TW201803915A - Fluoropolyether group-containing polymer-modified silane, surface treatment agent and article - Google Patents

Abstract

Provided are: a fluoropolyether group-containing polymer-modified silane represented by general formula (1), which is capable of forming a cured coating film that has excellent water repellent oil repellent properties and excellent wear resistance; a surface treatment agent which contains this silane and/or a partial hydrolysis condensation product thereof; and an article which is surface-treated with this surface treatment agent. (In the formula, Rf represents a monovalent or divalent fluorooxyalkylene group-containing polymer residue; Q represents a divalent hydrocarbon group having 2 to 6 carbon atoms, which may contain an ether bond; Y represents a hydrocarbon group having a functionality of 2 to 6, which may contain a silicon atom, a silylene group and/or a siloxane bond; each R independently represents an alkyl group having 1 to 4 carbon atoms; each X independently represents a hydroxyl group or a hydrolyzable group; n represents an integer of 1 to 3; [gamma] represents an integer of 1 to 5; m represents an integer of 1 to 5; R' represents an alkyl group having 1 to 4 carbon atoms; [beta] represents an integer of 1 to 3; and [alpha] represents 1 or 2).

Description

Fluoropolyether-based polymer modified silanes, surface treatment agents and articles

The present invention relates to a fluorine-containing polyether-based polymer modified silane, and in particular, it relates to a fluorine-containing polyether-based polymer modified silane that forms a film excellent in water repellency, oil repellency, and abrasion resistance, and contains the silane And / or a partial (hydrolyzed) condensate thereof as a surface treatment agent, and an article subjected to a surface treatment with the surface treatment agent (that is, a hardened film having the surface treatment agent on the surface).

In recent years, led by the display of mobile phones, the touch panel of the screen has been accelerated. However, the touch panel is in a state of exposing the screen, and there are many opportunities for direct contact between fingers or cheeks, and it is easy to attach dirt such as sebum. Therefore, in order to improve the appearance or the visibility, the technology that does not easily attach fingerprints to the display surface, or the technology that easily causes dirt to drop, has increased year by year, and it is desirable to develop materials that can meet these requirements. Particularly, since fingerprints are easily attached to the surface of the touch panel display, it is desirable to provide a water- and oil-repellent layer. However, although the conventional water- and oil-repellent layer has high water- and oil-repellent properties and excellent dirt wiping properties, there are problems in that the antifouling performance deteriorates during use.

Generally, fluorinated polyether-based compounds Since the energy is very small, it has water and oil repellency, chemical resistance, lubricity, mold release, and antifouling. Utilizing its properties, it is widely used in paper in industry. Water and oil repellent antifouling agents for fibers, lubricants for magnetic recording media, oil repellents for precision machinery, release agents, cosmetics, protective films, etc. However, this property also means non-adhesion and non-adhesion to other substrates. Even if it can be coated on the surface of the substrate, it is difficult to make its film adhere.

On the other hand, a silane coupling agent is sufficiently known as a substrate for bonding a surface of a substrate such as glass or cloth to an organic compound, and is widely used as a coating agent for various substrate surfaces. The silane coupling agent has an organic functional group and a reactive silane group (usually a hydrolyzable silane group such as an alkoxysilane group) in one molecule. The hydrolyzable silane group forms a film by causing a self-condensation reaction with moisture or the like in the air. The coating is chemically oxidized through the surface of a hydrolyzable silane group and glass or metal. Physically bonded to form a strong, durable film.

Therefore, it was revealed that the modified fluoropolyether-based polymer modified silane obtained by introducing a hydrolyzable silane group into a fluorinated polyether-based compound is easily adhered to the surface of the substrate and can be formed on the surface of the substrate. Compositions of coatings such as water and oil repellency, chemical resistance, lubricity, release agent, and antifouling properties (Patent Documents 1 to 5: Japanese Patent Publication No. 2008-534696, Japanese Patent Publication No. 2008-537557, (Japanese Laid-Open Patent Publication No. 2012-072272, Japanese Laid-Open Patent Publication No. 2012-157856, and Japanese Laid-Open Patent Publication No. 2013-136833).

A composition containing a modified fluorine-containing polyether group polymer obtained by introducing a hydrolyzable silane group into the compound containing a fluorine-containing polyether group is used. Surface-treated lenses, anti-reflection films, and other hardened films are excellent in slipperiness and releasability. However, in recent years, users have demanded high abrasion resistance, and cannot fulfill the performance that fully meets the requirements. In addition, although coating with a thick film is more likely to exhibit performance, haze occurs on the glass surface, which impairs visibility.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 2008-534696

[Patent Document 2] Japanese Patent Publication No. 2008-537557

[Patent Document 3] Japanese Patent Application Publication No. 2012-072272

[Patent Document 4] Japanese Patent Laid-Open No. 2012-157856

[Patent Document 5] Japanese Patent Laid-Open No. 2013-136833

The present invention has been made in view of the above circumstances, and an object thereof is to provide a fluoropolyether-based polymer modified silane that can form a hardened film with excellent water and oil repellency and abrasion resistance, and the silane and / or a portion thereof (hydrolyzed) ) A surface treatment agent for a condensate, and an article subjected to a surface treatment (a hardened film having the surface treatment agent on the surface) by the surface treatment agent.

As a result of active review by the present inventors in order to solve the above-mentioned object, it was found that the modification of the silane by the fluoropolyether-based polymer described above makes the The silane is modified by a fluorine-containing polyether-based polymer represented by the general formula (1) described later, whereby the surface-treating agent containing the silane and / or a partial (hydrolyzed) condensate thereof can form water-repellent, oil-repellent, and abrasion-resistant properties. The present invention has completed a hardened film having excellent wearability and visibility.

Therefore, the present invention provides the following fluoropolyether-based polymer modified silanes, surface treatment agents, and articles.

[1]

A fluoropolyether-based polymer modified silane represented by the following general formula (1),

(In the formula, Rf is a monovalent or divalent fluorooxyalkylene-containing polymer residue, Q is a divalent hydrocarbon group having 2 to 6 carbon atoms which may contain an ether bond, and Y is a silicon atom or a silane group. Radicals and / or siloxane groups of 2 to 6 valences, R is independently an alkyl group having 1 to 4 carbon atoms, X is independently a hydroxyl group or a hydrolyzable group, n is an integer of 1 to 3, and γ is an integer of 1 to 5 Integer, m is an integer of 1 to 5, R 'is an alkyl group of 1 to 4 carbons, β is an integer of 1 to 3, and α is 1 or 2).

[2]

The fluoropolyether-based polymer modified silane as described in [1] above, wherein α in the aforementioned formula (1) is 1, and the Rf group is a monovalent fluorine-containing oxyalkylene group represented by the following general formula (2) Polymer residues,

(In the formula, p, q, r, and s are integers from 0 to 200, and p + q + r + s = 3 to 200. Each repeating unit can be linear or branched. Each repeating unit They can be randomly bonded to each other, d is an integer of 1 to 3, and the unit (-C _d F _2d- ) can be linear or branched).

[3]

For example, the polymer modified silane containing fluorinated polyether group in [1], wherein α of the aforementioned formula (1) is 2, and the Rf group is a polymerization of a divalent fluorine-containing oxyalkylene group represented by the following general formula (3) Residues,

(In the formula, p, q, r, and s are integers from 0 to 200, and p + q + r + s = 3 to 200. Each repeating unit can be linear or branched. Each repeating unit They can be randomly bonded to each other, d is an integer of 1 to 3, and the units (-C _d F _2d- ) can be independently linear or branched).

[4]

The fluoropolyether-based polymer modified silane according to any one of [1] to [3], wherein in the foregoing formula (1), Y is selected from an alkylene group having a carbon number of 3 to 10 and a carbon number 6 to 8 aryl alkyl groups, dialkyl groups through silicon atoms, silane groups, silane groups, silane groups, or siloxane groups bonded to divalent groups, and 2 to 10 silicon atoms Straight-chain or branched or cyclic 2- to 4-valent organic polysiloxane residues with 3 to 10 silicon atoms, or bonded to a bond of a silicon atom At least one type of group consisting of a 2 to 4 valence group of an alkylene group having 2 to 10 carbon atoms.

[5]

The fluoropolyether-based polymer modified silane according to any one of [1] to [4], wherein in the aforementioned formula (1), Q is -CH ₂ OCH _2- .

[6]

The fluoropolyether-based polymer modified silane according to any one of [1] to [5], wherein in the foregoing formula (1), X is selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, At least one selected from the group consisting of alkoxyalkoxy having 2 to 10 carbon atoms, fluorenyloxy having 2 to 10 carbon atoms, alkenyloxy having 2 to 10 carbon atoms, and halo groups.

