) sale.The silicon industry of Japanese Unika (strain) Business, Dong Li DOW CORNING Co., Ltd. was transferred in 2004, it now is possible to obtain corresponding product from the assignee.

A~n, p~y and R¹~R²⁹With reference to above description, and properly select so that the molecular weight of monomer (a) is 400 To 2500.

From the viewpoint of silicon atoms resin is from soil resistance, low friction performance and/or to excellent adaptation of substrate etc., Also it may include two or more derivative by the monomer (a) selected from monomer (a1), monomer (a2), monomer (a3) and monomer (a4) Structural unit.

Wherein, it as a kind of preferred embodiment, can enumerate and the siliceous original acrylic acid modified with one end (methyl) Sub- polymerizable monomer [monomer (a1) and/or monomer (a2)] and both ends (methyl) acrylic acid modified silicon atoms polymerism list The mode of body [monomer (a3) and/or monomer (a4)].

From the viewpoint of from soil resistance, low friction performance and/or to excellent adaptation of substrate etc., spread out by monomer (a) The content of raw structural unit (A), in the entire infrastructure unit that silicon atoms resin includes, preferably 5 mass % to 80 matter Measure %, more preferably 10 mass % to 70 mass %, further preferably 20 mass % to 60 mass %.

By making the 5 mass % of content or more of structural unit (A), even if available not in addition containing anti-fouling agent In the case of, also show the coating composition of enough soil resistances.By make the 80 mass % of content of structural unit (A) with Under, be conducive to synthetically improve soil resistance and low friction performance and the adaptation to substrate.

(3) monomer (b)

Silicon atoms resin further can also have the structural unit as derived from monomer (b) (B), monomer (b) have from By at least one selected in the group indicated with above-mentioned general formula (V) and the group formed with the group that above-mentioned general formula (VI) indicates Group containing metallic atom.By making silicon atoms resin that further there is structural unit (B) other than structural unit (A), energy Enough further increase soil resistance, low friction performance and/or the adaptation to substrate of film.

Silicon atoms resin also can have the group indicated with above-mentioned general formula (V) and be indicated with above-mentioned general formula (VI) Both groups.

Preferably, monomer (b) is from the monomer (b1) by being indicated with above-mentioned general formula (V ') and with above-mentioned general formula (VI ') table At least one selected in the group of monomer (b2) composition shown.By the inclusion of the polymerization of the monomer composition of monomer (b) so, The silicon atoms resin of (methyl) acrylic resin is obtained, which includes by from monomer (b1) and singly Structural unit (B) derived from the monomer (b) selected in the group of body (b2) composition.This silicon atoms resin has from by with above-mentioned logical Group that formula (V) indicates and what is selected in the group that form with the group that above-mentioned general formula (VI) indicates at least one contain metal original Subbase group.

Silicon atoms resin also may include the two or more structural units as derived from monomer (b) (B).

It is [same for general formula (V) as general formula (V ').] and general formula (VI ') is [similarly for general formula (VI).] in Divalent metal atom M, Mg, Zn, Cu etc. can be enumerated, it is therefore preferable to Zn or Cu.

General formula (V ') is [same for general formula (V).] in R³⁰, preferably organic acid residue.

Monomer (b1) is indicated with above-mentioned general formula (V ').Monomer (b) is used as by using monomer (b1), is further had There is the silicon atoms resin of (methyl) acrylic resin of the group containing metallic atom indicated with above-mentioned general formula (V).

In R³⁰In, as the organic acid for forming organic acid residue, enumerate unitary organic acids such as acetic acid, chloroacetic acid, one Fluoroacetic acid, propionic acid, caproic acid, octanoic acid, 2 ethyl hexanoic acid, capric acid, versatic acid, isostearic acid, palmitinic acid, sucrose acid, oleic acid, anti-oil Acid, linoleic acid, linolenic acid, stearic acid, ricinoleic acid, ricinoleic acid, rape acid, erucic acid, α-naphthoicacid, β-naphthoic acid, benzene first It is acid, 2,4,5 T 2,4,5 trichlorophenoxy acetic acid, 2,4 dichloro benzene ethoxyacetic acid, quinoline carboxylic acid, nitrobenzoic acid, nitro naphthalene-carboxylic acid, fast Purine acid etc..

Wherein, when organic acid residue is fatty acid residue, it is however preferred to have interior for a long time film can be kept not split Line or the tendency of peeling.Particularly as monomer (b1), it is preferred to use oleic acid (methyl) zinc acrylate resin of high thermoplasticity Or versatic acid (methyl) zinc acrylate resin.

