WO2019065035A1

WO2019065035A1 - Fluorine-containing coating agent composition, surface treating agent, and article

Info

Publication number: WO2019065035A1
Application number: PCT/JP2018/031529
Authority: WO
Inventors: 理佐片山; 祐治山根; 松田　高至; 隆介酒匂
Original assignee: 信越化学工業株式会社
Priority date: 2017-09-27
Filing date: 2018-08-27
Publication date: 2019-04-04
Also published as: JPWO2019065035A1; TWI779101B; TW201925383A; CN111148804A; JP6891968B2; CN111148804B; KR20200058409A; KR102589656B1

Abstract

This surface treating agent is capable of forming a water-repellent and oil-repellent layer that has excellent abrasion resistance for resin and metal surfaces. The surface treating agent comprises a fluorine-containing coating agent composition that mixes and uses, in a specific mixing ratio, perhydropolysilazane and a hydroxyl group which comprises at least three siloxane bonds and/or at least two silphenylene bonds in the molecule and which is denatured by a fluorooxyalkylene group-containing polymer or a hydrolyzable group-containing organic silicon compound and/or a partial (hydrolysis) condensate thereof.

Description

Fluorine-containing coating composition, surface treatment agent and article

The present invention relates to a fluorine-containing coating composition, and in particular, a fluorine-containing coating composition that forms a film excellent in water and oil repellency and abrasion resistance, a surface treatment agent containing the composition, and the above The present invention relates to an article surface-treated with a surface treatment agent.

The surface treatment agent until now has many surface treatment agents showing good water and oil repellency to glass, but adhesion and water and oil repellency to surfaces other than glass such as resin and metal, There is no one that sufficiently indicates surface characteristics such as abrasion resistance. In addition, when a water and oil repellent layer is provided on a resin or metal surface, direct application of a surface treatment agent has insufficient performance.

In general, the fluoropolyether group-containing compound has water and oil repellency, chemical resistance, lubricity, releasability, antifouling property and the like because its surface free energy is very small. Industrially, it is widely used in industrial applications such as water and oil repellent soiling agents such as paper and fiber, lubricants for magnetic recording media, oil repellent agents for precision equipment, mold release agents, cosmetics, and protective films. ing. However, its properties mean that it is at the same time non-adhesive and non-adhesive to other substrates, and even though it can be applied to the substrate surface, it was difficult to adhere the film. .

On the other hand, silane coupling agents are well known as those for bonding a substrate surface such as glass or cloth to an organic compound, and are widely used as coating agents for various substrate surfaces. The silane coupling agent has an organic functional group and a reactive silyl group (generally, a hydrolyzable silyl group such as an alkoxysilyl group) in one molecule. The hydrolyzable silyl group causes a self condensation reaction due to moisture in the air or the like to form a film. The coating becomes a durable and durable coating by chemically and physically bonding the hydrolyzable silyl group to a surface such as glass or metal.

Therefore, by using a fluoropolyether group-containing polymer-modified silane in which a hydrolyzable silyl group is introduced to the fluoropolyether group-containing compound, the base material easily adheres to the substrate surface, and water and oil repellency and oil resistance on the substrate surface. There is disclosed a composition capable of forming a film having chemical properties, lubricity, releasability, antifouling properties, etc. (Patent Documents 1 to 8: Japanese Patent Application Laid-Open No. 2003-238577, Patent No. 2860979, Patent No. 4672095, JP-A-2008-534696, JP-A-2008-537557, JP-A-2012-072272, JP-A-2012-157856, JP-A-2013-136833).

When surface-treating a substrate with the composition containing the fluoropolyether group-containing polymer-modified silane described above, a film is formed on the substrate using various coating methods, but after coating, the hydrolyzable silyl group is coated In the process of hydrolyzing and curing the film, the hydrolysis reaction is promoted by high temperature conditions such as 80.degree. C. and 120.degree. C. and humidified conditions. In addition, a cured film can be formed by gradually reacting with moisture in the air even at room temperature. However, the curing process requires high-temperature humidification conditions, takes a long time to cure at room temperature, and so forth, which may cause a rate-determining factor (delay factor) in manufacturing. Furthermore, the film (water and oil repellent layer) cured in a short time under mild conditions such as room temperature curing has a problem that the anti-soiling property and the antifouling performance are deteriorated during use.

In patent document 9 (Unexamined-Japanese-Patent No. 2008-144144), it forms into a film in mild conditions and a short time by promoting hardening by adding a fluorine-containing carboxylic acid as a curing catalyst in a coating composition. . However, reducing the amount of catalyst results in inferior wear resistance, and increasing the amount of catalyst lowers the initial performance. In addition, there is a high possibility that the carboxyl group which is a polar group is exposed to the outermost surface of the film, and in that case, the performance is lowered.

There is also a method of adding a catalyst to accelerate the hydrolysis reaction of the alkoxysilyl group. Conventionally known catalysts include organic titanates such as tetrabutyl titanate and tetraisopropyl titanate; organic titanium chelate compounds such as diisopropoxybis (ethylacetoacetate) titanium; aluminum tris (acetylacetonate), aluminum tris Organoaluminum compounds such as (ethyl acetoacetate); Organozirconium compounds such as zirconium tetra (acetylacetonate) and zirconium tetrabutyrate; Dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin di (2-ethylhexanoate), dioctyltin Organotin compounds such as dilaurate, dioctyltin diacetate, dioctyltin dioctoate, etc .; tin naphthenate, tin oleate, tin butylate, naphthenate Metal salts of organic carboxylic acids such as zinc stearate; amine compounds such as hexylamine and dodecylamine phosphate and salts thereof; quaternary ammonium salts such as benzyltriethylammonium acetate; alkali metals such as potassium acetate and lithium nitrate Lower fatty acid salts; dialkylhydroxylamines such as dimethylhydroxylamine and diethylhydroxylamine; guanidyl group-containing organosilicon compounds such as tetramethylguanidylpropyltrimethoxysilane; organic acids (acetic acid, methanesulfonic acid etc.), inorganic acids (hydrochloric acid) , Sulfuric acid, etc.). However, these catalysts do not dissolve in a fluorine-based solvent, or dissolve only in very small amounts, so that the catalyst efficiency is poor. In addition, the residual metal component may cause deterioration of the properties of the cured film.

Patent Document 10 (Japanese Patent Application Laid-Open No. 2004-145283) proposes a fluoropolyalkylene ether group-containing silane. The lens treated with the fluoropolyalkylene ether group-containing silane is excellent in oil repellency and fingerprint wiping properties but is not sufficiently abrasion resistant.

In addition, various coating compositions have been studied as antifouling surface treatment agents for resins and metals. For example, Patent Document 11 (Japanese Patent Laid-Open No. 2012-017374) proposes a surface treatment composition containing polysilazane, polysiloxane and a curing catalyst. However, the composition of this document contains a curing catalyst, and during the formation of a cured film, there is a possibility that defects due to the catalyst may occur, and it is not excellent in both water and oil repellency performance. The

JP 2003-238577 A Patent No. 2860979 Patent No. 4672095 Japanese Patent Publication No. 2008-534696 Japanese Patent Application Publication No. 2008-537557 Unexamined-Japanese-Patent No. 2012-072272 JP 2012-157856 A JP, 2013-136833, A JP 2008-144144 A JP 2004-145283 A Unexamined-Japanese-Patent No. 2012-017374

The present invention has been made in view of the above-mentioned circumstances, and in particular, at least three siloxane bonds and / or at least two in a molecule capable of forming a water and oil repellent layer excellent in abrasion resistance on resin and metal surfaces. Fluorine-containing coating composition containing hydroxyl- or hydrolyzable-group-containing organosilicon compound and / or partial (hydrolyzable) condensate thereof modified with a fluorooxyalkylene group-containing polymer and containing a number of silphenylene bonds It is an object of the present invention to provide a surface treatment agent comprising the composition, and an article surface-treated with the surface treatment agent.