[7]

The fluoropolyether-based polymer modified silane according to any one of [1] to [6], wherein the polymer modified silane represented by the formula (1) is expressed by any one of the following formulas,

(In the formula, p1 is an integer from 5 to 100, q1 is an integer from 5 to 100, and p1 + q1 is an integer from 10 to 105).

[8]

A surface treating agent containing a fluoropolyether-based polymer modified silane and / or a partial (hydrolyzed) condensate thereof according to any one of [1] to [7].

[9]

An article having a hardened coating having a surface treating agent such as [8] on the surface.

The fluoropolyether-based polymer-modified silane of the present invention has a large number of reactive functional groups and ether linkage groups, so it improves the adhesion and wettability to the substrate, thereby containing the silane and / or Some (hydrolyzed) condensates are treated with a surface treatment agent, which has excellent water and oil repellency, abrasion resistance and visibility.

The fluoropolyether-based polymer modified silane of the present invention is represented by the following general formula (1).

(Where Rf is a monovalent or divalent fluorooxyalkylene-containing polymer residue Q is a divalent hydrocarbon group having 2 to 6 carbon atoms which may contain an ether bond, Y is a 2 to 6 valent hydrocarbon group which may have silicon atom, silyl and / or siloxane bond, and R is independently 1 to carbon number An alkyl group of 4, X is independently a hydroxyl group or a hydrolyzable group, n is an integer of 1 to 3, γ is an integer of 1 to 5, m is an integer of 1 to 5, R 'is an alkyl group of 1 to 4, β is an integer from 1 to 3, and α is 1 or 2).

The fluoropolyether-based polymer modified silane of the present invention is characterized by a hydrolyzable silane group such as a monovalent or divalent fluorooxyalkylene-containing polymer residue (Rf) and an alkoxysilane group. Hydroxy-containing silyl groups (-Si (R) _3-n (X) _n ) are 2 to 6 valences which may have a silicon atom, a silyl group and / or a siloxane bond via a hydrocarbon chain (Q) and an ether group The structure of the hydrocarbon group (Y) bond, it is preferable to have more than 3 reactive functional groups (X) in the polymer, and to have a plurality of ether linking groups, so as to improve the adhesiveness of the substrate, and the wear resistance and visibility Excellent.

As Rf, α is 1 and a polymer residue of a monovalent fluorine-containing oxyalkylene group represented by the following general formula (2) (hereinafter sometimes referred to as a monovalent fluorooxyalkyl group) is preferred.

(In the formula, p, q, r, and s are integers from 0 to 200, and p + q + r + s = 3 to 200. Each repeating unit can be linear or branched. Each repeating unit They can be randomly bonded to each other, d is an integer of 1 to 3, and the unit (-C _d F _2d- ) can be linear or branched).

Rf is 2 at α, and is preferably represented by the following general formula (3) Shown is a polymer residue of a divalent fluorooxyalkylene group (hereinafter sometimes referred to as a divalent fluorooxyalkylene group).

(In the formula, p, q, r, and s are integers from 0 to 200, and p + q + r + s = 3 to 200. Each repeating unit can be linear or branched. Each repeating unit They can be randomly bonded to each other, d is an integer of 1 to 3, and the units (-C _d F _2d- ) can be linear or branched, respectively).

In the above formulas (2) and (3), p, q, r, and s are integers of 0 to 200, preferably p is an integer of 5 to 100, q is an integer of 5 to 100, and r is an integer of 0 to 100. Integer, s is an integer from 0 to 100, p + q + r + s = an integer from 3 to 200, preferably an integer from 10 to 105, each repeating unit can be linear or branched, each repeating unit Can be randomly bonded to each other. More preferably, p + q is an integer of 10 ~ 105, especially an integer of 15 ~ 60, r = s = 0. When the value of p + q + r + s is less than the above-mentioned upper limit value, adhesion or hardenability is good, and when it is more than the above-mentioned lower limit value, the characteristics of the fluoropolyether group can be fully utilized, so it is preferable.

In the formulae (2) and (3), d is an integer of 1 to 3, preferably 1 or 2. The units (-C _d F _2d- ) may be linear or branched, respectively.

Specific examples of Rf include the following.

(In the formula, p ', q', r ', and s' are each an integer of 1 or more, and the upper limit is Same as the upper limit of p, q, r, and s, u is an integer from 1 to 24, and v is an integer from 1 to 24, and each repeating unit can be randomly bonded).

In the above formula (1), Y is preferably 2 to 6 valences, preferably 2 to 4 valences, more preferably a divalent hydrocarbon group, and may have a silicon atom, a silyl group, and / or a siloxane bond. The molecule does not contain a linking group with low bonding energy, and can provide a coating film with excellent abrasion resistance.

Specific examples of Y include 3 to 10 carbon atoms such as propylene (trimethylene, methylethylene), butyl (tetramethylene, methylethylene), and hexamethylene. Alkyl groups, alkylene groups containing 6 to 8 carbons such as phenylene (for example, alkylenes having 8 to 16 carbons, etc.), alkylenes pass through silicon atoms, and silylene Divalent radicals bonded to the base, silylene structure or silylene structure, and 2 to 6 valences of straight, branched or cyclic silicon with 2 to 10 silicon atoms, preferably 2 to 5 silicon atoms Organic polysiloxane residues, or 2 to 6 valence groups of 2 to 10 carbonized alkylene groups, etc., bonded to silicon atoms, preferably 3 to 10 carbonized alkylene groups, containing Divalent radicals of phenylene groups, dialkyl groups that are bonded to each other through a silicon alkylene structure or a silicon aryl structure, and a straight chain with 2 to 10 silicon atoms or 3 to 10 silicon atoms Branched or cyclic 2 to 4 valent organopolysiloxane residues, or 2 to 4 valence groups of 2 to 10 carbonized alkyl groups bonded to silicon atom bonds, more preferably Alkyl group having 3 to 6 carbon atoms.

Here, examples of the silicon alkylene structure and the silicon alkylene structure include the following.

(In the formula, R ¹ is a methyl group, an ethyl group, a propyl group, a butyl group, etc., an alkyl group having 1 to 4 carbon atoms, and a phenyl group, such as an aryl group having 6 to 10 carbon atoms, R ¹ may be the same or different. R ² is methylene, ethylidene, propylidene (trimethylene, methylethylidene), etc., carbonized 1-4 alkylene, phenylene, etc., carbonized 6-10 base).

In addition, as the linear, branched, or cyclic 2 to 6-valent organic polysiloxane residue having 2 to 10 silicon atoms, preferably 2 to 5, the following can be exemplified.

(In the formula, R ¹ is the same as above, g is an integer of 1 to 9, preferably an integer of 1 to 4, h is an integer of 2 to 6, preferably an integer of 2 to 4, and j is an integer of 0 to 8. An integer is preferably 0 or 1, h + j is an integer of 3 to 10, preferably an integer of 3 to 5, and k is an integer of 1 to 3, preferably 2 or 3).

Specific examples of Y are exemplified by the following.

In the formula (1), Q is a divalent hydrocarbon group having 2 to 6 carbon atoms which may contain an ether bond. As Q, specific examples are ethylene, propyl (trimethylene Alkylene, methylene), butylene (tetramethylene, methylene), hexamethylene, and other alkylene groups having 2 to 6 carbon atoms, ether groups containing ether, Cyanene (trimethylene, methylethylene), butylene (tetramethylene, methylethylene), hexamethylene, and the like having a carbon number of 2 to 6, preferably It contains an alkylene group having 2 and 3 carbon atoms with an ether bond in between.

Specific examples of Q are exemplified by the following groups.

[Chem 14] -CH ₂ CH ₂ --CH ₂ CH ₂ CH ₂ --CH ₂ CH ₂ CH ₂ CH ₂ --CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ --CH ₂ -O-CH ₂ --CH ₂ -O-CH ₂ CH ₂ -

In the formula (1), X is a hydroxyl group or a hydrolyzable group which may be different from each other. Examples of this X are alkoxy, methoxymethoxy, and methoxyethyl having 1 to 10 carbon atoms, such as hydroxyl, methoxy, ethoxy, propoxy, isopropoxy, and butoxy. Alkoxy substituted with 2 to 10 carbons such as alkoxy, alkoxy substituted with alkoxy, ethoxyl, etc. 2 to 10 carbons with alkoxy, isopropenyloxy, etc., alkenyl with 2 to 10 carbons , Chlorine atom, bromine atom, iodine atom and the like. Among them, a methoxy group, an ethoxy group, an isopropoxy group, and a chlorine atom are preferred.

In the formula (1), R is an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, or butyl, and among them, methyl and ethyl are preferred. n is an integer of 1 to 3, preferably 2 or 3, based on the reactivity and the adhesion to the substrate Viewpoint is better for 3.