In addition, enumerating the unitary cyclic organic acids in addition to aromatic organic acid as other preferred organic acids.As Unitary cyclic organic acids are enumerated for example: the organic acid with naphthenic base of aphthenic acids etc., the resin acid of tricyclic resin acid etc., and These salt.

It as tricyclic resin acid, enumerates for example: the monoacid with Diterpenes hydrocarbon skeleton.As with Diterpenes hydrocarbon skeleton Monoacid, enumerate for example: with abietane-type, pimarane type, isopimarane type, laudanum alkane type skeleton compound.More Specifically, enumerate for example: abietic acid, neoabietic acid, dehydroabietic acid, hydroabietic acid, secondary rhzomorph acid, pimaric acid, isodextropimaric acid, Levopimaric acid, dextrorotation triphosphoric acid, salad alkane pimaric acid and these salt.Wherein, from the viewpoint of soil resistance of film etc., It is preferred that the salt of abietic acid, hydroabietic acid and these acid.

As unitary cyclic organic acids, do not need it is highly purified, for example, it is also possible to use pine tar, resin acid etc..As Such pine tar, resin acid are enumerated for example: rosin, hydrogenated rosin, disproportionated rosin class, aphthenic acids etc..Rosin refers to Rosin, wood rosin, toll oil rosin etc..It is preferred that rosin, hydrogenated rosin and disproportionated rosin class, are cheap because of it and are easy to obtain , with it is excellent it is operational, be easy to show long-term soil resistance.

The acid value of unitary cyclic organic acids, preferably 100mgKOH/g are to 220mgKOH/g, more preferably 120mgKOH/ G to 190mgKOH/g, further preferably 140mgKOH/ are to 185mgKOH/g.

As formation R³⁰Unitary cyclic organic acids, use the unitary cyclic organic acids with the acid value in above range When, there is the tendency for the good soil resistance that can for longer periods keep film.

The organic acid residue that monomer (b1) has can both be formed by a kind of organic acid, can also be had by two or more Machine acid is formed.

With as R³⁰Organic acid residue monomer (b1) manufacturing method, enumerate for example: making inorganic metal compound, (it is residual to constitute above-mentioned organic acid with carboxylic free radical polymerization monomer such as (methyl) acrylic acid and non-polymerization organic acid The organic acid of base), the method to react in the organic solvent containing alcohol compound.

The structural unit (B) as derived from monomer (b1), can also be by making by comprising carboxylic free-radical polymerised list The resin and metallic compound and non-polymerization organic acid that the monomer composition of body such as (methyl) acrylic acid polymerize (are constituted The organic acid of above-mentioned organic acid residue) method that reacts formed.

Monomer (b2) is indicated with above-mentioned general formula (VI ').Monomer (b) is used as by using monomer (b2), is further had Having the group containing metallic atom that indicates with above-mentioned general formula (VI), (main polymer chain is cross-linked to each other by this group containing metallic atom Crosslinked group.) (methyl) acrylic resin silicon atoms resin.

It as monomer (b2), enumerates for example: Magnesium Acrylate Prepared [(CH₂=CHCOO)₂Mg], magnesinm methacrylate [(CH₂=C (CH₃)COO)₂Mg], zinc acrylate resin [(CH₂=CHCOO)₂Zn], zinc methacrylate [(CH₂=C (CH₃)COO)₂Zn], propylene Sour copper [(CH₂=CHCOO)₂Cu], methacrylic acid copper [(CH₂=C (CH₃)COO)₂Cu] etc..These can according to need, suitably Ground selection is one or two kinds of used above.

It as the manufacturing method of monomer (b2), enumerates for example: making polymerism unsaturated organic acid such as (methyl) acrylic acid, and Metallic compound, in the organic solvent containing alcohol compound and method that water reacts together.In this case, excellent The content of water in reactant is adjusted to 0.01 mass % to 30 mass % by selection of land.

Silicon atoms resin also may include the structural unit as derived from monomer (b1) and the structure as derived from monomer (b2) Both units.

From the viewpoint of from the raising of soil resistance, low friction performance and/or to raising of adaptation of substrate etc., siliceous In the case that atom resin includes structural unit (B), the content of structural unit (B), in whole knots that silicon atoms resin includes In structure unit, preferably 2 mass % to 30 mass %, more preferably 4 mass % to 25 mass %, further preferably 6 matter Measure % to 20 mass %.