As a result of intensive studies to solve the above object, the present inventors contain at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule, and are modified with a fluorooxyalkylene group-containing polymer Hydroxylated or hydrolyzable group-containing organosilicon compound and / or a partial (hydrolyzing) condensate thereof, preferably at least three siloxanes in a molecule represented by the general formula (1) or (2) described later A hydroxylated or hydrolysable group-containing organosilicon compound containing a bond and / or at least two silphenylene bonds and modified with a fluorooxyalkylene group-containing polymer and / or a partial (hydrolysis) condensate thereof; Surface containing a fluorine-containing coating composition using a mixture of perhydropolysilazane in a specific mixing ratio Physical agent, found that it is possible to form an excellent water- and oil-repellent layer on the wear resistance to the resin and the metal surface, the present invention has been accomplished.

Accordingly, the present invention provides the following fluorine-containing coating composition, a surface treatment agent containing the coating agent composition, an article surface-treated with the surface treatment agent, and the like.
[1]
(A) A hydroxy or hydrolysable group-containing organosilicon compound containing at least three siloxane bonds and / or at least two silphenylene bonds in the molecule and modified with a fluorooxyalkylene group-containing polymer and / or Or a partial (hydrolyzed) condensate thereof and (B) perhydropolysilazane, and the mixing mass ratio of the (A) component to the (B) component is 5: 95 to 95: 5 (however, the (A) component The total of the mixing mass ratio of and (B) component is 100), The fluorine-containing coating agent composition characterized by the above-mentioned.
[2]
The component (A) is represented by the following general formula (1)

(Wherein R f is a monovalent or divalent fluorooxyalkylene group-containing polymer residue, and A is a siloxane bond, a silphenylene bond, and a group forming a siloxane bond or a silphenylene bond with Si bonded to A A divalent to hexavalent organic group having one or more selected, R independently represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, and X independently represents a hydroxyl group or a hydrolysable group , N is an integer of 1 to 3, m is an integer of 1 to 15, and α is 1 or 2.)
And at least three siloxane bonds and / or at least two silphenylene bonds in the molecule represented by and modified by a fluorooxyalkylene group-containing polymer, a hydroxyl group- or hydrolyzable group-containing organosilicon compound, And / or a partial (hydrolyzing) condensate thereof, or the following general formula (2)

[Wherein, Rf ′ is a divalent fluorooxyalkylene group-containing polymer-polysiloxane copolymer-containing group, and each of Q and Q ′ may contain a single bond or an ether bond, and is fluorine-substituted And Z is a single bond, -JC = [J is an alkyl group, a hydroxyl group or K ₃ SiO- (where K is independently a hydrogen atom, an alkyl group, an aryl group or an alkoxy group) A silyl ether group], a trivalent group represented by -LSi = (L is an alkyl group), a tetravalent group represented by -C≡, a tetravalent group represented by -Si≡ And a divalent to octavalent siloxane residue, m 'is an integer of 1 to 7, and X, R and n are the same as above. )
And / or a hydrolyzable hydroxyl group containing at least three siloxane bonds and / or at least two silphenylene bonds in the molecule represented by and modified with a fluorooxyalkylene group-containing polymer-polysiloxane copolymer A group-containing organosilicon compound and / or a partial (hydrolytic) condensate thereof,
The component (B) is represented by the following general formula (3)
-(SiH ₂ -NH) _x- (3)
(In the formula, x is a number representing the degree of polymerization.)
The fluorine-containing coating agent composition as described in [1] which is perhydropolysilazane represented by these.
[3]
The molecule represented by the formula (1) contains at least three siloxane bonds and / or at least two silphenylene bonds, and contains a hydroxyl group or a hydrolyzable group modified with a fluorooxyalkylene group-containing polymer The organosilicon compound is represented by the following general formula (4a) or (4b)

[Wherein, R f is a monovalent or divalent fluorooxyalkylene group-containing polymer residue, and Y is independently at least one selected from a silicon atom, a siloxane bond, a silalkylene structure and a silarylene structure R 2 is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolysable group, and n is 1 And is an integer of to 3, a is an integer of 1 to 5, W is a hydrogen atom, or the following formula (4a ')

(Wherein, Y ′ is a silicon atom and / or a divalent to hexavalent organic group which may have a siloxane bond, b is an integer of 1 to 5, and R, X, n are the same as above) Is)
And at least three siloxane bonds and / or at least two silphenylene bonds in the sum of Y and Y ′. α is 1 or 2. ]

(Wherein, U is - (CH ₂₎ _z1 O- and, z1 is an integer of ¹ ~ 20, A 1 is - (CH ₂₎ _z2 - a, z2 is an integer of 1 ~ 20, V is A divalent to hexavalent hydrocarbon group having a siloxane bond and / or a silphenylene bond and optionally having a silalkylene structure and / or a silarylene structure other than a silphenylene bond, and c is 1 to 5; R f, X, R, n and α are the same as above.)
A hydroxyl or hydrolyzable group-containing organosilicon compound containing at least three siloxane bonds and / or at least two silphenylene bonds in the molecule represented by and modified with a fluorooxyalkylene group-containing polymer The fluorine-containing coating agent composition as described in [2].
[4]
In the above formulas (1), (4a) and (4b), α is 1 and Rf is a monovalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (5) [2] Or the fluorine-containing coating agent composition as described in [3].

(Wherein p, q, r and s are each an integer of 0 to 200, and p + q + r + s = 3 to 200, and each repeating unit may be linear or branched, and each repeating unit Each other may be randomly bonded, d is an integer of 1 to 3, and the unit may be linear or branched.)
[5]
In the above formulas (1), (4a) and (4b), α is 2 and Rf is a divalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (6) [2] Or the fluorine-containing coating agent composition as described in [3].

(Wherein p, q, r and s are each an integer of 0 to 200, and p + q + r + s = 3 to 200, and each repeating unit may be linear or branched, and each repeating unit Each other may be randomly bonded, d is an integer of 1 to 3, and the unit may be linear or branched.)
[6]
In the above formula (4a), Y is an alkylene group having 5 to 10 carbon atoms, an alkylene group containing an arylene group having 6 to 8 carbon atoms, or the alkylene groups are mutually bonded via a silalkylene structure or a silarylene structure An alkylene group having 2 to 10 carbon atoms is bonded to a bond of a divalent group and a linear or branched or cyclic divalent to tetravalent organopolysiloxane residue having 2 to 100 silicon atoms. The fluorine-containing coating agent composition according to any one of [3] to [5], which is a group selected from the group consisting of a divalent to tetravalent group.
[7]
In the above formula (4a ′), Y ′ is an alkylene group having 2 to 10 carbon atoms, an alkylene group having 6 to 8 carbon atoms, an arylene group having 6 to 8 carbon atoms, an alkylene group having 2 to 6 carbon atoms including a diorganosilylene group, alkylene Groups: a divalent group in which the groups are linked via a silalkylene structure or a silarylene structure; and a linear or branched 2 to 10 silicon atoms or a branched or cyclic 2 to 10 silicon atoms Any one of [3] to [6] which is a group selected from the group consisting of a divalent to tetravalent group in which an alkylene group having 2 to 10 carbon atoms is bonded to a bond of a tetravalent organopolysiloxane residue. The fluorine-containing coating agent composition as described in 4.
[8]
The fluorine-containing compound as described in [2], wherein Rf ′ in the formula (2) is a divalent fluorooxyalkylene group-containing polymer-polysiloxane copolymer-containing group represented by the following general formula (7) or (8) Coating composition.
_{- (Z'-Q) e -Rf} 1 - (Q-Z ') e - (7)
^{-Rf 1 - (Q-Z'-} Q-Rf 1) f - (8)
(Wherein, Q represents a single bond or an ether bond and may be a fluorine-substituted divalent organic group, and Rf ¹ represents a divalent fluorooxyalkylene group-containing polymer residue) And Z 'each represents a divalent polysiloxane residue, which may be the same or different, e is independently 0 or 1, and f is an integer of 1 to 3).
[9]
Z ′ in the formulas (7) and (8) is a polysiloxane chain represented by the following general formula (9) or (10), and a divalent fluoro Rf ¹ is represented by the following general formula (6) The fluorine-containing coating agent composition as described in [8] which is an oxyalkylene group containing polymer residue.