In the formula (1), m is an integer of 1 to 5, and is preferably 1 or 2 from the viewpoint of obtaining raw materials. In addition, γ is an integer of 1 to 5, and is preferably an integer of 1 to 3 from the viewpoints of easy synthesis and stability of the product.

In the above formula (1), R 'is an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, or butyl. Among them, methyl and ethyl are preferred. β is an integer of 1 to 3, and is more preferably 2 or 3 from the viewpoints of reactivity and adhesion to the substrate.

Examples of the fluorine-containing polyether-based polymer modified silane represented by the formula (1) include those represented by the following formula. In each formula, the repeating number (or degree of polymerization) of each repeating unit constituting the fluorooxyalkyl group or the fluorooxyalkylene group may be any number that satisfies the above formulas (2) and (3).

(In the formula, p1 is an integer from 5 to 100, q1 is an integer from 5 to 100, and p1 + q1 is an integer from 10 to 105).

Examples of the method for preparing the fluoropolyether group-modified polymer silane when α is 1 represented by the above formula (1) include the following method.

A fluorine-containing oxyalkyl group-containing polymer having at least two (especially two or three) olefinic sites at the single end of the molecular chain is dissolved in a fluorine system such as 1,3-bis (trifluoromethyl) benzene In a solvent, an organosilicon compound having a SiH group and a hydrolyzable terminal group (such as an alkoxy group such as a methoxy group) in a molecule such as trimethoxysilane and a hydrosilylation reaction catalyst such as platinum chloride / vinyl In the presence of a toluene solution of the siloxane complex, a temperature of 40 to 120 ° C, preferably 60 to 100 ° C, more preferably about 80 ° C, 1 to 48 hours, preferably 2 to 10 hours, and more preferably about 5 hours Under the conditions, hydrosilylation addition reaction is performed and matured.

In addition, as another method for preparing a fluoropolyether-group-modified polymer silane when α is 1 represented by the above formula (1), the following method is exemplified.

A fluorine-containing oxyalkyl group-containing polymer having at least two (especially two or three) olefinic sites at the single end of the molecular chain is dissolved in a fluorine system such as 1,3-bis (trifluoromethyl) benzene In a solvent, an organosilicon compound having a SiH group and a hydrolyzable terminal group in a molecule such as trichlorosilane, in the presence of a toluene solution of a hydrosilation reaction catalyst such as a platinum chloride / vinylsiloxane complex At a temperature of 40 to 120 ° C, preferably 60 to 100 ° C, more preferably about 80 ° C, for 1 to 48 hours, preferably 2 to 10 hours, and more preferably about 5 hours, the hydrosilylation addition reaction is carried out and After maturation, the substituent on the silane group (A chlorine atom or the like bonded to a silicon atom) is converted into a hydrolyzable group such as an alkoxy group such as a methoxy group.

Alternatively, instead of the organic silicon compound having a SiH group and a hydrolyzable terminal group in the molecule, an SiH group-containing organic silicon compound having no hydrolyzable terminal group may be used. In this case, as the organic silicon compound, a molecule is used An organosilicon compound which does not have a hydrolyzable terminal group and has two or more SiH groups. In this case, it is preferable to carry out the same method as described above so that the polymer having a single-terminus of the molecular chain having two or more (especially two or three) olefinic sites and a fluorooxyalkyl group-containing polymer do not have hydrolyzable terminal groups in the molecule. An organosilicon compound containing more than two SiH groups is subjected to a hydrosilylation addition reaction to form a reactant (intermediate) having at least two (especially two or three) residual SiH groups at the single end of the molecular chain, and then Residual SiH groups at the polymer end of the reaction product (intermediate), and organosilicon compounds having olefin sites and hydrolyzable end groups in molecules such as allyltrimethoxysilane, etc., are used in hydrosilylation reaction catalysts such as chlorine In the presence of a toluene solution of platinic acid / vinylsiloxane complex, at a temperature of 40 to 120 ° C, preferably 60 to 100 ° C, more preferably about 80 ° C, 1 to 48 hours, preferably 2 to 10 hours Under better conditions of about 5 hours, the hydrosilylation addition reaction is performed again and matured.

Here, examples of the fluorooxyalkyl group-containing polymer having an olefin site at the single end of the molecular chain include a fluorooxyalkyl group-containing polymer represented by the following formula (4).

(In the formula, Rf, R ', Q, m, and β are the same as described above, and Z is a divalent hydrocarbon group.)

In the above formula (4), Z is a divalent hydrocarbon group, preferably a divalent hydrocarbon group having 1 to 8 carbon atoms, and particularly 1 to 4 divalent hydrocarbon groups. Specific examples include methylene, ethylidene, and propylidene (trimethylene). 1 to 8 carbon atoms, including methylene, methylene, tetramethylene (tetramethylene, methylpropyl), hexamethylene, octamethylene, etc. The alkylene group having 6 to 8 carbon atoms (such as the alkylene group having 7 to 8 carbon atoms, etc.) and the like. Z is preferably a linear alkylene group having 1 to 4 carbon atoms.

The fluorooxyalkyl group-containing polymer represented by the formula (4) is preferably exemplified below. In each formula, the repeating number (or degree of polymerization) of each repeating unit constituting the fluorooxyalkyl group is any number that can satisfy the formula (2) in the above-mentioned Rf.

(In the formula, r1 is an integer from 1 to 100, and p1, q1, and p1 + q1 are the same as above).

As a method for preparing the fluorooxyalkyl group-containing polymer represented by the above formula (4), for example, a fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of a molecular chain and an olefin introducing agent are used, in the presence of a base, as required Additives or solvents are ripened at a temperature of 0 to 90 ° C, preferably 50 to 80 ° C, more preferably about 60 ° C, 1 to 40 hours, preferably 10 to 30 hours, and more preferably about 20 hours.

Examples of the fluorooxyalkyl group-containing polymer having a hydroxyl group at a single end of the molecular chain used for the preparation of the fluorooxyalkyl group-containing polymer represented by the formula (4) include the following examples.

(Where u1 is an integer from 1 to 24, r1, p1, q1, p1 + q1 are the same as above)

As the olefin introduction agent used for the preparation of the fluorooxyalkyl group-containing polymer represented by the formula (4), examples are shown below. It is preferable that the single end of the molecular chain has two or more (especially two or three) olefins. The site is similar to those having a sulfonate residue represented by -S (= O) ₂ O- at the other end.

The olefin introduction agent can be prepared by a known method.

The amount of the olefin introduction agent has a hydroxyl group content at the single end of the molecular chain The reactive end group (terminal hydroxyl) of the fluorooxyalkyl polymer is 1 equivalent, and 1 to 5 equivalents, more preferably 1 to 3 equivalents, and more preferably about 1.5 equivalents based on the sulfonic acid ester residues.

As the base used for preparing the fluorooxyalkyl group-containing polymer represented by formula (4), for example, amines or alkali metal-based bases can be used. Specifically, examples of the amines include triethylamine and diisopropylethyl. Amine, pyridine, DBU, imidazole, etc. Examples of the alkali metal base are sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, lithium alkyl, potassium third butoxide, lithium diisopropylammonium amide, lithium bis (trimethylsilyl) ammonium amine, Sodium bis (trimethylsilyl) phosphonium, potassium bis (trimethylsilyl) phosphonium and the like.

The amount of base used is 1 equivalent to the reactive terminal group of the fluorooxyalkyl-containing polymer having a hydroxyl group at the single end of the molecular chain, and 1 to 20 equivalents can be used, more preferably 5 to 15 equivalents, and still more preferably about 9 equivalents.

In the preparation of the fluorooxyalkyl group-containing polymer represented by the formula (4), tetrabutylammonium halide, an alkali metal halide, or the like can also be used as an additive to improve reactivity or to move the catalyst between phases. Specific examples of the additives include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydrogen sulfate, sodium iodide, potassium iodide, cesium iodide, and crown ether. These additives improve reactivity by performing a catalytic halogen exchange with an olefin introduction agent in the reaction system, and improve the reactivity by disposing a crown ether on a metal.

The amount of the additive used is 1 equivalent to the reactive end group of the fluorooxyalkyl-containing polymer having a hydroxyl group at a single end of the molecular chain, and 0.005 to 0.2 equivalents, more preferably 0.01 to 0.15 equivalents, and still more preferably about 0.1 equivalents.