By making the 2 mass % of content or more of structural unit (B), it can be further improved the soil resistance of film, low rub Wipe performance and/or the adaptation to substrate.The content of structural unit (B) is 30 mass % hereinafter, being then conducive to synthetically improve Soil resistance and low friction performance and adaptation to substrate.

In the case where silicon atoms resin includes structural unit (B), in silicon atoms resin, structural unit (B) phase For the ratio { (B)/[(A)+(B)] } of total content of structural unit (A) and structural unit (B), as a percentage, preferably For 10 mass % to 70 mass %, more preferably 10 mass % to 50 mass %, further preferably 15 mass % to 40 matter Measure %.This is conducive to synthetically improve soil resistance and low friction performance and the adaptation to substrate.

(4) monomer (c)

Silicon atoms resin further can also have the structural unit as derived from monomer (c) (C), monomer (c) have with The group that above-mentioned general formula (VII) indicates.By making silicon atoms resin that further there is structure list other than structural unit (A) First (C), can further increase the soil resistance of film.

Preferably, monomer (c) is the monomer (c1) indicated with above-mentioned general formula (VII ').By the inclusion of the monomer of monomer (c1) The polymerization of composition obtains the siliceous original of (methyl) acrylic resin comprising the structural unit (C) as derived from monomer (c1) Subtree rouge.This silicon atoms resin has the group indicated with above-mentioned general formula (VII).

Silicon atoms resin also may include the two or more structural units as derived from monomer (c) (C).

General formula (VII ') is [same for general formula (VII).] in R⁴⁰、R⁴¹And R⁴²It is same or different, indicate carbon atom number 1~20 hydrocarbon residue (alkyl of monovalence).Silicon atoms resin also can have the two of the group indicated with above-mentioned general formula (VII) Kind or more.

As the hydrocarbon residue of carbon atom number 1~20, enumerate for example:

Carbon atom be 20 straight-chains below or branched-chain alkyl such as: methyl, ethyl, n-propyl, isopropyl, normal-butyl, Isobutyl group, sec-butyl, tert-butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecane Base, myristyl etc.；

Cyclohexyl, the cyclic alkyl such as substituted cyclohexyl that can have substituent group etc.；

Aryl, the aryl such as substituted aryl that can have substituent group etc..

As the cyclic alkyl that can have substituent group, enumerate by halogen, carbon atom number most about 18 alkyl, acyl group, The substituted cyclic alkyl such as nitro or amino.

As the aryl that there can be substituent group, enumerate by halogen, carbon atom number most about 18 alkyl, acyl group, nitro Or the aryl that amino etc. is substituted.

Wherein, from the point of view of it can keep the good soil resistance of film long-term and stably, it is preferable that R⁴⁰、R⁴¹And R⁴²'s More than one is isopropyl, it is further preferred that R⁴⁰、R⁴¹And R⁴²It is isopropyl.

From the viewpoint of raising from soil resistance etc., in the case where silicon atoms resin includes structural unit (C), structure The content of unit (C), in the entire infrastructure unit that silicon atoms resin includes, preferably 2 mass % to 55 mass %, more Preferably 5 mass % to 50 mass %, further preferably 10 mass % are to 45 mass %.

By making the 2 mass % of content or more of structural unit (C), the soil resistance of film can be further increased.Structure The content of unit (C) is 55 mass % hereinafter, being then conducive to synthetically improve soil resistance and low friction performance and to the close of substrate Conjunction property.

In the case where silicon atoms resin includes structural unit (C), in silicon atoms resin, structural unit (C) phase For the ratio { (C)/[(A)+(C)] } of total content of structural unit (A) and structural unit (C), as a percentage, preferably For 10 mass % to 90 mass %, more preferably 20 mass % to 80 mass %, further preferably 30 mass % to 70 matter Measure %.This is conducive to synthetically improve soil resistance and low friction performance and the adaptation to substrate.

(5) other monomers (d)

Silicon atoms resin also may include to be spread out by the other monomers (d) except demonomerization (a), monomer (b) and monomer (c) Raw structural unit (D).