(Wherein R ′ is the same or different alkyl group having 1 to 4 carbon atoms, phenyl group or phenylethyl group. T is an integer of 10 to 200 and y is an integer of 1 to 5) , W1 and w2 are each an integer of 1 to 200, and may be the same or different.)

(Wherein p, q, r and s are each an integer of 0 to 200, and p + q + r + s = 3 to 200, and each repeating unit may be linear or branched, and each repeating unit Each other may be randomly bonded, d is an integer of 1 to 3, and the unit may be linear or branched.)
[10]
In the formulas (1), (2), (4a) and / or (4b), X represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, or 1 to 10 carbon atoms, respectively. The fluorine-containing coating agent composition according to any one of [2] to [9], which is selected from the group consisting of an acyloxy group of 10, an alkenyloxy group of 2 to 10 carbon atoms and a halogen group.
[11]
A hydroxy or hydrolysable group-containing organosilicon compound containing at least three siloxane bonds and / or at least two silphenylene bonds in the molecule of component (A) and modified with a fluorooxyalkylene group-containing polymer 11. The fluorine-containing coating composition according to any one of claims 1 to 10, which is represented by any one of the following formulas.

(In the formula, p1 is an integer of 5 to 100, q1 is an integer of 5 to 100, p1 + q1 is an integer of 10 to 105, and these repeating units may be randomly combined.)

(Wherein, p2 is an integer of 5 to 100, q2 is an integer of 5 to 100, p2 + q2 is an integer of 10 to 105, t1 is an integer of 4 to 199, and t2 is an integer of 0 to 99 Each repeating unit shown in parentheses may be randomly combined.)
[12]
A hydroxy or hydrolysable group-containing organosilicon compound containing at least three siloxane bonds and / or at least two silphenylene bonds in the molecule of component (A) and modified with a fluorooxyalkylene group-containing polymer The fluorine-containing coating composition according to any one of [1] to [11], wherein the partial (hydrolyzed) condensate thereof is soluble in dibutyl ether.
[13]
A surface treatment agent comprising the fluorine-containing coating composition according to any one of [1] to [12].
[14]
A cured film comprising a cured product of the surface treatment agent according to [13].
[15]
An article having a cured coating of the surface treatment agent according to [13] on the surface.

The fluorine-containing coating composition of the present invention preferably contains at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule, which is soluble in dibutyl ether, and is hydroxyl group or hydrolyzed. Perhydropolysilazane is a base material by mixing a fluorooxyalkylene group-containing polymer modified organosilicon compound containing an anionic group and / or a partial (hydrolysis) condensate thereof with a perhydropolysilazane at a specific blending ratio The adhesion as a surface treatment agent is strengthened by the reaction between the hydroxyl group on the perhydropolysilazane layer and the hydroxyl group or hydrolyzable group portion of the fluorooxyalkylene group-containing polymer-modified organosilicon compound. . Thus, an article surface-treated with a surface treatment agent containing a fluorine-containing coating composition containing the organosilicon compound and / or a partial (hydrolyzed) condensate thereof and a perhydropolysilazane has water and oil repellency, And abrasion resistance, particularly cloth abrasion resistance.

The fluorine-containing coating composition of the present invention contains (A) at least three siloxane bonds and / or at least two silphenylene bonds in the molecule and is a hydroxyl group modified with a fluorooxyalkylene group-containing polymer. Or a hydrolyzable group-containing organosilicon compound and / or a partial (hydrolyzable) condensate thereof and (B) perhydropolysilazane, and the mixing mass ratio of the (A) component to the (B) component is 5: 95 A composition having a ratio of 95: 5, preferably 30:70 to 95: 5, particularly preferably 40:60 to 95: 5 (provided that the total of the mass ratio of the components (A) and (B) is 100). By mixing these components at the above-mentioned specific blending ratio, the adhesion to a substrate is improved, and a cured film excellent in water and oil repellency and abrasion resistance, particularly cloth abrasion resistance can be formed. table Characterized in that it is possible to provide a treatment agent. If the content of the component (A) is too large, the adhesion to the substrate is poor. As a result, a cured film excellent in wear durability can not be obtained, and even if the content of the component (A) is too small It is not possible to obtain a cured film with excellent properties.

Component (A) Component (A) Component hydroxyl group or hydrolyzable group containing at least 3 siloxane bonds and / or at least 2 silphenylene bonds and modified with a fluorooxyalkylene group-containing polymer The organosilicon compound containing and / or partial (hydrolyzed) condensate thereof comprises at least three siloxane bonds (ie, Si-O-Si bonds) and / or at least two silphenylene bonds (ie, Si) in the molecule. It is a component that contains a —C ₆ H ₅ —Si bond, and contains a hydroxyl group or a hydrolyzable group in the molecule, and is preferably soluble in dibutyl ether.

At least 3, preferably 3 to 100, more preferably 3 to 40, more preferably 3 to 20 siloxane bonds in the molecule of component (A) and / or at least 2, preferably 2 in the molecule. As a hydroxyl group- or hydrolyzable group-containing organosilicon compound containing ~ 10 silphenylene bonds and modified with a fluorooxyalkylene group-containing polymer, the following general formula (1) is preferable

[Wherein, Rf ′ is a divalent fluorooxyalkylene group-containing polymer-polysiloxane copolymer-containing group, and each of Q and Q ′ may contain a single bond or an ether bond, and is fluorine-substituted And Z is a single bond, -JC = [J is an alkyl group, a hydroxyl group or K ₃ SiO- (where K is independently a hydrogen atom, an alkyl group, an aryl group or an alkoxy group) A silyl ether group], a trivalent group represented by -LSi = (L is an alkyl group), a tetravalent group represented by -C≡, a tetravalent group represented by -Si≡ And a divalent to octavalent siloxane residue, m 'is an integer of 1 to 7, and X, R and n are the same as above. )
And / or a hydrolyzable hydroxyl group containing at least three siloxane bonds and / or at least two silphenylene bonds in the molecule represented by and modified with a fluorooxyalkylene group-containing polymer-polysiloxane copolymer Group-containing organosilicon compounds and / or partial (hydrolytic) condensates thereof can be mentioned.

In the above formula (1), Rf is a monovalent or divalent fluorooxyalkylene group-containing polymer residue, and when α is 1, Rf is a monovalent fluorooxyalkylene group-containing polymer residue, and Rf is It is preferable that it is a monovalent | monohydric fluoro oxy alkylene group containing polymer residue represented by following formula (5).