Preparation of fluorooxyalkyl group-containing polymer represented by formula (4) It is also possible to use a solvent. Examples of the solvent to be used include fluorine-containing aromatic hydrocarbon solvents such as 1,3-bis (trifluoromethyl) benzene and trifluoromethylbenzene, and 1,1,1,2,3,4 , 4,5,5,5-Decafluoro-3-methoxy-2- (trifluoromethyl) benzene and other hydrofluoroether (HFE) solvents (manufactured by 3M, trade name: Novec series), and Perfluorinated solvents (produced by 3M Corporation, trade name: FLUORINERT series) composed of fully fluorinated compounds. Further, as the organic solvent, dimethylformamide, dimethylacetamide, dimethylmethane, acetonitrile, THF, and the like can be used. And water can also be used.

The amount of solvent used is 100 parts by mass of a polymer containing a fluorooxyalkyl group having a hydroxyl group at one end of the molecular chain, and 10 to 300 parts by mass, more preferably 30 to 150 parts by mass, and more preferably about 50 parts by mass .

Then, the reaction was stopped, and the aqueous layer and the fluorine solvent layer were separated by a liquid separation operation. The obtained fluorinated solvent layer was further washed with an organic solvent, and the solvent was distilled off to obtain a fluorooxyalkyl group-containing polymer represented by the formula (4).

In the preparation of the fluoropolyether-based polymer modified silane when α is 1 represented by the above formula (1), the solvent used is preferably a fluorine-based solvent, and as the fluorine-based solvent, 1,3-bis is exemplified. (Trifluoromethyl) benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1, 2,3,4,4,5,5,5-Decafluoro-3-methoxy-2- (trifluoromethyl) benzene and other hydrofluoroether (HFE) solvents (manufactured by 3M, trade name: Novec series), a perfluorinated solvent composed of a fully fluorinated compound (manufactured by 3M Corporation, trade name: FLUORINERT series), and the like.

The amount of the solvent is 100 parts by mass of the fluorooxyalkyl group-containing polymer having an olefin moiety at the single end of the molecular chain, and 10 to 300 parts by mass can be used. 50 ~ 150 parts by mass, and about 100 parts by mass is even better.

In the preparation of the fluoropolyether group-modified polymer silane when α is 1 represented by the above formula (1), as the organic silicon compound having a SiH group and a hydrolyzable terminal group in the molecule, the following general formula is preferable: (5) to (8) Compounds.

(Wherein, R, X, n, R 1, R 2, g, j are as defined above, R ³ is a C 2-8 monovalent hydrocarbon group of 2, i is an integer of 1 to 5, preferably from 1 to 3 Integer, i + j is an integer of 2-9, preferably an integer of 2-4).

Here, R ³ is a divalent hydrocarbon group having 2 to 8 carbon atoms, and preferably 2 to 3 carbon atoms. Examples include ethylene, propyl (trimethylene, methylethyl), and butyl (tetramethylene). (Methyl, methylpropene), hexamethylene, octamethylene and other alkylene groups, phenylene and other aryl groups, or a combination of two or more of these groups (alkylene. Aryl, etc.), etc. Among these, preferred are ethylene and trimethylene.

Examples of such an organic silicon compound having a SiH group and a hydrolyzable terminal group in the molecule include, for example, trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tributoxysilane, Triisopropoxysilane, triethoxysilane, trichlorosilane, tribromosilane, triiodosilane, and the following silanes.

In the preparation of fluoropolyether-containing polymer modified silane when α is 1 represented by the above formula (1), a polymer having a fluorooxyalkyl group having an olefin site at the single end of the molecular chain and a SiH group in the molecule The amount of the organic silicon compound having SiH group and hydrolyzable terminal group in the molecule when reacting with the hydrolyzable terminal organic silicon compound, the reactivity to the fluorooxyalkyl group-containing polymer having an olefin moiety at the single end of the molecular chain 1 equivalent of terminal group, can be used 1 ~ 3 equivalents, more preferably 1.5 ~ 2.5 equivalents, and even better about 2 equivalents.

In the preparation of the fluoropolyether group-modified polymer silane when α is 1 represented by the above formula (1), an organic silicon compound having two or more SiH groups without having a hydrolyzable terminal group in the molecule is preferred. It is a compound represented by the following general formulas (9) to (11).

(Wherein R ¹ , R ² , g, j, i, i + j are the same as described above).

Examples of such an organic silicon compound which does not have a hydrolyzable terminal group and contains two or more SiH groups include, for example, the following.

In the preparation of fluoropolyether-based polymer modified silane when α is 1 represented by the formula (1), the polymer containing a fluorooxyalkyl group having an olefin site at the single end of the molecular chain and the molecule does not have hydrolysis. The amount of organic silicon compounds that do not have hydrolyzable terminal groups and contain more than two SiH groups when the organic silicon compounds containing two or more SiH groups are reacted at the end of the molecular chain. Fluorooxyalkyl polymer The reactive terminal group is 1 equivalent, and 7 to 30 equivalents can be used, more preferably 10 to 20 equivalents, and still more about 15 equivalents.

In addition, in the preparation of fluoropolyether-group-modified polymer silane when α is 1 represented by formula (1), the organic silicon compound having an olefin site and a hydrolyzable terminal group in the molecule is preferably represented by the following general formula (12) The compound shown.

(In the formula, R, X, and n are the same as described above, and U is a single bond or a divalent hydrocarbon group having 1 to 6 carbon atoms.)

In the above formula (12), U is a single bond or a divalent hydrocarbon group having 1 to 6 carbon atoms, and as the divalent hydrocarbon group having 1 to 6 carbon atoms, examples are methylene, ethylidene, and propylidene (trimethylene , Methylene), butylene (tetramethylene, methylphenyl), hexamethylene, etc., alkylene, phenylene, etc. U is preferably a single bond or a methylene group.

In the preparation of fluoropolyether-containing polymer modified silane when α is 1 represented by formula (1), the polymer having a fluorooxyalkyl group having an olefin site at the single end of the molecular chain and the molecule do not have hydrolyzability A reactant of an organosilicon compound having a terminal group and containing two or more SiH groups when reacting with an organosilicon compound having an olefin site and a hydrolyzable terminal group in the molecule. The amount used is for the combination of a fluorooxyalkyl group polymer having an olefin moiety at the single end of the molecular chain and an organosilicon compound that does not have a hydrolyzable terminal group and contains more than two SiH groups in the molecule. The reactant has 1 equivalent of the reactive terminal group, and 3 to 9 equivalents can be used, more preferably 5 to 7 equivalents, and still more about 6 equivalents.

In the preparation of fluoropolyether-based polymer modified silane when α is 1 represented by formula (1), as a hydrosilylation reaction catalyst, examples include platinum black, chloroplatinic acid, and chloroplatinic acid alcohols. Modified products, complexes of chlorinated platinum acid with olefins, aldehydes, vinyl siloxanes, ethynyl alcohols, etc., platinum group metals such as (triphenylphosphine) palladium, chloroshen (triphenylphosphine) rhodium, etc. catalyst. Platinum-based compounds such as vinylsiloxane complexes are preferred.

The amount of the hydrosilylation reaction catalyst is used for a polymer containing a fluorooxyalkyl group having an olefin moiety at a single end of a molecular chain, or an organic polymer which does not have a hydrolyzable terminal group and contains two or more SiH groups in the molecule. The mass of the reactant of the silicon compound is 0.1 to 100 ppm, more preferably 1 to 50 ppm, in terms of transition metal (mass).

Finally, the solvent and unreacted substances were distilled off under reduced pressure to obtain the target compound.

For example, as a polymer containing a fluorooxyalkyl group having an olefin moiety at the single end of the molecular chain, a compound represented by the following formula is used.

When trimethoxysilane is used as the organic silicon compound having a SiH group and a hydrolyzable terminal group in the molecule, a compound represented by the following formula is obtained.

As a method for preparing a fluoropolyether-group-modified polymer silane when α is 2 represented by the above formula (1), the following method is exemplified.

Fluorine-oxyalkylene-containing polymers having two or more (especially two or three) olefinic sites at both ends of the molecular chain, and dissolved in a solvent such as 1,3-bis (trifluoromethyl) benzene, etc. Organosilicone compounds with SiH groups and hydrolyzable end groups in molecules such as trimethoxysilane in a fluorine-based solvent, and toluene in a hydrosilation reaction catalyst such as platinum chloride / vinylsiloxane complex In the presence of the solution, hydrosilylation is carried out at a temperature of 40 to 120 ° C, preferably 60 to 100 ° C, more preferably about 80 ° C, for 1 to 48 hours, preferably for 2 to 10 hours, and more preferably for about 5 hours. Reaction and ripening.

In addition, as another method for preparing a fluoropolyether-group-modified polymer silane when α is 2 represented by the formula (1), the following method is exemplified.