As monomer (d), as long as the unsaturated monomer that can be copolymerized with monomer (a), monomer (b) and monomer (c), not It particularly limits, enumerates for example:

(methyl) acrylate monomer is such as: (methyl) methyl acrylate, (methyl) ethyl acrylate, 2- methoxy ethyl (methyl) acrylate, 2- ethoxyethyl group (methyl) acrylate, Phenoxyethyl (methyl) acrylate, 2- (2- ethyl Hexyloxy) ethyl (methyl) acrylate, 1- methyl -2- methoxy ethyl (methyl) acrylate, 3- methoxybutyl (first Base) it is acrylate, 3- methyl -3- methoxybutyl (methyl) acrylate, m- methoxyphenyl (methyl) acrylate, right Methoxyphenyl (methyl) acrylate, o-methoxyphenyl ethyl (methyl) acrylate, m-methoxyphenyl ethyl (first Base) acrylate, p-methoxyphenyl ethyl (methyl) acrylate, n-propyl (methyl) acrylate, isopropyl (methyl) Acrylate, normal-butyl (methyl) acrylate, isobutyl group (methyl) acrylate, tert-butyl (methyl) acrylate, 2- second Base hexyl (methyl) acrylate, dodecyl (methyl) acrylic acid, stearyl (methyl) acrylate, benzyl (methyl) propylene Acid esters, phenyl (methyl) acrylate, isobornyl (methyl) acrylate, cyclohexyl (methyl) acrylate, glycidol Base (methyl) acrylate etc.；

(methyl) acrylic monomer of hydroxyl is such as: 2- hydroxyethyl (methyl) acrylate, 2- hydroxypropyl (first Base) acrylate, 3- hydroxypropyl (methyl) acrylate, 2- hydroxybutyl (methyl) acrylate, 4- hydroxybutyl (first Base) acrylate etc.；

2- hydroxyethyl (methyl) acrylate or 2- hydroxypropyl (methyl) acrylate and ethylene oxide, epoxy The addition product of propane, gamma-butyrolacton or 6-caprolactone etc.；

The dimer or trimerization of 2- hydroxyethyl (methyl) acrylate, 2- hydroxypropyl (methyl) acrylate etc. Body；

Glycerol (methyl) acrylate etc. has (methyl) acrylic monomer of multiple hydroxyls；

Vinyl monomer containing primary or secondary amino is such as: Butylaminoethyl (methyl) acrylate, (methyl) acrylamide Deng；

The vinyl monomer of tertiary-amino-containing is such as: dimethyl aminoethyl (methyl) acrylate, diethylamino ethyl (first Base) acrylate, dimethylaminopropyl (methyl) acrylate, dimethrlaminobutyl (methyl) acrylate, dibutyl Amino-ethyl (methyl) acrylate, dimethyl aminoethyl (methyl) acrylamide, dimethylaminopropyl (methyl) propylene Amide etc.；

Heterocyclic alkaline monomer is such as: vinyl pyrrolidone, vinylpyridine, vinyl carbazole；

Other vinyl monomers such as styrene, vinyltoluene, α-methylstyrene, (methyl) acrylonitrile, vinyl acetate Ester, vinyl propionate etc..

The content of the structural unit as derived from monomer (d) (D), in the entire infrastructure unit that silicon atoms resin includes, Usually 0.1 mass % to 95 mass %, it is therefore preferable to 5 mass % to 90 mass %, further preferably extremely for 10 mass % 70 mass %.

By making the 0.1 mass % of content or more of structural unit (D), it can adjust the various spies of resulting coating composition The balance of property.By making the 95 mass % of content of structural unit (D) hereinafter, can obtain even if in addition not containing anti-fouling agent In the case where, also show the coating composition of enough soil resistances.

(6) manufacturing method of silicon atoms resin

The manufacturing method of silicon atoms resin, although not particularly limiting, however, it is possible on for example, by that will be mixed with It is small that the monomer composition for the monomer stated carries out 5~14 in the presence of radical initiators, with 60 DEG C~180 DEG C of reaction temperature When reaction and prepare.The condition of polymerization reaction can also suitably adjust.

It as radical initiator, enumerates for example: bis- (2, the 4- dimethyl-pentens of 2,2- azodiisobutyronitriles, 2,2- azo Nitrile), 2,2- azo bis- (2- methylbutyronitriles), benzoyl peroxide, cumene hydroperoxide, lauroyl peroxide, peroxidating two Tert-butyl, peroxide -2 ethyl hexanoic acid tert-butyl ester etc..

It as polymerization, enumerates: solution polymerization process, emulsion polymerization, the suspension polymerization carried out in organic solvent Deng.From the viewpoint of manufacture efficiency from silicon atoms resin etc., preferred solution polymerization process.

As organic solvent, general organic solvent such as toluene, dimethylbenzene, methyl iso-butyl ketone (MIBK), n-butyl acetate are enumerated Deng.

Using monomer (b2), for the raising of the high solidification or manufacture efficiency of coating composition, and suppression The generation of waterglass, also can be used chain-transferring agent when system polymerization.As chain-transferring agent, from the sight of the intermiscibility with monomer (b) From the point of view of point, the chain-transferring agent preferably except mercaptan, optimization styrene dimer etc..