(Wherein p, q, r and s are each an integer of 0 to 200, and p + q + r + s = 3 to 200, and each repeating unit may be linear or branched, and each repeating unit Each other may be randomly bonded, d is an integer of 1 to 3, and the unit may be linear or branched.)

In the above formula (1), when α is 2, Rf is a divalent fluorooxyalkylene group-containing polymer residue, and Rf is a divalent fluorooxyalkylene group-containing compound represented by the following formula (6) It is preferably a polymer residue.

(Wherein p, q, r and s are each an integer of 0 to 200, and p + q + r + s = 3 to 200, and each repeating unit may be linear or branched, and each repeating unit Each other may be randomly bonded, d is independently an integer of 1 to 3 for each unit, and the units may be linear or branched.)

In the above formulas (5) and (6), p, q, r and s are each an integer of 0 to 200, preferably p is an integer of 5 to 100, q is an integer of 5 to 100 and r is 0 to 100 And s is an integer of 0 to 100, p + q + r + s = 3 to 200, preferably 10 to 105, and each repeating unit may be linear or branched, and each repeating unit May be randomly combined. More preferably, p + q is an integer of 10 to 105, in particular 15 to 60, and r = s = 0. If p + q + r + s is smaller than the above upper limit, adhesion and curability are good, and if larger than the above lower limit, the characteristics of the fluoropolyether group can be sufficiently exhibited, which is preferable.

Specifically, the following can be illustrated as monovalent or divalent Rf.

(Wherein, p ′, q ′, r ′, s ′ are each an integer of 1 or more, and the upper limit is the same as the upper limit of the above p, q, r, s. U is an integer of 1 to 24, v is an integer of 1 to 24. Each repeating unit may be randomly combined.)

In the above formula (1), A forms a siloxane bond or a silphenylene bond with a siloxane bond, a silphenylene bond, and Si bonded to A (that is, a -SiO- group or -SiC ₆ H ₅ -group at the end) 2 to 16 valences, preferably 2 or more selected from one or more selected from groups having 3 to 100 in the case of siloxane bond, and preferably 2 to 10 in the case of silphenylene bond It is an organic group of 8 to 8 and more preferably 2 to 7 and is a linking group between a fluorooxyalkylene group-containing polymer residue and a hydroxyl group and / or a hydrolyzable group-containing silyl group. As the organic group of A, preferably, hetero such as oxygen atom (ether bond), amide bond, hydroxyl group, linear, branched or cyclic organosiloxane residue, silarylene residue such as silphenylene residue, etc. A siloxane bond and / or a silphenylene bond which may be substituted with an atom-containing structure, or a group forming a siloxane bond and / or a silphenylene bond with Si bonded to A is preferably 3 in the case of a siloxane bond Examples thereof include a divalent to hexavalent, preferably a divalent to octavalent, especially a divalent to tetravalent hydrocarbon group having from 1 to 100, and preferably from 2 to 10, in the case of a silphenylene bond. Specifically, the following groups may be mentioned as A.

In the above formula (1), R is independently an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl or butyl, or a phenyl group, preferably a methyl group.
X is independently a hydroxyl group or a hydrolyzable group, and as the hydrolyzable group, an alkoxy group having 1 to 10 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group, methoxymethoxy group, methoxyethoxy group, etc. C2-10 alkoxyalkoxy, C1-10 acyloxy such as acetoxy, and C2-10 alkenyloxy such as isopropenoxy, chlor such as chloro, bromo and iodo Etc. Among them, methoxy and ethoxy are preferable.
n is an integer of 1 to 3, preferably 3, m is an integer of 1 to 15, preferably an integer of 1 to 7, more preferably an integer of 1 to 6, and α is 1 or 2.

Furthermore, a hydroxyl group or hydrolysis which contains at least three siloxane bonds and / or at least two silphenylene bonds in the molecule represented by the general formula (1) and is modified with a fluorooxyalkylene group-containing polymer The organic group-containing organosilicon compound preferably contains at least three siloxane bonds and / or at least two silphenylene bonds in a molecule represented by the following general formula (4a) or (4b), and And a hydroxy or hydrolysable group-containing organosilicon compound modified with a fluorooxyalkylene group-containing polymer.

[Wherein, R f, R, X, n and α are the same as above, and Y independently has one or more selected from a silicon atom, a siloxane bond, a silalkylene structure and a silarylene structure A divalent divalent to hexavalent organic group, a is an integer of 1 to 5, W is a hydrogen atom, or the following formula (4a ′):

(Wherein, Y ′ is a silicon atom and / or a divalent to hexavalent organic group which may have a siloxane bond, b is an integer of 1 to 5, and R, X, n are the same as above) Is)
And at least three siloxane bonds and / or at least two silphenylene bonds in the sum of Y and Y ′. ]

(Wherein, U is _{_{- (CH 2) z1 O-,}} z1 is an integer of ¹ ~ 20, A 1 is - (CH ₂₎ _z2 - a, z2 is an integer of 1 ~ 20, V siloxane A divalent to hexavalent hydrocarbon group having a bond and / or a silphenylene bond and optionally having a silalkylene structure and / or a silarylene structure other than a silphenylene bond, and c is an integer of 1 to 5 Rf, X, R, n and α are the same as above.)

In the above formula (4a), Y is a divalent to hexavalent, preferably a divalent to tetravalent, which may have one or more selected from a silicon atom, a siloxane bond, a silalkylene structure and a silarylene structure. More preferably, it is a divalent organic group, and as Y, specifically, carbon such as an alkylene group having 4 to 10 carbon atoms such as butylene group (tetramethylene group, methylpropylene group), hexamethylene group, phenylene group, etc. An alkylene group containing an arylene group having a number of 6 to 8 (for example, an alkylene arylene group having a carbon number of 8 to 16), a divalent group in which the alkylene groups are linked via a silalkylene structure or a silarylene structure, 2 to 100, preferably 5 to 100, more preferably 10 to 50 linear, branched or cyclic divalent to hexavalent organopolysilicons having silicon atoms And a divalent to hexavalent group in which an alkylene group having 2 to 10 carbon atoms is bonded to the bond of carbon atoms, and the like, and preferably an alkylene group having 5 to 10 carbon atoms and an arylene group having 6 to 8 carbon atoms In particular, an alkylene group containing a phenylene group, a divalent group in which the alkylene groups are linked to each other via a silalkylene structure or a silarylene structure, a straight chain having 2 to 100 silicon atoms, or 3 to 100 silicon atoms A divalent to tetravalent group in which an alkylene group having 2 to 10 carbon atoms is bonded to the bond of two branched or cyclic divalent to tetravalent organopolysiloxane residues, and more preferably a carbon number of 3 to 3 carbon atoms 6 alkylene group.

Here, as a silalkylene structure and a silarylene structure, the thing shown below can be illustrated.

(Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl or butyl, or an aryl group having 6 to 10 carbons such as phenyl), and R ¹ may be the same or different R ² is an alkylene group having 1 to 4 carbon atoms such as methylene group, ethylene group, propylene group (trimethylene group, methyl ethylene group) or the like, and an arylene group having 6 to 10 carbon atoms such as phenylene group. )

In addition, as a linear, branched or cyclic divalent to hexavalent organopolysiloxane residue having 2 to 100, preferably 5 to 100, and more preferably 10 to 50 silicon atoms, the following are listed. Can be illustrated.

(Wherein, R ¹ is the same as above. G is an integer of 1 to 99, preferably 4 to 99, preferably 9 to 49, h is an integer of 2 to 6, preferably 2 to 4, j Is an integer of 0 to 8, preferably 0 or 1, h + j is an integer of 3 to 100, preferably 5 to 100, more preferably 10 to 50, k is an integer of 1 to 3, preferably 2 Or 3.)

