WO2017141707A1

WO2017141707A1 - Fluoropolyether group-containing polymer-modified silane, surface treatment agent and article

Info

Publication number: WO2017141707A1
Application number: PCT/JP2017/003613
Authority: WO
Inventors: 隆介酒匂; 愛里朝倉; 高至松田; 祐治山根
Original assignee: 信越化学工業株式会社
Priority date: 2016-02-17
Filing date: 2017-02-01
Publication date: 2017-08-24
Also published as: JP6680350B2; KR20180110105A; CN108699237A; JPWO2017141707A1; TW201803915A; TWI780042B; CN108699237B

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; γ 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; β represents an integer of 1 to 3; and α represents 1 or 2.)

Description

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

TECHNICAL FIELD The present invention relates to a fluoropolyether group-containing polymer-modified silane, and more specifically, a fluoropolyether group-containing polymer-modified silane that forms a film excellent in water and oil repellency and abrasion resistance, and the silane and / or part thereof. The present invention relates to a surface treatment agent containing a (hydrolysis) condensate and an article surface-treated with the surface treatment agent (that is, having a cured film of the surface treatment agent on the surface).

In recent years, the use of touch panels on screens such as mobile phone displays has been accelerating. However, the touch panel has an exposed screen, and there are many opportunities for direct contact with fingers, cheeks, and the like, and it is a problem that dirt such as sebum is easily attached. Therefore, the demand for technology that makes it difficult to attach fingerprints to the surface of the display to improve the appearance and visibility, and technology that makes it easier to remove dirt is increasing year by year, and the development of materials that can meet these requirements has been developed. It is desired. In particular, since the surface of the touch panel display is easily contaminated with fingerprints, it is desired to provide a water / oil repellent layer. However, the conventional water / oil repellent layer has high water / oil repellency and excellent dirt wiping property, but has a problem that the antifouling performance deteriorates during use.

Generally, a 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. Utilizing its properties, it is widely used industrially for water and oil repellent and antifouling agents such as paper and fiber, lubricants for magnetic recording media, oil repellents for precision equipment, mold release agents, cosmetics, and protective films. ing. However, the property means that it is non-adhesive and non-adhesive to other substrates at the same time, and even if it can be applied to the surface of the substrate, it was difficult to make the film adhere to it. .

On the other hand, a silane coupling agent is well known as a material for bonding a substrate surface such as glass or cloth and 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 silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group) in one molecule. The hydrolyzable silyl group causes a self-condensation reaction with moisture in the air to form a film. The coating becomes a strong coating having durability by chemically and physically bonding the hydrolyzable silyl group to the surface of glass or metal.

Therefore, by using a fluoropolyether group-containing polymer-modified silane in which a hydrolyzable silyl group is introduced into a fluoropolyether group-containing compound, it is easy to adhere to the substrate surface, and the substrate surface has water and oil repellency, resistance to water. Compositions capable of forming a film having chemical properties, lubricity, releasability, antifouling properties, etc. are disclosed (Patent Documents 1 to 5: JP-T 2008-534696, JP-T 2008-537557) JP, 2012-072272, JP 2012-157856, JP 2013-136833).

Cured coatings such as lenses and antireflective coatings that have been surface treated with a composition containing a fluoropolyether group-containing polymer-modified silane in which a hydrolyzable silyl group has been introduced into the fluoropolyether group-containing compound are slippery and releasable. However, in recent years, there is a high demand for wear resistance by users, and it has not been able to exhibit sufficient performance. Moreover, although it becomes easy to exhibit performance by coating with a thick film, cloudiness (haze) will generate | occur | produce on the glass surface and visibility will be impaired.

Special table 2008-534696 Special table 2008-537557 JP 2012-072272 A JP 2012-157856 A JP 2013-136833 A

The present invention has been made in view of the above circumstances, and is a fluoropolyether group-containing polymer-modified silane capable of forming a cured film excellent in water and oil repellency and abrasion resistance, and the silane and / or part thereof ( It is an object of the present invention to provide a surface treatment agent containing a hydrolyzate condensate and an article surface-treated with the surface treatment agent (having a cured film of the surface treatment agent on the surface).