Dissolve a fluorooxyalkylene-containing polymer having at least two (especially two or three) olefinic sites at each end of the molecular chain in a solvent such as 1,3-bis (trifluoromethyl) benzene, etc. In a fluorine-based solvent, an organosilicon compound having a SiH group and a hydrolyzable terminal group in a molecule such as trichlorosilane is present in a hydrosilylation reaction catalyst such as a toluene solution of platinum chloride / vinylsiloxane complex At 40 ~ 120 ℃, preferably 60 ~ 100 ℃, more preferably about 80 ℃, 1 ~ 48 hours, preferably 2 ~ 10 hours, more preferably about 5 hours After undergoing a hydrosilylation addition reaction and ripening, the substituent on the silane group is converted into, for example, a methoxy group.

Alternatively, instead of the organic silicon compound having a SiH group and a hydrolyzable terminal group in the molecule, an SiH group-containing organic silicon compound having no hydrolyzable terminal group may be used. In this case, as the organic silicon compound, a molecule is used An organosilicon compound which does not have a hydrolyzable terminal group and has two or more SiH groups. At this time, it is carried out in the same manner as the above-mentioned method, so that both ends of the molecular chain preferably have two or more (especially two or three) olefin sites. The fluorooxyalkylene-containing polymer and the molecule do not have hydrolyzable ends Organic silicon compounds containing more than two SiH groups undergo hydrosilylation addition reaction to form reactants (intermediates) having two or more (especially two or three) residual SiH groups at each end of the molecular chain. After that, it is preferred that the polymer end of the reactant (intermediate) has two or more (especially two or three) SiH groups and allyltrimethoxysilanes in the molecule to have an olefin moiety and hydrolysis. Organic terminal silicon compounds, in the presence of a hydrosilylation catalyst such as a toluene solution of platinum chloride / vinylsiloxane complex at 40 ~ 120 ° C, preferably 60 ~ 100 ° C, more preferably At a temperature of about 80 ° C, for 1 to 48 hours, preferably 2 to 10 hours, and more preferably about 5 hours, the hydrosilylation addition reaction is again performed and matured.

Here, examples of the fluorine-containing oxyalkylene group-containing polymer having an olefin site at both ends of the molecular chain include a fluorine-containing oxyalkylene group represented by the following formula (13).

(In the formula, Rf, R ', Q, m, Z, β are the same as described above).

Examples of the fluorine-containing oxyalkylene-containing polymer represented by the formula (13) include those shown below. In each formula, the repeating number (or degree of polymerization) of each repeating unit constituting the fluorooxyalkylene group is any number that can satisfy the formula (3) in the above-mentioned Rf.

(Wherein p1, q1, and p1 + q1 are the same as described above).

As a method for preparing the fluorine-containing oxyalkylene-containing polymer represented by the above formula (13), for example, a fluorine-containing oxyethylene having hydroxyl groups at both ends of the molecular chain is used. Alkyl polymer and olefin introduction agent, in the presence of alkali, use additives or solvents as needed, at a temperature of 0 ~ 90 ° C, preferably 50 ~ 80 ° C, more preferably about 60 ° C, 1 ~ 40 hours, preferably 10 to 30 hours, preferably about 20 hours.

The fluorooxyalkylene group-containing polymer having a hydroxyl group at both ends of the molecular chain used for the preparation of the fluorooxyalkylene group-containing polymer represented by the formula (13) can be exemplified by the following formula.

(Where v1 is an integer from 1 to 24, u1, p1, q1, p1 + q1 are the same as above)

As the olefin introduction agent used for the preparation of the fluorine-containing oxyalkylene-containing polymer represented by the above formula (13), examples can be shown as follows. It is preferable that the single end of the molecular chain has two or more (especially two or three). ) An olefin site and those having a sulfonate residue represented by -S (= O) ₂ O- at the other end.

The olefin introduction agent can be prepared by a known method.

The amount of olefin introduction agent used has hydroxyl groups at both ends of the molecular chain The reactive terminal group (terminal hydroxyl group) of the fluorooxyalkylene polymer is 1 equivalent, and 1 to 5 equivalents, more preferably 1 to 3 equivalents, and more preferably about 1.5 equivalents based on the sulfonate residue.

As the base used for the preparation of the fluorooxyalkylene-containing polymer represented by formula (13), for example, amines or alkali metal-based bases can be used. Specifically, examples of the amines include triethylamine and diisopropyl. Ethylamine, pyridine, DBU, imidazole, etc. Examples of the alkali metal base are sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, lithium alkyl, potassium third butoxide, lithium diisopropylammonium amide, lithium bis (trimethylsilyl) ammonium amine, Sodium bis (trimethylsilyl) phosphonium, potassium bis (trimethylsilyl) phosphonium and the like.

The amount of base used is 1 equivalent to the reactive end group of the fluorooxyalkylene-containing polymer having hydroxyl groups at both ends of the molecular chain, and 1 to 20 equivalents can be used, more preferably 5 to 15 equivalents, and still more about 9 equivalents. .

In the preparation of the fluorine-containing oxyalkylene-containing polymer represented by the formula (13), tetrabutylammonium halide, an alkali metal halide, or the like can also be used as an additive to improve reactivity or interphase movement catalyst. Specific examples of the additives include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydrogen sulfate, sodium iodide, potassium iodide, cesium iodide, and crown ether. These additives improve reactivity by performing a catalytic halogen exchange with an olefin introduction agent in the reaction system, and improve the reactivity by disposing a crown ether on a metal.

The amount of the additive used is 1 equivalent to the reactive terminal group of the fluorooxyalkylene-containing polymer having hydroxyl groups at both ends of the molecular chain, and 0.005 to 0.2 equivalents, more preferably 0.01 to 0.15 equivalents, and still more preferably about 0.1 equivalents.

Preparation of fluorooxyalkyl group-containing polymer represented by formula (13) It is also possible to use a solvent. The solvent is not necessarily used, but examples of the solvent used include fluorine-containing aromatic hydrocarbon solvents such as 1,3-bis (trifluoromethyl) benzene and trifluoromethylbenzene, and 1,1, 1,2,3,4,4,5,5,5-Decafluoro-3-methoxy-2- (trifluoromethyl) benzene and other hydrofluoroether (HFE) solvents (manufactured by 3M Corporation, products (Name: Novec series), perfluorinated solvents (made by 3M Corporation, trade name: FLUORINERT series) composed of fully fluorinated compounds. Further, as the organic solvent, dimethylformamide, dimethylacetamide, dimethylmethane, acetonitrile, THF, and the like can be used. And water can also be used.

The amount of solvent used is 100 parts by mass of a fluorine-containing oxyalkylene polymer having a hydroxyl group at both ends of the molecular chain. 10 to 300 parts by mass, more preferably 30 to 150 parts by mass, and more preferably about 50 parts by mass Serving.

Then, the reaction was stopped, and the aqueous layer and the fluorine solvent layer were separated by a liquid separation operation. The obtained fluorinated solvent layer was further washed with an organic solvent, and the solvent was distilled off to obtain a fluorooxyalkylene-containing polymer represented by the formula (13).

In the preparation of the fluoropolyether-based polymer modified silane when α is 2 represented by the above formula (1), the solvent used is preferably a fluorine-based solvent, and as the fluorine-based solvent, 1,3-bis is exemplified. (Trifluoromethyl) benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1, 2,3,4,4,5,5,5-Decafluoro-3-methoxy-2- (trifluoromethyl) benzene and other hydrofluoroether (HFE) solvents (manufactured by 3M, trade name: Novec series), a perfluorinated solvent composed of a fully fluorinated compound (manufactured by 3M Corporation, trade name: FLUORINERT series), and the like.

The amount of solvent used is 100 parts by mass of a fluorine-containing oxyalkylene-containing polymer having an olefin moiety at both ends of the molecular chain, and 10 to 300 masses can be used. Parts, more preferably 50 to 150 parts by mass, and still more preferably about 100 parts by mass.

In addition, in the preparation of a fluoropolyether group-modified polymer silane when α is 2 represented by formula (1), as the organic silicon compound having a SiH group and a hydrolyzable terminal group in the molecule, the following general formula is preferable: (5) to (8) Compounds.

(Wherein R, X, n, R ¹ , R ² , R ³ , g, i, j, i + j are the same as described above).

Examples of such an organic silicon compound having a SiH group and a hydrolyzable terminal group in the molecule include, for example, trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tributoxysilane, Triisopropyl Alkenylsilane, triethoxysilane, trichlorosilane, tribromosilane, triiodosilane, and the following silane.