Specific examples of Y include, for example, the following groups.

(Wherein, g1 is an integer of 2 to 99 and h1 is an integer of 2 to 10)
Y is preferably a group having a siloxane bond and / or a silphenylene bond.

In the above formula (4a), W is a hydrogen atom or a group represented by the following formula (4a ′).

(Wherein, Y ′ is a silicon atom and / or a divalent to hexavalent organic group optionally having a siloxane bond, b is an integer of 1 to 5, preferably an integer of 1 to 3, R , X, n are the same as above.)

In the above formula (4a ′), Y ′ is a divalent to hexavalent, preferably divalent to tetravalent, more preferably divalent organic group, and may have a silicon atom and / or a siloxane bond.
As Y ′, specifically, it has 2 to 10 carbon atoms, particularly 3 carbon atoms, such as ethylene group, propylene group (trimethylene group, methyl ethylene group), butylene group (tetramethylene group, methyl propylene group) and hexamethylene group. Alkylene groups containing an arylene group having 6 to 10 carbon atoms, especially 6 to 8 carbon atoms, such as an alkylene group to 10, a phenylene group, etc. (for example, an alkylene arylene group having 8 to 16 carbon atoms), 2 to 10 carbon atoms Or an alkylene group having 2 to 6 carbon atoms including a diorganosilylene group such as dimethylsilylene group and diethylsilylene group, and a divalent group in which the alkylene groups are linked to each other via a silalkylene structure or a silarylene structure Or linear, branched or cyclic divalent to hexavalent organopolysiloxane residue having 2 to 10, preferably 2 to 5 silicon atoms And an alkylene group having 2 to 6 carbon atoms, and 2 to 10 silicon atoms, preferably 2 to 5 straight-chain, branched or cyclic divalent or hexavalent organopolysiloxane residues bonded with carbon atoms. Examples thereof include a divalent to hexavalent group to which an alkylene group of 2 to 10 is bonded, and the like, preferably an alkylene group having 3 to 10 carbon atoms, an alkylene group containing a phenylene group, and a carbon number of 2 to 2 containing a dimethylsilylene group. 6 alkylene groups, a divalent group in which the alkylene groups are mutually bonded via a silalkylene structure or a silarylene structure, and a linear divalent organopolysiloxane residue having 2 to 10 silicon atoms The carbon number of the bond of an alkylene group having 2 to 6 carbon atoms, a linear having 2 to 10 silicon atoms, or a branched or cyclic divalent to tetravalent organopolysiloxane residue having 3 to 10 silicon atoms 2 to 10 A divalent to tetravalent radical which alkylene group is bonded, more preferably an alkylene group having 3 to 6 carbon atoms.

Here, the silalkylene structure, the silarylene structure, and the linear, branched or cyclic divalent to hexavalent organopolysiloxane residue having 2 to 10, and preferably 2 to 5 silicon atoms, are as described above. The same ones as those described above can be exemplified.

Specific examples of Y ′ include, for example, the following groups.

In the above formula (4a), at least 3 and preferably 3 to 100 siloxane bonds in the total of Y and Y ′, and at least 2 and preferably 2 in the total of Y and Y ′ are silphenylene bonds. It has ~ 10 pieces.

In the above formula (4a), a is an integer of 1 to 5, preferably an integer of 1 to 3.

In the above formula (4b), U is — (CH ₂ ) _z 1 O—, and z 1 is an integer of 1 to 20, preferably an integer of 1 to 10, more preferably an integer of 1 to 5. A ¹ is — (CH ₂ ) _z ₂ — and _z ₂ is an integer of 1 to 20, preferably an integer of 1 to 10, more preferably an integer of 1 to 5.

In the above formula (4b), V preferably has 3 to 100 siloxane bonds and / or preferably 2 to 10 silphenylene bonds, and has silarylene structures other than silalkylene structures and / or silphenylene bonds. It is a divalent to hexavalent hydrocarbon group which may be substituted.
Specifically, an alkylene having 2 to 10 carbon atoms is bonded to a straight, branched or cyclic divalent to tetravalent organopolysiloxane residue having 3 to 100, preferably 5 to 100 silicon atoms. A divalent to tetravalent group having a group attached thereto, a linear organo (poly) silphenylene residue having 2 to 10 silicon atoms, and an alkylene group having a carbon number of 2 to 10 attached to the bond divalent ^{_{^{group, -Si (OSiR 3 2 -R 4}}} -) a group represented by _3. Here, R ³ is independently an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl or butyl, or a phenyl group, and R ⁴ is independently a methylene group having 1 to 4 carbon atoms And an alkylene group such as ethylene group, propylene group (trimethylene group, methyl ethylene group) or phenylene group.
As V, those shown below are preferable.

In the above formula (4b), c is an integer of 1 to 5, preferably an integer of 1 to 3.

Fluorooxyalkylene group-containing polymer having at least three siloxane bonds and / or at least two silphenylene bonds in a molecule represented by the above formula (4a) or (4b) and having a hydrolyzable group Specific examples of the modified organosilicon compound include the following structures. In the following formulas, p1 is an integer of 5 to 100, q1 is an integer of 5 to 100, and p1 + q1 is an integer of 10 to 105. Preferred values of p1 and q1 of each formula are shown in parentheses.

In the above general formula (2), Q and Q ′ each represent a single bond or a divalent organic group which may contain a single bond or an ether bond, and which may be substituted with fluorine, and preferably contains an ether bond An unsubstituted or fluorine-substituted divalent organic group having 2 to 12 carbon atoms, preferably an unsubstituted or fluorine-substituted divalent hydrocarbon group having 2 to 12 carbon atoms which may contain an ether bond is there.

Here, examples of the unsubstituted or fluorine-substituted divalent hydrocarbon group having 2 to 12 carbon atoms include ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), It may be an alkylene group such as hexamethylene group or octamethylene group, an arylene group such as phenylene group, or a combination of two or more of these groups (alkylene arylene group etc.) What substituted one part or all part by the fluorine atom etc. are mentioned, An unsubstituted or substituted C2-C4 alkyl group and a phenyl group are especially preferable.

Examples of such Q and Q ′ include the following groups.

(In the formula, b1 is an integer of 2 to 4)

In the above general formula (2), Rf ′ is a divalent fluorooxyalkylene group-containing polymer-polysiloxane copolymer-containing group, preferably a divalent group represented by the following general formula (7) or (8) And a fluorooxyalkylene group-containing polymer-polysiloxane copolymer-containing group.
_{- (Z'-Q) e -Rf} 1 - (Q-Z ') e - (7)
^{-Rf 1 - (Q-Z'-} Q-Rf 1) f - (8)
(Wherein, Q is the same as above, R f ¹ is a divalent fluorooxyalkylene group-containing polymer residue, and Z ′ is a divalent polysiloxane residue, which may be the same or different, respectively. E Is independently 0 or 1, and f is an integer of 1 to 3, preferably 1 or 2.)

In the above (7) and (8), Rf ¹ is a divalent fluorooxyalkylene group-containing polymer residue, and the same as in the above formula (6) can be exemplified.

In the above (7) and (8), Z ′ is a divalent polysiloxane residue, preferably a polysiloxane chain represented by the following general formula (9) or (10).