The number-average molecular weight of silicon atoms resin is usually 1000 to 100000, and preferably 3000 to 50000, more preferably It is 5000 to 30000.

When the number-average molecular weight of silicon atoms resin is 1000 or more, the film formed by coating composition has can Show the tendency of soil resistance.When the number-average molecular weight of silicon atoms resin is 100000 or less, silicon atoms resin has It is easy to be evenly dispersed in the tendency in coating composition.

The number-average molecular weight of silicon atoms resin, what the polystyrene to be measured by gel permeation chromatography (GPC) converted Number-average molecular weight.

<coating composition>

Coating composition of the invention includes the above-mentioned silicon atoms resin and defoaming agent as carrier components.

(1) content of silicon atoms resin

The content of the silicon atoms resin of coating composition, in the solid component that coating composition contains, preferably 30 Quality % to 99 mass %, more preferably 40 mass % are to 90 mass %, or 85 mass % or less.

When the content of silicon atoms resin is less than 30 mass %, have film to the adaptation of substrate, the low friction of film The tendency that performance and the soil resistance of film reduce.

The solid component that coating composition contains refers to, the summation for the ingredient in addition to solvent that coating composition contains.

(2) defoaming agent

Coating composition of the invention includes defoaming agent.Coating composition both can only include a kind of defoaming agent, can also be with Include two or more defoaming agents.

Defoaming agent refers to have the function of keeping the surface of foam to be formed uneven and inhibit the examination of the formation of foam Agent, alternatively, having the reagent for making established foam partial dilution and destroying foam.

The content of defoaming agent is 0.7 mass parts to 24 mass parts, from film relative to 100 mass parts of silicon atoms resin From the viewpoint of the adaptation of substrate, preferably 20 below the mass, and more preferably 16 below the mass, further preferably Below the mass for 14, especially preferably 12 below the mass.

From the viewpoint of from the low friction performance of the viewpoint of defoaming and/or film, the content of defoaming agent is relative to siliceous 100 mass parts of atom resin, it is more than preferably 1 mass parts, it is more than more preferably 2 mass parts, further preferably 3 mass parts More than, it is more than particularly preferably 4 mass parts.From the viewpoint of from the low friction performance of the viewpoint of defoaming and/or film, defoaming The content of agent is relative to 100 mass parts of silicon atoms resin, more than preferably also 5 mass parts or more than 10 mass parts.

It as defoaming agent, enumerates: silicon class defoaming agent, non-silicon class defoaming agent.

Silicon class defoaming agent is comprising the defoaming agent with the polysiloxanes of surface-active or its modifier, the defoaming of non-silicon class Agent is the defoaming agent (defoaming agent not comprising polysiloxanes or its modifier) except silicon class defoaming agent.

It as non-silicon class defoaming agent, enumerates: higher alcohols, higher alcohol derivative species, fatty acid, derivative of fatty acid Class, paraffin class, (methyl) acrylic polymer class, mineral oils etc..

It as silicon systems defoaming agent, enumerates: the type of oil type, compound, self-emulsifying type, emulsion-type etc..

From the defoaming of coating composition (particularly, save defoaming) after a certain period of time, the low friction performance of film And/or from the viewpoint of film is to the adaptation of substrate, defoaming agent preferably comprises silicon class defoaming agent, more preferably only includes silicon class Defoaming agent.Wherein, from the defoaming of coating composition (particularly, save defoaming) after a certain period of time, the low friction of film From the viewpoint of performance and/or film are to the adaptation of substrate, defoaming agent preferably comprises fluorine richness silicon class defoaming agent, more preferably It only include fluorine richness silicon class defoaming agent.Fluorine richness silicon systems defoaming agent refers to, the defoaming agent of the polysiloxanes comprising fluorine richness.

As defoaming agent, commercially available product also can be used.

As the commercially available product of non-silicon systems defoaming agent, enumerate for example: the mineral oils of " BYK-030 " of BYK corporation etc. disappear Infusion；Nanmu be melted into " the Supreme Being Si Balong OX68 " of Co. Ltd. system, BYK corporation " BYK-1790 " etc. the defoaming of polymerization species Agent etc..

It as the commercially available product of the silicon systems defoaming agent except fluorine richness silicon systems defoaming agent, enumerates: SHIN-ETSU HANTOTAI's chemical industry strain formula meeting The silicone oil defoaming agent etc. of " BYK-081 " of " KF-96 " of society, BYK corporation etc..