In the preparation of fluoropolyether-based polymer modified silane when α is 2 represented by the above formula (1), a polymer having a fluorine-containing oxyalkylene group having an olefin site at each end of the molecular chain and a molecule having The amount of organic silicon compounds having SiH groups and hydrolyzable terminal groups in the molecule when the organic silicon compounds having SiH groups and hydrolyzable terminal groups are reacted. Polymers containing fluorooxyalkyl groups having olefinic sites at both ends of the molecular chain. The reactive terminal group is 1 equivalent, and 1 to 3 equivalents can be used, more preferably 1.5 to 2.5 equivalents, and still more preferably about 2 equivalents.

In addition, in the preparation of fluoropolyether-group-modified polymer silane when α is 2 represented by formula (1), the organic silicon compound, which does not have a hydrolyzable terminal group and contains two or more SiH groups, is It is preferably a compound represented by the following general formulae (9) to (11).

(Wherein R ¹ , R ² , g, j, i, i + j are the same as described above).

Examples of such an organic silicon compound which does not have a hydrolyzable terminal group and contains two or more SiH groups include, for example, the following.

In the preparation of fluoropolyether-based polymer modified silane when α is 2 represented by formula (1), the polymer containing fluorooxyalkylene group having olefinic sites at both ends of the molecular chain and the molecule do not have When an organic silicon compound having a hydrolyzable terminal group and containing two or more SiH groups is reacted, the amount of the organic silicon compound not having a hydrolyzable terminal group and containing two or more SiH groups in the molecule has olefins at both ends of the molecular chain. Oxyfluorine 1 equivalent of the reactive terminal group of the polymer of the base can be used 7 to 30 equivalents, more preferably 10 to 20 equivalents, and more preferably about 15 equivalents.

In addition, in the preparation of a fluoropolyether group-modified polymer silane when α is 2 represented by formula (1), the organic silicon compound having an olefin site and a hydrolyzable terminal group in the molecule is preferably represented by the following general formula: (12) The compound shown.

(Wherein R, X, U, and n are the same as above).

In the preparation of fluoropolyether-based polymer modified silane when α is 2 represented by the formula (1), the polymer having fluorooxyalkylene group containing olefin sites at the both ends of the molecular chain and the molecule does not have A reactant of an organosilicon compound having a hydrolyzable terminal group and containing two or more SiH groups, when reacted with an organosilicon compound having an olefin moiety and a hydrolyzable terminal group in the molecule, the organosilicon compound having an olefin moiety and a hydrolyzable end group in the molecule The amount of compound used is reactivity to the reactants of fluorooxyalkylene-containing polymers having olefinic sites at both ends of the molecular chain and organic silicon compounds that do not have hydrolyzable terminal groups and contain more than two SiH groups. The terminal group is 1 equivalent, and 3 to 9 equivalents can be used, more preferably 5 to 7 equivalents, and still more about 6 equivalents.

In the preparation of fluoropolyether-based polymer modified silane when α is 2 represented by formula (1), as a hydrosilylation reaction catalyst, for example, platinum black, platinum chloride, and platinum chloride alcohol Modified products, chloroplatinic acid and olefins, Platinum group metal catalysts such as aldehydes, vinyl siloxanes, ethynyl alcohols, etc., palladium (triphenylphosphine) palladium, chloroshen (triphenylphosphine) rhodium, etc. Platinum-based compounds such as vinylsiloxane complexes are preferred.

The amount of the hydrosilylation reaction catalyst is used for a polymer containing a fluorooxyalkylene group having an olefin moiety at each end of the molecular chain, or the polymer and the molecule do not have hydrolyzable terminal groups and contain more than two SiH groups. The mass of the reactant of the organosilicon compound can be used in the amount of 0.1 to 100 ppm, more preferably 1 to 50 ppm, in terms of transition metal (mass).

Finally, the solvent and unreacted substances were distilled off under reduced pressure to obtain the target compound.

For example, as a fluorine-containing oxyalkylene polymer having an olefin moiety at each end of the molecular chain, a compound represented by the following formula is used.

When trimethoxysilane is used as the organic silicon compound having a SiH group and a hydrolyzable terminal group in the molecule, a compound represented by the following formula is obtained.

The present invention further provides a surface-treating agent containing the above-mentioned fluorine-containing polyether-based polymer-modified silane. The surface treatment agent may also include The hydroxyl group of the fluoropolyether-based polymer modified silane or a portion obtained by condensing the hydroxyl group of the terminal hydrolyzable group of the fluoropolyether-based polymer modified silane in advance by conventional methods (hydrolysis) Condensate.

Hydrolytic condensation catalysts can also be added to the surface treatment agent as needed, such as organic tin compounds (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), organic titanium compounds (tetra-n-butyl titanate, etc.), and organic acids ( Acetic acid, methanesulfonic acid, fluorine modified carboxylic acid, etc.), inorganic acids (hydrochloric acid, sulfuric acid, etc.). Among these, acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid, and the like are particularly desirable.

The addition amount of the hydrolysis condensation catalyst is the amount of the catalyst, usually 0.01 to 5 parts by mass, especially 0.1 to 100 parts by mass of the fluoropolyether-based polymer modified silane and / or a part (hydrolysis) condensate thereof. 1 part by mass.

The surface treatment agent may also contain a suitable solvent. Examples of such solvents include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), and fluorine-modified aromatic hydrocarbon solvents (1,3-bis (trifluoromethyl) benzene, etc.) Fluorine-modified ether solvents (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro (2-butyltetrahydrofuran), etc.), fluoro-modified alkylamine solvents (perfluorotributylamine) , Perfluorotriamylamine, etc.), hydrocarbon solvents (petroleum benzine, toluene, xylene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, a fluorine-modified solvent is desirable in terms of solubility, wettability, and the like, and particularly preferred are 1,3-bis (trifluoromethyl) benzene, perfluoro (2-butyltetrahydrofuran), and Fluorotributylamine, ethyl perfluorobutyl ether.

The above solvents may be mixed with two or more kinds thereof, and it is preferable to make the fluorine-containing polymer The ether-based polymer modified silane and / or its partial (hydrolyzed) condensate are uniformly dissolved. The optimum concentration of the fluoropolyether-based polymer modified silane and / or its partial (hydrolyzed) condensate dissolved in the solvent varies depending on the treatment method, as long as it is an amount that can be easily weighed, but it is applied directly In the case of a solvent and a fluorine-containing polyether-based polymer modified silane (and a part thereof (hydrolyzed) condensate), a total of 100 parts by mass, preferably 0.01 to 10 parts by mass, particularly preferably 0.05 to 5 parts by mass, When performing the vapor deposition treatment, the total amount of the solvent and the fluorine-containing polyether-based polymer-modified silane (and its partial (hydrolyzed) condensate) is 100 parts by mass, preferably 1 to 100 parts by mass, and particularly preferably 3 ~ 30 parts by mass.

The surface treatment agent of the present invention can be applied to a substrate by conventional methods such as bristle coating, dipping, spraying, and evaporation treatment. The heating method in the vapor deposition process may be either a resistance heating method or an electron beam heating method, and is not particularly limited. And the hardening temperature varies with the hardening method, but when it is directly applied (bristle coating, dipping, spraying, etc.), it is preferably 25 ~ 200 ° C, especially 25 ~ 80 ° C for 30 minutes ~ 36 hours, especially 1 ~ 24 hours. When applied by a vapor deposition treatment, the temperature is preferably in the range of 20 to 200 ° C. In addition, it can be hardened under humidification. The thickness of the cured coating film is appropriately selected depending on the type of the substrate, but it is usually 0.1 to 100 nm, especially 1 to 20 nm. In addition, for example, during spray coating, it is previously diluted in a fluorine-based solvent containing water and hydrolyzed, that is, after Si-OH is formed, and spray coating is performed, the hardening after coating is fast.

The substrate treated with the surface treatment agent of the present invention is not particularly limited, and may be various materials such as paper, cloth, metal and its oxide, glass, plastic, ceramic, quartz, and the like. The surface treating agent of the present invention can impart water and oil repellency to the aforementioned substrate. In particular, it can be preferably used as a surface treatment agent for SiO ₂ -treated glass or film.

Examples of articles treated with the surface treatment agent of the present invention are automotive satellite navigation, mobile phones, digital cameras, digital cameras, PDAs, portable video displays, car audio, game consoles, spectacle lenses, camera lenses, lens filters, sun Optical items such as medical equipment for eyeglasses and gastroscopes, photocopiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflection films, etc. The surface-treating agent of the present invention can prevent fingerprints and sebum from adhering to the aforementioned articles, and can further prevent scratches. Therefore, the surface-treating agent can be used as a water-repellent and oil-repellent layer for touch panel displays and anti-reflection films.