In the above general formula (2), Z is a single bond, -JC = [J is preferably an alkyl group having 1 to 3 carbon atoms, a hydroxyl group or K ₃ SiO- (K is independently a hydrogen atom, preferably 1 carbon atom A trivalent group represented by an alkyl group of to 3, an aryl group such as a phenyl group, or a silyl ether group represented by an alkoxy group preferably having 1 to 3 carbon atoms], -LSi = (L is preferably a carbon number of 1 A trivalent group represented by -3 alkyl group, a tetravalent group represented by -C≡, a tetravalent group represented by -Si≡, and a divalent to octavalent, preferably a divalent to tetravalent siloxane When it contains a siloxane bond, it is preferably a chain or cyclic organopolysiloxane residue having 2 to 13 silicon atoms, preferably 2 to 5 silicon atoms. .
The organopolysiloxane residue preferably has an alkyl group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, such as methyl, ethyl, propyl and butyl, or a phenyl group.

As such Z, those shown below can be mentioned.

(Wherein, l is an integer of 1 to 12, preferably an integer of 1 to 4)

In the above general formula (2), m 'is an integer of 1 to 7, preferably an integer of 1 to 3.

As the fluorooxyalkylene group-containing polymer-modified organosilicon compound which contains at least three siloxane bonds and / or at least two silphenylene bonds in the molecule represented by the above formula (2), Can be mentioned. In the following formulae, p2 is an integer of 5 to 100, q2 is an integer of 5 to 100, p2 + q2 is an integer of 10 to 105, t1 is an integer of 4 to 199, preferably an integer of 9 to 99, , T2 is an integer of 0 to 99, preferably an integer of 4 to 49, but the parenthesized values show the more preferable values of p2, q2, t1, and t2 of the respective formulas.

(In the formula, each unit shown in parentheses may be randomly combined.)

The component (A) contains at least three siloxane bonds and / or at least two silphenylene bonds in the molecule described above, and contains a hydroxyl group or a hydrolyzable group modified with a fluorooxyalkylene group-containing polymer A hydroxyl group of an organosilicon compound (hereinafter, also referred to as a fluoropolyether group-containing polymer) or a terminal hydrolyzable group of the fluoropolyether group-containing polymer is obtained by condensing partially hydrolyzed hydroxyl groups in advance by a known method. Component (hydrolytic) condensate may be included.

Component (B) The fluorine-containing coating composition of the present invention contains at least three siloxane bonds and / or at least two silphenylene bonds in the molecule of component (A) described above, and is fluorooxyalkylene A perhydropolysilazane as component (B) is co-blended with the above-described specific ratio to the hydroxyl group- or hydrolyzable group-containing organosilicon compound modified with the group-containing polymer. As perhydropolysilazane of this (B) component, the perhydropolysilazane preferably represented by following General formula (3) is mentioned.
-(SiH ₂ -NH) _x- (3)
(In the formula, x is a number representing the degree of polymerization.)

The degree of polymerization of perhydropolysilazane as the component (B) is preferably about 800 to 8,000, and more preferably about 1,000 to 5,000. In addition, this polymerization degree can be normally measured as a weight average polymerization degree of standard polystyrene conversion by gel permeation chromatography (GPC) analysis which made toluene the developing solvent.

As a specific example of perhydropolysilazane as the component (B), AZ NAX 120-20 (manufactured by Merck Performance Materials Manufacturing Co., Ltd.) and the like are put on the market.

The perhydropolysilazane as the component (B) may be blended so as to have a specific mixing mass ratio with the component (A) in the form of a perhydropolysilazane solution previously dissolved in an organic solvent such as dibutyl ether.

The fluorine-containing coating agent composition of the present invention can be prepared by mixing the (A) component and the (B) component, but the (B) component is previously included in the raw material for synthesizing the (A) component. The component (A) may be synthesized in the stationary state.

The present invention further provides a hydroxyl group or a hydrolyzable group which contains at least three siloxane bonds and / or at least two silphenylene bonds in the (A) molecule and is modified with a fluorooxyalkylene group-containing polymer Containing organosilicon compound and / or partial (hydrolyzing) condensate thereof and (B) perhydropolysilazane, wherein the mass ratio of the (A) component to the (B) component is 5:95 to 95: 5 Provided is a surface treatment agent containing a certain fluorine-containing coating composition.

The surface treatment agent may, if necessary, be a hydrolysis condensation catalyst, for example, an organic tin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organic titanium compound (tetra n-butyl titanate, etc.), an organic acid (acetic acid, Methanesulfonic acid, fluorine-modified carboxylic acid, etc.), inorganic acid (hydrochloric acid, sulfuric acid, etc.) may be added. Among these, acetic acid, tetra n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid and the like are particularly desirable.
The amount of the hydrolytic condensation catalyst added is a catalytic amount, usually 0.01 to 5 parts by mass, particularly 0.1 parts by mass per 100 parts by mass of the fluoropolyether group-containing polymer and / or the partial (hydrolyzed) condensate thereof. 1 part by mass.

The surface treatment agent contains at least three siloxane bonds and / or at least two silphenylene bonds in the molecule of the component (A), and is modified with a fluorooxyalkylene group-containing polymer with hydroxyl groups or hydrolysis. A suitable solvent for dissolving the organic group-containing organosilicon compound and / or the partial (hydrolyzed) condensate thereof may be included. As such solvents, fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (1,3-bis (trifluoromethyl) benzene, etc.), fluorine Modified ether solvents (methylperfluorobutyl ether, ethylperfluorobutyl ether, perfluoro (2-butyltetrahydrofuran) etc.), fluorine modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine etc.), hydrocarbon solvents (Petroleum benzine, toluene, xylene and the like) and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone and the like) can be exemplified. Among these, fluorine-modified solvents are preferable in terms of solubility, wettability and the like, and in particular, 1,3-bis (trifluoromethyl) benzene, perfluoro (2-butyltetrahydrofuran), perfluorotriol Butylamine and ethyl perfluorobutyl ether are preferred.

The solvent may be a mixture of two or more thereof, and it is preferable to uniformly dissolve the fluoropolyether group-containing polymer and the partial (hydrolyzed) condensate thereof. The optimum concentration of the fluoropolyether group-containing polymer to be dissolved in the solvent and the partial (hydrolyzed) condensate thereof may differ depending on the treatment method, and it may be an amount that is easy to measure. The amount is preferably 0.01 to 10 parts by mass, particularly preferably 0.05 to 5 parts by mass, based on 100 parts by mass in total of the fluoropolyether group-containing polymer (and the partial (hydrolyzing) condensate thereof). When it is used, it is preferably 1 to 100 parts by mass, particularly preferably 3 to 30 parts by mass with respect to 100 parts by mass in total of the solvent and the fluoropolyether group-containing polymer (and its partial (hydrolyzing) condensate).

The surface treatment agent of the present invention can be applied to a substrate by known methods such as brushing, dipping, and spraying. The curing temperature varies depending on the curing method. For example, in the case of direct coating (brush coating, dipping, spray, etc.), the temperature is 25 to 200 ° C., particularly 50 to 150 ° C. for 30 minutes to 36 hours, particularly 1 It is preferable to set to 24 hours. Moreover, you may make it harden | cure under humidification. The film thickness of the cured film is appropriately selected depending on the type of the base material, and is usually 0.1 to 100 nm, particularly 1 to 20 nm.

The base material to be treated with the surface treatment agent of the present invention is not particularly limited, and may be made of various materials such as paper, cloth, metals and oxides thereof, resins such as glass and plastics, ceramics, quartz and the like. The surface treatment agent of the present invention can impart water and oil repellency to the substrate.