It as the commercially available product of fluorine richness silicon systems defoaming agent, enumerates for example: " BYK-063 ", the SHIN-ETSU HANTOTAI's chemical industry of BYK society The fluorosilicon oil class defoaming agent of " FA-630 " of Co. Ltd. system etc. etc..

(3) thermoplastic resin/plasticizer

Coating composition can contain thermoplastic resin and/or plasticizer.By making it contain thermoplastic resin and/or increasing Agent is moulded, the crack resistance of film can be made to improve.In addition, due to that the polishing speed (grinding rate) of film can be controlled appropriate Speed in, therefore be conducive to the long-term soil resistance of film.

It as thermoplastic resin, enumerates: chlorinated paraffin；Chloridized polyolefin such as chlorinated rubber, haloflex, chlorination poly- third Alkene etc.；Polyvinylether；Poly- diethyl sebacate；Partially hydrogenated terphenyl；Polyvinyl acetate；Poly- (methyl) alkyl acrylate As (methyl) methyl acrylate analog copolymer, (methyl) ethyl acrylate analog copolymer, (methyl) propyl acrylate analog copolymer, (methyl) butyl acrylate analog copolymer, (methyl) acrylate lipin polymer etc.；Polyether polyol；Alkyd resin；It is poly- Ester resin；Vinyl chloride resin such as vinyl chloride vinyl acetate copolymer, vinyl chloride-vinyl propionate copolymer, vinyl chloride-are different Butyl vinyl ether copolymer, vinyl chloride-isopropyl-ethylene base ether copolymer, vinyl chloride-ethyl vinyl ether copolymer etc.；Silicon Oil；Grease and its purified；Vaseline；Atoleine；Rosin, hydrogenated rosin, aphthenic acids, fatty acid and these divalent metal Salt.

If enumerating the example of above-mentioned grease and its purified, such as solid grease such as wax (includes beeswax under room temperature Wax, the wax of plant origin etc. of equal animal origins) etc. or room temperature under liquid grease such as castor oil etc..

One kind both can be only used alone in thermoplastic resin, also can be used together two or more.

Among above-mentioned, preferably chlorinated paraffin, polyvinylether, polyether polyol, rosin, vinyl chloride-isobutyl vinyl base ether Copolymer, particularly, chlorinated paraffin, polyvinylether, rosin and vinyl chloride-isobutyl vinyl ether copolymer, due to being suitble to apply The thermoplasticity of film and the adjustment of film consumption, therefore more preferably.

It as plasticizer, enumerates for example: phthalic ester plasticizer such as dioctyl phthalate (DOP), adjacent benzene Dicarboxylic acid dimethyl ester, dicyclohexyl phthalate, diisooctyl phthalate (DIDP) etc.；Aliphatic dibasic acid ester increases Mould agent such as adipic acid isobutyl ester, dibutyl sebacate etc.；Ethylene glycol ester plasticizer such as diethylene glycol dibenzoate, pentaerythrite Arrcostab etc.；Phosphate plasticizer such as tricresyl phosphate (tricresyl phosphate), triaryl phosphate (phosphoric acid triaryl Ester), trichloroethyl phosphate etc.；Epoxy plasticiser such as epoxidized soybean oil, epoxy octyl stearate etc.；Organic tin plasticizer Such as dioctyltin laurate, dibutyl tin laurate；Trioctyl trimellitate (TOTM), three acetylene.

One kind both can be only used alone in plasticizer, also can be used together two or more.

Among above-mentioned, phthalic ester plasticizer such as dioctyl phthalate (DOP), phthalic acid diformazan Ester, dicyclohexyl phthalate, diisooctyl phthalate (DIDP) etc. and phosphate plasticizer such as phosphate trimethylbenzene Ester (tricresyl phosphate), triaryl phosphate (triaryl phosphate), trichloroethyl phosphate etc., due to silicon atoms resin And the compatibility of thermoplastic resin is especially excellent, and can cover film and integrally improve crack resistance in heterogeneity, therefore preferably.

The thermoplastic resin of coating composition and/or total content of plasticizer, relative to 100 mass of silicon atoms resin Part, it is therefore preferable to 3 mass parts to 100 mass parts, more preferably 5 mass parts to 50 mass parts, further preferably 5 mass parts To 30 mass parts.