In addition, the surface treatment agent of the present invention can also be used as an antifouling coating film for sanitary products such as bathtubs, washstands, etc., an antifouling coating film for window glass, reinforced glass, headlight covers and the like for automobiles, trams, airplanes, etc., and for external walls. Water-repellent oil-repellent coating film for building materials, oil-repellent coating film for kitchen building materials, anti-fouling and sticker for telephone booths. Duck coating film, fingerprint-proof coating film for art products, fingerprint-proof coating film for optical discs, DVDs, mold release agent or coating additive for molds, resin modifier, and inorganic filler flow It is used as a lubricity-improving agent such as a modifier, a dispersive modifier, a tape, or a film.

[Example]

The following examples and comparative examples illustrate the present invention in more detail, but the present invention is not limited by the following examples.

[Example 1]

In a reaction vessel, 100 g (2.9 × 10 ^-2 mol) of a compound represented by the following formula (A) was mixed:

37 g (4.3 × 10 ^-2 mol) of a compound represented by the following formula (B):

Tetrabutylammonium hydrogen sulfate 0.89 g (2.6 × 10 ^-3 mol). Next, 35 g (2.6 × 10 ^-1 mol) of a 30% by mass sodium hydroxide aqueous solution was added, and then heated at 60 ° C. for 20 hours. After the heating was completed, the mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was added dropwise. After a liquid separation operation, the lower fluorine compound layer was recovered and then washed with acetone. The lower layer, which is the fluorine compound layer, was recovered again after washing, and the residual solvent was distilled off under reduced pressure. The above operation was performed again to obtain 103 g of a fluorine-containing polyether group polymer represented by the following formula (C).

The molecular structure analysis results of the fluorine-containing polyether-based polymer represented by the formula (C) by NMR are as follows.

¹ H-NMR

δ 3.4-3.5 (CC H ₂ -O-CH ₂ CH = CH ₂ ) 6H

δ 3..6-3.7 (-CF ₂ -CH ₂ -OC H ₂ -C) 2H

δ 3.7-3.8 (-CF ₂ -C H ₂ -OC H ₂ -C) 2H

δ 3.8-3.9 (C-CH ₂ -OC H ₂ CH = CH ₂ ) 6H

δ 5.0-5.2 (C-CH ₂ -O-CH ₂ CH = C H ₂ ) 6H

δ 5.7-5.9 (C-CH ₂ -O-CH ₂ C H = CH ₂ ) 3H

In a reaction vessel, mix 50 g of the compound represented by the following formula (C) obtained above (1.5 × 10 ^-2 mol, that is, the terminal allyl ether group; equivalent to 4.5 × 10 ^-2 mol):

50g of 1,3-bis (trifluoromethyl) benzene, 11g of trimethoxysilane (9.0 × 10 ^-2 mol), and toluene solution of platinum chloride / vinylsiloxane complex 5.0 × 10 ^-2 g (containing 1.5 × 10 ^-7 mol based on Pt monomer), and aged at 80 ° C. for 5 hours. Subsequently, the solvent and unreacted matter were distilled off under reduced pressure to obtain 55 g of a liquid product.

The obtained compound was confirmed to have a structure represented by the following formula (D) by NMR.

¹ H-NMR

δ 0.4-0.6 (-CH ₂ CH ₂ C H ₂ -Si) 6H

δ 1.4-1.6 (-CH ₂ C H ₂ CH ₂ -Si) 6H

δ 3.1-3.7 (-Si (OC H ₃ ) ₃ , -C H ₂ CH ₂ CH ₂ -Si, CC H ₂ -OC H ₂ CH ₂ CH ₂ -Si, -CF ₂ -CH ₂ -OC H _2- C, -CF ₂ -C H ₂ -O-CH ₂ -C) 43H

[Example 2]

In a reaction vessel, 100 g (2.9 × 10 ^-2 mol) of a compound represented by the following formula (A) was mixed:

26 g (4.3 × 10 ^-1 mol) of a compound represented by the following formula (E):

Tetrabutylammonium hydrogen sulfate 0.89 g (2.6 × 10 ^-3 mol). Next, 35 g (2.6 × 10 ^-1 mol) of a 30% by mass sodium hydroxide aqueous solution was added, and then heated at 60 ° C. for 20 hours. After the heating was completed, the mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was added dropwise. After a liquid separation operation, the lower fluorine compound layer was recovered and then washed with acetone. The lower layer, which is the fluorine compound layer, was recovered again after washing, and the residual solvent was distilled off under reduced pressure. The above operation was performed again to obtain 101 g of a fluorine-containing polyether-based polymer represented by the following formula (F).

The molecular structure analysis results of the fluorine-containing polyether-based polymer represented by the formula (F) by NMR are as follows.

¹ H-NMR

δ 0.7-0.9 (-CH ₂ C H ₃ ) 3H

δ 1.3-1.5 (-C H ₂ CH ₃ ) 2H

δ 3.2-3.2 (CC H ₂ -O-CH ₂ CH = CH ₂ ) 4H

δ 3.4-3.5 (-CF ₂ -CH ₂ -OC H ₂ -C) 2H

δ 3.δ-3.7 (-CF ₂ -C H ₂ -OC H ₂ -C) 2H

δ 3.8-3.9 (C-CH ₂ -OC H ₂ CH = CH ₂ ) 4H

δ 4.9-5.2 (C-CH ₂ -O-CH ₂ CH = C H ₂ ) 4H

δ 5.7-5.8 (C-CH ₂ -O-CH ₂ C H = CH ₂ ) 2H

In a reaction vessel, mix 50 g of the compound represented by the following formula (F) obtained above (1.5 × 10 ^-2 mol, that is, a terminal allyl ether group; equivalent to 3.0 × 10 ^-2 mol):

1,3-bis (trifluoromethyl) benzene 50g, trimethoxy Silane ^{7.3g (6.0 × 10 -2 mol)} , and a chloroplatinic acid / vinyl toluene silicon of siloxane complexes was 5.0 × 10 ^{- 2} g (containing 1.5 × 10 ^-7 mol based on Pt monomer), and aged at 80 ° C. for 5 hours. Subsequently, the solvent and unreacted matter were distilled off under reduced pressure to obtain 52 g of a liquid product.

The obtained compound was confirmed to have a structure represented by the following formula (G) by NMR.

¹ H-NMR

δ 0.4-0.6 (-CH ₂ CH ₂ C H ₂ -Si) 4H

δ 0.6-0.8 (-CH ₂ C H ₃ ) 3H

δ 1.2-1.4 (-C H ₂ CH ₃ ) 2H

δ 1.5-1.7 (-CH ₂ C H ₂ CH ₂ -Si) 4H

δ 3.1-3.7 (-Si (OC H ₃ ) ₃ , -C H ₂ CH ₂ CH ₂ -Si, CC H ₂ -OC H ₂ CH ₂ CH ₂ -Si, -CF ₂ -CH ₂ -OC H _2- C, -CF ₂ -C H ₂ -O-CH ₂ -C) 30H

[Example 3]

In a reaction container, 100 g of a compound represented by the following formula (H) (2.7 × 10 ^-2 mol, that is, a terminal hydroxyl group; equivalent to 5.4 × 10 ^-2 mol) was mixed:

69 g (8.1 × 10 ^-2 mol) of a compound represented by the following formula (B):

Tetrabutylammonium hydrogen sulfate 1.7 g (4.9 × 10 ^-3 mol). Next, 65 g (4.9 × 10 ^-1 mol) of a 30% by mass sodium hydroxide aqueous solution was added, and then heated at 60 ° C. for 20 hours. After the heating was completed, the mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was added dropwise. After a liquid separation operation, the lower fluorine compound layer was recovered and then washed with acetone. The lower layer, which is the fluorine compound layer, was recovered again after washing, and the residual solvent was distilled off under reduced pressure. The above operation was performed again to obtain 107 g of a fluorine-containing polyether group polymer represented by the following formula (I).

The molecular structure analysis results of the fluorinated polyether-based polymer represented by the formula (I) by NMR are as follows.

¹ H-NMR

δ 3.4-3.5 (CC H ₂ -O-CH ₂ CH = CH ₂ ) 12H

δ 3.6-3.7 (-CF ₂ -CH ₂ -OC H ₂ -C) 4H

δ 3.7-3.8 (-CF ₂ -C H ₂ -OC H ₂ -C) 4H

δ 3.8-3.9 (C-CH ₂ -OC H ₂ CH = CH ₂ ) 12H

δ 4.9-5.1 (C-CH ₂ -O-CH ₂ CH = C H ₂ ) 12H

δ 5.7-5.9 (C-CH ₂ -O-CH ₂ C H = CH ₂ ) 6H

In a reaction vessel, mix 50 g of the compound represented by the following formula (I) obtained above (1.33 × 10 ^-2 mol, that is, the terminal allyl ether group; equivalent to 8.0 × 10 ^-2 mol):

50g of 1,3-bis (trifluoromethyl) benzene, 20g of trimethoxysilane (1.6 × 10 ^-1 mol), and toluene solution of platinum chloride / vinylsiloxane complex 5.0 × 10 ^-2 g (containing 1.5 × 10 ^-7 mol based on Pt monomer), and aged at 80 ° C. for 5 hours. Subsequently, the solvent and unreacted matter were distilled off under reduced pressure to obtain 60 g of a liquid product.