Articles to be treated with the surface treatment agent of the present invention include car navigations, mobile phones, smart phones, digital cameras, digital video cameras, PDAs, portable audio players, car audio systems, game machines, game lenses, eyeglass lenses, camera lenses, lens filters, Optical articles such as sunglasses, medical instruments such as a stomach camera, copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflection films and the like can be mentioned. The surface treatment agent of the present invention can prevent fingerprints and sebum from adhering to the article and can further impart scratch resistance, so that the adhesion to a touch panel display, resin, or metal is particularly good. Therefore, it is useful as a water and oil repellent layer of a housing portion of a smartphone.

In addition, the surface treatment agent of the present invention is an antifouling coating for sanitary products such as bathtubs and washbasins, window glass or tempered glass for automobiles, trains, aircrafts, etc., antifouling coatings such as headlamp covers, building materials for outer walls Water- and oil-repellent coating, coating for preventing oil stains on kitchen building materials, anti-staining of telephone box and anti-sticking and anti-graffiti coating, coating for anti-fingerprint adhesion such as artworks, anti-fingerprint coating for compact disc, DVD, etc. It is also useful as a mold release agent or a coating additive, a resin modifier, a flowability modifier or a dispersability modifier for an inorganic filler, a lubricity improver for a tape, a film or the like for a mold.

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited by the following examples.

A hydroxy or hydrolysable group-containing organosilicon compound containing at least three siloxane bonds and / or at least two silphenylene bonds in the molecule of component (A) and modified with a fluorooxyalkylene group-containing polymer [Compound 1] to [Compound 3] below were prepared. [Compound 1] to [Compound 3] are all components soluble in dibutyl ether at room temperature (25 ° C.). Also, for comparison, a fluoropolyether group-containing polymer which does not contain at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule and is insoluble in dibutyl ether at room temperature (25 ° C.) As [compound 4] and [compound 5] were prepared.

[Compound 1]

[Compound 2]

[Compound 3]

[Compound 4]

[Compound 5]

As perhydropolysilazane of component (B), AZ NAX 120-20 (manufactured by Merck Performance Materials Manufacturing Co., Ltd.) was used.

[Examples 1 to 10, Comparative Examples 1 to 5]
Preparation of surface treatment agent and formation of cured film [Compound 1] to [Compound 3] which is the component (A) and the compound for comparison [Compound 4] and [Compound 5] at the mixing ratio shown in Table 1 A surface treatment agent was prepared by mixing a hydrolyzable group-containing organosilicon compound modified with an alkylene group-containing polymer with a 10% by mass dibutyl ether solution of perhydropolysilazane of component (B) or dibutyl ether as a solvent. Each surface treatment agent was dip-coated on duralumin, PMMA (polymethyl methacrylate resin) or PC (polycarbonate resin). The coating conditions were a pulling speed of 350 mm / min and an immersion time of 30 seconds. The glass immediately after coating was cured at 80 ° C. under an atmosphere of humidity 50% RH for 1 hour to form a cured film having a thickness of about 100 nm. In Comparative Examples 1 to 3, they were dissolved in dibutyl ether as a solvent to prepare a 10% by mass solution. Moreover, in Comparative Examples 4 and 5, the [compound 4] and [compound 5] which are the component (A) did not dissolve in dibutyl ether in the component (B), and it was not possible to prepare a coating liquid.

The cured coatings of Examples 1 to 10 and Comparative Examples 1 to 3 were evaluated by the following methods. Both tests were performed at 25 ° C. and 40% RH.

[Evaluation of solubility]
The component (A) and the component (B) were mixed, and the solubility was evaluated as “○” if not white when visually observed, and as “×” if white. The results (solubility) are shown in Table 2.

Evaluation of water repellency [ Evaluation of initial water repellency]
The contact angle (water repellency) of the cured film to water was measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) for the substrate on which the cured film formed above was formed (droplets: 2 μl, Temperature: 25 ° C., humidity: 40% RH). The water contact angle was measured one second after 2 μl droplets were deposited on the sample surface. The results (initial contact angles) are shown in Table 2.
In the early stage, both the examples and the comparative examples showed good water repellency.

[Evaluation of wear resistance]
In the obtained cured film, the abrasion resistance to a cloth (bencot) was measured using Tribogear TYPE: 30S (manufactured by Shinto Scientific Co., Ltd.).
The fabric resistance test was carried out under the following conditions, and the contact angle (water repellency) to the water of the cured film after being rubbed 4,000 times was measured in the same manner as described above, and the abrasion resistance was evaluated. The results (contact angle after wear) are shown in Table 2.
Contact area: 10 mm x 30 mm
Load: 1 kg
Cloth abrasion resistance <br> Cloth: BEMCOT M-3 II (manufactured by Asahi Kasei Corporation)
Travel distance (one way) 20 mm
Movement speed 3,600 mm / min Load: 0.5 kg / cm ²

The surface treatment agent of Examples 1 to 10 contains at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecule described above, and is modified with a fluorooxyalkylene group-containing polymer The adhesion to the metal substrate was improved by mixing the hydrolyzable group-containing organosilicon compound and the perhydropolysilazane dissolved in a dibutyl ether solution at a specific blending ratio. From this, the cured film of the surface treatment agent of Examples 1 to 10 contains at least 3 siloxane bonds and / or at least 2 silphenylene bonds in the molecules of Comparative Examples 1 to 3 and is fluoro Compared with a cured film of a surface treatment agent using only hydrolyzable group-containing organosilicon compounds modified with an oxyalkylene group-containing polymer, the contact angle of 100 ° or more can be maintained after 4,000 times of fabric abrasion and excellent Demonstrated excellent wear resistance.
In addition, the hydrolyzable group-containing organosilicon compound ([compound 4], [compound 5]) modified with the fluorooxyalkylene group-containing polymer used in Comparative Examples 4 and 5 does not satisfy the above structure, It did not dissolve in the dibutyl ether solution, and the coating liquid could not be prepared.

Claims

(A) A hydroxy or hydrolysable group-containing organosilicon compound containing at least three siloxane bonds and / or at least two silphenylene bonds in the molecule and modified with a fluorooxyalkylene group-containing polymer and / or Or a partial (hydrolyzed) condensate thereof and (B) perhydropolysilazane, and the mixing mass ratio of the (A) component to the (B) component is 5: 95 to 95: 5 (however, the (A) component The total of the mixing mass ratio of and (B) component is 100), The fluorine-containing coating agent composition characterized by the above-mentioned.
The component (A) is represented by the following general formula (1)

(Wherein R f is a monovalent or divalent fluorooxyalkylene group-containing polymer residue, and A is a siloxane bond, a silphenylene bond, and a group forming a siloxane bond or a silphenylene bond with Si bonded to A A divalent to hexavalent organic group having one or more selected, R independently represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, and X independently represents a hydroxyl group or a hydrolysable group , N is an integer of 1 to 3, m is an integer of 1 to 15, and α is 1 or 2.)
And at least three siloxane bonds and / or at least two silphenylene bonds in the molecule represented by and modified by a fluorooxyalkylene group-containing polymer, a hydroxyl group- or hydrolyzable group-containing organosilicon compound, And / or a partial (hydrolyzing) condensate thereof, or the following general formula (2)