When total content of thermoplastic resin and/or plasticizer relative to 100 mass parts of silicon atoms resin less than 3 mass When part, it is believed that the tendency of the improvement without crack resistance brought by the addition as thermoplastic resin and/or plasticizer, separately Outside, it is believed that the long-term soil resistance improvement without film brought by the addition as thermoplastic resin and/or plasticizer Tendency.

When total content of thermoplastic resin and/or plasticizer is more than 100 matter relative to 100 mass parts of silicon atoms resin When measuring part, having not only reduces film to the tendency of the soil resistance of the adaptation of substrate but also reduction film.

(4) anti-fouling agent

The film obtained by coating composition of the invention, by based on silicon atoms resin shown from polishability Anti-fouling effect, therefore good soil resistance can be played.

However, in order to further increase the soil resistance of film, alternatively, in order to more improve the long duration of soil resistance, As needed, coating composition can also contain anti-fouling agent.

It as anti-fouling agent, can be used well known, enumerate for example: inorganic compound, metalliferous organic compound and not Metalliferous organic compound etc..

As anti-fouling agent, enumerate for example: zinc oxide；Cuprous oxide；Ethylidene dithiocarbamate manganese；Dimethyl two Zinc thiocarbamate；2- methyl mercapto -4- tert-butylamino -6- cyclopropylamino-s- triazine；2,4,5,6- tetrachloro isophthalic two Nitrile；N, N- dimethyl dichlorophenyl urea；Zinc ethylene bisdithiocarbamate；Luo Dantong (cuprous sulfocyanide)；4,5- bis- is chloro- Kathon (chloro- 2- n-octyl -3 (2H) isothiazolone of 4,5- bis-)；N- (fluorine dichloro methyl mercapto) is adjacent Phthalimide；N, N'- dimethyl-N'- phenyl-(N- fluorine dichloro methyl mercapto) sulfonamide；Metal salt such as 2- pyridine mercaptan -1- Aoxidize zinc salt (zinc pyrithione) or mantoquita (copper pyrithione)；Tetramethylthiuram disulfide；2,4,6- trichlorophenyl horse Carry out acid imide；2,3,5,6- tetra- chloro- 4- (methyl sulphonyl) pyridine；3-Iodo-2-propynyl butyl carbamate；Diiodomethyl P-methylphenyl sulfone；Phenyl (double pyridyl groups) dichloride bismuth；2- (4- thiazolyl)-benzimidazole；Pyridinium triphenylboron salt；Octadecane Base-triphenyl；Dodecyl-triphenyl；Dimethyl disulfide is for carbamoyl zinc ethylenebis dithiocarbamate；1, The fluoro- N- phenyl methanesulfonamide amide of the chloro- N- of 1- bis- [(dimethylamino) sulfonyl] -1-；Chloro- N- [(dimethylamino) sulphur of 1,1- bis- Acyl group] the fluoro- N- of -1- (4- aminomethyl phenyl) Methanesulfomide；N'- (3,4- dichlorophenyl)-N, N'- dimethyl urea；N'- tert-butyl- N- cyclopropyl -6- (methyl mercapto) -1,3,5- triazine -2,4- diamines；The bromo- 2- of 4- (4- chlorphenyl) -5- (trifluoromethyl) -1H- pyrrole Cough up -3- formonitrile HCN.

One kind both can be only used alone in anti-fouling agent, also can be used together two or more.

The content of the anti-fouling agent of coating composition, relative to 100 mass parts of silicon atoms resin, it is therefore preferable to 30 mass parts Hereinafter, more preferably 20 below the mass, further preferably 10 below the mass.

(5) other compositions

Coating composition can also contain the other compositions except mentioned component.As other compositions, enumerate for example: face Material, water-binding agent, anti-sagging agent, stainblocker, sagging inhibitor, film consume regulator, ultraviolet absorbing agent, surface modulation Additive and solvent of agent, viscosity modifier, levelling agent, pigment dispersing agent etc. etc..

As pigment, enumerate for example:

Extender pigment, such as: precipitability barium, talcum, clay, chalk, white carbon black, alumina white, bentonite, calcium carbonate, carbonic acid Magnesium, silicic acid, silicate, hydrated alumina, calcium sulfate etc.；

Coloring pigment, such as: titanium oxide, zirconium oxide, basic lead sulphate, tin oxide, carbon black, zinc powder, graphite, zinc sulphide, oxygen Change zinc, chromium oxide, nickel titanium yellow, chromium titan yellow, iron oxide yellow, iron oxide red (red ocher), black iron oxide, the red yellow color of azo Pigment, chrome yellow, phthalocyanine green, phthalocyanine blue, ultramarine blue, quinacridone etc..