The obtained compound was confirmed to have a structure represented by the following formula (J) by NMR.

¹ H-NMR

δ 0.4-0.7 (-CH ₂ CH ₂ C H ₂ -Si) 12H

δ 1.4-1.7 (-CH ₂ C H ₂ CH ₂ -Si) 12H

δ 3.1-3.8 (-Si (OC H ₃ ) ₃ , -C H ₂ CH ₂ CH ₂ -Si, CC H ₂ -OC H ₂ CH ₂ CH ₂ -Si, -CF ₂ -CH ₂ -OC H _2- C, -CF ₂ -C H ₂ -O-CH ₂ -C) 86H

[Comparative Example 1]

The following polymers were used as Comparative Example 1.

[Chem 55] CF ₃ O- (CF ₂ O) _p1 -(C ₂ F ₄ O) _q1 -CF ₂ -O-CH ₂ CH ₂ CH ₂ -Si (OCH ₃ ) ₃    (K) p1: q1 = 47: 53, p1 + q1 ≒ 43

[Comparative Example 2]

The following polymers were used as Comparative Example 2.

Preparation of surface treatment agent and formation of hardened film

Among the fluoropolyether-based polymer modified silanes obtained in Examples 1 to 3, the fluoropolyether-based polymer modified silanes obtained in Examples 1 and 2 were used as surface treatment agents for the following evaluations. That is, the fluoropolyether-based polymer modified silanes obtained in Examples 1 and 2 and the polymers of Comparative Examples 1 and 2 were dissolved in Novec 7200 (manufactured by 3M Corporation, ethyl group) so as to have a concentration of 20% by mass. Perfluorobutyl ether) to prepare a surface treatment agent.

[Film coating]

6 mg of each surface treatment agent (treatment conditions, pressure: 2.0 × 10 ^-2 Pa, heating temperature: 700 ° C.) were vacuum-deposited on glass (Gorilla, manufactured by Corning Corporation) with SiO ₂ based on the outermost surface treated at 10 nm. Hardened for 12 hours at ℃ and 40% humidity to form a hardened film with a thickness of 7nm.

[Thick film coating]

10 mg of each surface treatment agent (treatment conditions, pressure: 2.0 × 10 ^-2 Pa, heating temperature: 700 ° C.) was vacuum-deposited on glass (Gorilla, manufactured by Corning Corporation) with the highest surface SiO ₂ system treated at 10 nm. Hardened for 12 hours under the environment of ℃ and humidity of 40% to form a hardened film with a thickness of 14nm.

Evaluation of water repellency [Evaluation of initial water repellency]

For the above-mentioned glass formed by thin film coating, a contact angle meter (Drop Master (produced by Kyowa Interface Science Co., Ltd.)) was used to measure the contact angle (water repellency) of the cured film with respect to water (droplet: 2 μl, temperature: 25 ° C., Humidity: 40%). The results (initial water contact angle) are shown in Table 1.

In the initial stage, both Examples and Comparative Examples showed good water repellency.

[Evaluation of abrasion resistance]

The above-mentioned glass (for evaluation of abrasion resistance) formed by thin film coating using a friction tester (manufactured by Shinto Science Co., Ltd.) was rubbed under the following conditions for 10,000 times, and the cured film was performed in the same manner as above The contact angle (water repellency) with respect to water was measured and evaluated as abrasion resistance. The test environmental conditions were 25 ° C and 40% humidity. The results (water contact angle after abrasion) are shown in Table 1.

Abrasion resistance of steel wool

Steel wool: BONSTAR # 0000 (made by Japan Steel wool Co., Ltd.)

Contact area: 10mmΦ

Travel distance (single trip) 30mm

Movement speed: 1,800mm / min

Load: 1kg / cm ²

The compounds of Examples 1 and 2 have a plurality of ether linkage groups in the molecule, and the adhesion to the substrate is improved. Therefore, the hardened film using the surface treatment agent of the compounds of Examples 1 and 2 exhibits contact with the comparative example. Good abrasion resistance at angles above 100 °.

[Evaluation of haze value]

For the above-mentioned glass (for evaluation of haze value) for forming a hardened film by thin film coating and thick film coating, a turbidimeter (NDH-5000) (manufactured by Nippon Denshoku Industries Co., Ltd.) was used in accordance with JIS K 7136: 2000. Determine the haze value. The results (haze value) are shown in Tables 1 and 2. The haze value was 0.3 or more, and haze was visually confirmed. When the film (7 nm) was applied, the haze value of the examples and comparative examples were both lower than 0.3. On the other hand, when the thick film (14 nm) is applied, the compounds of Examples 1 and 2 have an ether linkage group having a plurality of polar groups in the molecule to improve the wettability with the substrate. Therefore, the compounds of Examples 1 and 2 are used. As compared with the comparative example, the cured coating of the surface treatment agent was confirmed to have a haze value of 0.3 or less and improved visibility.

Claims (9)

A fluoropolyether-based polymer modified silane represented by the following general formula (1),

(In the formula, Rf is a monovalent or divalent fluorooxyalkylene-containing polymer residue, Q is a divalent hydrocarbon group having 2 to 6 carbon atoms which may contain an ether bond, and Y is a silicon atom or a silane group. Radicals and / or siloxane groups of 2 to 6 valences, R is independently an alkyl group having 1 to 4 carbon atoms, X is independently a hydroxyl group or a hydrolyzable group, n is an integer of 1 to 3, and γ is an integer of 1 to 5 Integer, m is an integer of 1 to 5, R 'is an alkyl group of 1 to 4 carbons, β is an integer of 1 to 3, and α is 1 or 2). For example, the fluoropolyether-based polymer modified silane of claim 1, wherein α of the aforementioned formula (1) is 1, and the Rf group is a polymerization of a monovalent fluorine-containing oxyalkylene group represented by the following general formula (2) Residues,

(In the formula, p, q, r, and s are integers from 0 to 200, and p + q + r + s = 3 to 200. Each repeating unit can be linear or branched. Each repeating unit They can be randomly bonded to each other, d is an integer of 1 to 3, and the unit (-C _d F _2d- ) can be linear or branched). For example, fluoropolyether-based polymer modified silane of claim 1, wherein α in the aforementioned formula (1) is 2, and Rf group is a polymerization of a divalent fluorine-containing oxyalkylene group represented by the following general formula (3) Residues,

(In the formula, p, q, r, and s are integers from 0 to 200, and p + q + r + s = 3 to 200. Each repeating unit can be linear or branched. Each repeating unit They can be randomly bonded to each other, d is an integer of 1 to 3, and the units (-C _d F _2d- ) can be independently linear or branched). For example, the fluorine-containing polyether-based polymer modified silane of any one of claims 1 to 3, wherein in the formula (1), Y is selected from the group consisting of an alkylene group having 3 to 10 carbon atoms and a carbon number of 6 to Dialkyl radical of 8-arylene group, dialkyl groups through silicon atom, silyl group, silyl group structure or silyl group structure, and divalent groups with 2 to 10 silicon atoms Chain-shaped or branched or cyclic 2- to 4-valent organic polysiloxane residues with 3 to 10 silicon atoms, or alkylene groups with 2 to 10 carbon atoms bonded to the bond of silicon atoms At least one kind of group in a group of 2 to 4 valence groups. The fluoropolyether-based polymer modified silane according to any one of claims 1 to 4, wherein in the aforementioned formula (1), Q is -CH ₂ OCH _2- . The fluoropolyether-based polymer modified silane according to any one of claims 1 to 5, wherein in the foregoing formula (1), X is selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, and a carbon number. 2 to 10 alkoxyalkoxy, carbon number 2 to 10 At least one of the group consisting of a fluorenyloxy group, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen group. If the fluoropolyether-based polymer modified silane according to any one of claims 1 to 6, wherein the polymer modified silane represented by formula (1) is expressed by any one of the following formulas,

(In the formula, p1 is an integer from 5 to 100, q1 is an integer from 5 to 100, and p1 + q1 is an integer from 10 to 105). A surface treatment agent containing the fluoropolyether-based polymer modified silane according to any one of claims 1 to 7 and / or a partial (hydrolyzed) condensate thereof. An article having a hardened coating having a surface treating agent as claimed in claim 8 on the surface.