[Wherein, Rf ′ is a divalent fluorooxyalkylene group-containing polymer-polysiloxane copolymer-containing group, and each of Q and Q ′ may contain a single bond or an ether bond, and is fluorine-substituted And Z is a single bond, -JC = [J is an alkyl group, a hydroxyl group or K 3 SiO- (where K is independently a hydrogen atom, an alkyl group, an aryl group or an alkoxy group) A silyl ether group], a trivalent group represented by -LSi = (L is an alkyl group), a tetravalent group represented by -C≡, a tetravalent group represented by -Si≡ And a divalent to octavalent siloxane residue, m 'is an integer of 1 to 7, and X, R and n are the same as above. )
And / or a hydrolyzable hydroxyl group containing at least three siloxane bonds and / or at least two silphenylene bonds in the molecule represented by and modified with a fluorooxyalkylene group-containing polymer-polysiloxane copolymer A group-containing organosilicon compound and / or a partial (hydrolytic) condensate thereof,
The component (B) is represented by the following general formula (3)
-(SiH 2 -NH) x- (3)
(In the formula, x is a number representing the degree of polymerization.)
The fluorine-containing coating composition according to claim 1, which is a perhydropolysilazane represented by
The molecule represented by the formula (1) contains at least three siloxane bonds and / or at least two silphenylene bonds, and contains a hydroxyl group or a hydrolyzable group modified with a fluorooxyalkylene group-containing polymer The organosilicon compound is represented by the following general formula (4a) or (4b)

[Wherein, R f is a monovalent or divalent fluorooxyalkylene group-containing polymer residue, and Y is independently at least one selected from a silicon atom, a siloxane bond, a silalkylene structure and a silarylene structure R 2 is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolysable group, and n is 1 And is an integer of to 3, a is an integer of 1 to 5, W is a hydrogen atom, or the following formula (4a ')

(Wherein, Y ′ is a silicon atom and / or a divalent to hexavalent organic group which may have a siloxane bond, b is an integer of 1 to 5, and R, X, n are the same as above) Is)
And at least three siloxane bonds and / or at least two silphenylene bonds in the sum of Y and Y ′. α is 1 or 2. ]

(Wherein, U is - (CH 2) z1 O- and, z1 is an integer of 1 ~ 20, A 1 is - (CH 2) z2 - a, z2 is an integer of 1 ~ 20, V is A divalent to hexavalent hydrocarbon group having a siloxane bond and / or a silphenylene bond and optionally having a silalkylene structure and / or a silarylene structure other than a silphenylene bond, and c is 1 to 5; R f, X, R, n and α are the same as above.)
A hydroxyl or hydrolyzable group-containing organosilicon compound containing at least three siloxane bonds and / or at least two silphenylene bonds in the molecule represented by and modified with a fluorooxyalkylene group-containing polymer The fluorine-containing coating composition according to claim 2.
In the above formulas (1), (4a) and (4b), α is 1 and Rf is a monovalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (5). Or the fluorine-containing coating agent composition as described in 3.

(Wherein p, q, r and s are each an integer of 0 to 200, and p + q + r + s = 3 to 200, and each repeating unit may be linear or branched, and each repeating unit Each other may be randomly bonded, d is an integer of 1 to 3, and the unit may be linear or branched.)
In the above formulas (1), (4a) and (4b), α is 2 and Rf is a divalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (6). Or the fluorine-containing coating agent composition as described in 3.

(Wherein p, q, r and s are each an integer of 0 to 200, and p + q + r + s = 3 to 200, and each repeating unit may be linear or branched, and each repeating unit Each other may be randomly bonded, d is an integer of 1 to 3, and the unit may be linear or branched.)
In the above formula (4a), Y is an alkylene group having 5 to 10 carbon atoms, an alkylene group containing an arylene group having 6 to 8 carbon atoms, or the alkylene groups are mutually bonded via a silalkylene structure or a silarylene structure An alkylene group having 2 to 10 carbon atoms is bonded to a bond of a divalent group and a linear or branched or cyclic divalent to tetravalent organopolysiloxane residue having 2 to 100 silicon atoms. The fluorine-containing coating composition according to any one of claims 3 to 5, which is a group selected from the group consisting of a divalent to tetravalent group.
In the above formula (4a ′), Y ′ is an alkylene group having 2 to 10 carbon atoms, an alkylene group having 6 to 8 carbon atoms, an arylene group having 6 to 8 carbon atoms, an alkylene group having 2 to 6 carbon atoms including a diorganosilylene group, alkylene Groups: a divalent group in which the groups are linked via a silalkylene structure or a silarylene structure; and a linear or branched 2 to 10 silicon atoms or a branched or cyclic 2 to 10 silicon atoms The group selected from the group consisting of a divalent to tetravalent group in which an alkylene group having 2 to 10 carbon atoms is bonded to a bond of a tetravalent organopolysiloxane residue. The fluorine-containing coating agent composition as described in 4.
The fluorine-containing group according to claim 2, wherein Rf 'in the formula (2) is a divalent fluorooxyalkylene group-containing polymer-polysiloxane copolymer-containing group represented by the following general formula (7) or (8) Coating composition.
- (Z'-Q) e -Rf 1 - (Q-Z ') e - (7)
-Rf 1 - (Q-Z'- Q-Rf 1) f - (8)
(Wherein, Q represents a single bond or an ether bond and may be a fluorine-substituted divalent organic group, and Rf 1 represents a divalent fluorooxyalkylene group-containing polymer residue) And Z 'each represents a divalent polysiloxane residue, which may be the same or different, e is independently 0 or 1, and f is an integer of 1 to 3).
Z ′ in the formulas (7) and (8) is a polysiloxane chain represented by the following general formula (9) or (10), and a divalent fluoro Rf 1 is represented by the following general formula (6) The fluorine-containing coating composition according to claim 8, which is an oxyalkylene group-containing polymer residue.

(Wherein R ′ is the same or different alkyl group having 1 to 4 carbon atoms, phenyl group or phenylethyl group. T is an integer of 10 to 200 and y is an integer of 1 to 5) , W1 and w2 are each an integer of 1 to 200, and may be the same or different.)

(Wherein p, q, r and s are each an integer of 0 to 200, and p + q + r + s = 3 to 200, and each repeating unit may be linear or branched, and each repeating unit Each other may be randomly bonded, d is an integer of 1 to 3, and the unit may be linear or branched.)
In the formulas (1), (2), (4a) and / or (4b), X represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, or 1 to 10 carbon atoms, respectively. The fluorine-containing coating composition according to any one of claims 2 to 9, which is selected from the group consisting of an acyloxy group of 10, an alkenyloxy group having 2 to 10 carbon atoms and a halogen group.
A hydroxy or hydrolysable group-containing organosilicon compound containing at least three siloxane bonds and / or at least two silphenylene bonds in the molecule of component (A) and modified with a fluorooxyalkylene group-containing polymer 11. The fluorine-containing coating composition according to any one of claims 1 to 10, which is represented by any one of the following formulas.

(In the formula, p1 is an integer of 5 to 100, q1 is an integer of 5 to 100, p1 + q1 is an integer of 10 to 105, and these repeating units may be randomly combined.)

(Wherein, p2 is an integer of 5 to 100, q2 is an integer of 5 to 100, p2 + q2 is an integer of 10 to 105, t1 is an integer of 4 to 199, and t2 is an integer of 0 to 99 Each repeating unit shown in parentheses may be randomly combined.)
A hydroxy or hydrolysable group-containing organosilicon compound containing at least three siloxane bonds and / or at least two silphenylene bonds in the molecule of component (A) and modified with a fluorooxyalkylene group-containing polymer The fluorine-containing coating composition according to any one of claims 1 to 11, wherein the partial (hydrolysis) condensate thereof is soluble in dibutyl ether.
A surface treatment agent comprising the fluorine-containing coating composition according to any one of claims 1 to 12.
A cured film comprising the cured product of the surface treatment agent according to claim 13.
An article having a cured coating of the surface treatment agent according to claim 13 on the surface.