One kind both can be only used alone in pigment, also can be used together two or more.

As solvent, enumerate such as following:

Hydrocarbon is such as: toluene, dimethylbenzene, ethylbenzene, pentamethylene, octane, heptane, hexamethylene, petroleum solvent；

Ethers is such as: dioxanes, tetrahydrofuran, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol Butyl oxide, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, butyl cellosolve etc.；

Esters are such as: butyl acetate, propyl acetate, benzyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetic acid Ester etc.；

Ketone is such as: ethyl isobutylo ketone, methyl iso-butyl ketone (MIBK)；

Alcohols is such as: n-butanol, propyl alcohol.

One kind both can be only used alone in solvent, also can be used together two or more.

(6) preparation of coating composition

Coating composition of the invention, can be for example, by silicon atoms resin or containing its resin combination In (for example, solution or dispersion liquid comprising silicon atoms resin), defoaming agent is added, and pigment and molten is added as needed The other compositions such as agent are mixed using mixing machine such as ball mill, gravel mill, roller mill, sand mill, high speed disperser etc., To prepare.

<film and compelx coating>

Aforementioned coating composition, can be by being conventionally applied to the surface of coated article by film of the invention Afterwards, volatilize removal solvent at normal temperature or under heating as needed, to be formed.

As the coating method of coating composition, conventionally known method is enumerated for example: infusion process, spray coating method, brushing, roller Painting, electrostatic spraying, electrodeposition coating etc..

As coated article, such as ship, aouatic structure object are enumerated.It as aouatic structure object, enumerates: cultivation fishnet etc. Various fishing nets and other fishing gears；Port equipment；Petroleum fence；The intake equipment in power station etc.；Cooling aqueduct etc. is matched Pipe；Bridge；Buoy；Industrial water system facility；Seabed base etc..

The film formed using coating composition of the invention can have excellent soil resistance, low friction performance and right The adaptation of substrate.

The coating surface of above-mentioned coated article can according to need carry out pre-treatment, both alternatively, it is also possible to by coated article On the bottom film of other coating composition of the antirusting paint (anticorrosive coating) of upper formation etc., formed by coating group of the invention Close the film of object composition and as compelx coating.

Coating composition according to the present invention, due to the silicon atoms resin itself as carrier can show it is good Soil resistance, therefore may not need separately addition anti-fouling agent or reduce its formula ratio.Therefore, Coating material composition according to the present invention Object can form clear (high transparency) antifouling coat.

As anti-fouling agent, antifouling painting that the existing antifouling paint compositions by mainly containing a large amount of cuprous oxide are formed Film usually has slightly reddish tone due to the cuprous oxide contained, and the tone of film is defined, but according to the present invention, Various applications can be carried out using the transparency of obtained film.In addition, in the case where forming transparent film, painting of the invention Feed composition does not include coloring pigment preferably.

For example, having the bottom film being made of antirusting paint etc. and the painting of the invention formed on the bottom film In the compelx coating of film, by using film of the invention as transparent antifouling coat, using the coating of various tones as antirust Coating and use, the coated articles such as aouatic structure object can be provided, not only there is soil resistance, but also compelx coating forms surface tool There is unexistent tone in the past.

Alternatively, it is also possible to by being formed between the bottom film and transparent antifouling coat being made of antirusting paint etc. The intermediate film being made of the coating with various tones is capable of providing the coated article with tone no in the past.

As the coating for forming intermediate film, can be used for example: antifouling paint, epoxy resin coating, polyurethane tree Lipid coating, (methyl) acrylic resin-based coating, chlorinated rubber class coating, alkyd resin class coating, silicones class coating, fluorine The various coating such as resinae coating.

The antifouling paint of intermediate film is formed, either coating composition of the invention, is also possible to other antifouling Coating composition such as contains the existing antifouling paint compositions of relatively great amount of anti-fouling agent.

Intermediate film can both be formed in the entire surface of bottom film, can also be formed in a part on surface.It is intermediate Film and bottom film are also possible to the old film used.In this case, film of the invention can also be used as old The reparation of film and used.

If in addition, by the intermediate painting between the bottom film and transparent antifouling coat being made of antirusting paint etc. Film is formed as such as the text shape of various tones, textured, pattern-like, pattern shape, then can assign to coated article various each The design of sample.

It, can also as the substitution of the intermediate film by being formed in the coating between bottom film and transparent antifouling coat So that the film or seal member of the various tones of the shape with text shape, textured, pattern-like, pattern shape etc. are between it Between, assign the various designs of coated article.