As a result of intensive studies to solve the above object, the present inventors use a fluoropolyether group-containing polymer-modified silane represented by the following general formula (1) in the fluoropolyether group-containing polymer-modified silane. Thus, it is found that the surface treatment agent containing the silane and / or its partial (hydrolyzed) condensate can form a cured film excellent in water and oil repellency, abrasion resistance, and visibility. It came to.

Accordingly, the present invention provides the following fluoropolyether group-containing polymer-modified silane, surface treatment agent and article.
[1]
The following general formula (1)

(Wherein Rf is a monovalent or divalent fluorooxyalkylene group-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, a silylene group and / or a divalent to hexavalent hydrocarbon group optionally having a siloxane bond, R is independently an alkyl group having 1 to 4 carbon atoms, and X is independently a hydroxyl group or hydrolyzed 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 carbon atoms, β Is an integer from 1 to 3, and α is 1 or 2.)
A fluoropolyether group-containing polymer-modified silane represented by:
[2]
Α in the formula (1) is 1, and the Rf group is a monovalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (2): Ether group-containing polymer-modified silane.

(Wherein p, q, r and s are each an integer of 0 to 200 and p + q + r + s = an integer of 3 to 200, and each repeating unit may be linear or branched, May be randomly bonded, d is an integer of 1 to 3, and the unit (—C _d F _2d —) may be linear or branched.)
[3]
Α in the formula (1) is 2, and the Rf group is a divalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (3): Ether group-containing polymer-modified silane.

(Wherein p, q, r and s are each an integer of 0 to 200 and p + q + r + s = an integer of 3 to 200, and each repeating unit may be linear or branched, May be bonded at random, d is an integer of 1 to 3, and the units (—C _d F _2d —) may be each independently linear or branched.)
[4]
In the above formula (1), Y represents an alkylene group having 3 to 10 carbon atoms, an alkylene group containing an arylene group having 6 to 8 carbon atoms, an alkylene group having a silicon atom, a silylene group, a silalkylene structure, or a silarylene structure. A divalent group bonded via each other and a linear or branched or cyclic divalent to tetravalent organopolysiloxane residue having 2 to 10 silicon atoms or a silicon atom having 3 to 10 silicon atoms, or silicon Any one of [1] to [3], which is at least one group selected from the group consisting of divalent to tetravalent groups in which an alkylene group having 2 to 10 carbon atoms is bonded to an atom bond. Fluoropolyether group-containing polymer-modified silane.
[5]
In the formula (1), Q is
—CH ₂ OCH ₂ —
The fluoropolyether group-containing polymer-modified silane according to any one of [1] to [4].
[6]
In the formula (1), each X is a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms. And the fluoropolyether group-containing polymer-modified silane according to any one of [1] to [5], which is at least one selected from the group consisting of halogen groups.
[7]
The fluoropolyether group-containing polymer-modified silane according to any one of [1] to [6], wherein the polymer-modified silane represented by the formula (1) is represented by any one of the following formulas.

(Wherein 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)
[8]
A surface treating agent comprising the fluoropolyether group-containing polymer-modified silane and / or a partial (hydrolyzed) condensate thereof according to any one of [1] to [7].
[9]
[8] An article having a cured coating of the surface treatment agent according to [8] on its surface.

Since the fluoropolyether group-containing polymer-modified silane of the present invention has a large number of reactive functional groups and ether linking groups, adhesion to a substrate and wettability are improved, whereby the silane and / or part thereof ( Articles surface-treated with a surface treatment agent containing a (hydrolysis) condensate are excellent in water and oil repellency, wear resistance and visibility.

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

(Wherein Rf is a monovalent or divalent fluorooxyalkylene group-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, a silylene group and / or a divalent to hexavalent hydrocarbon group optionally having a siloxane bond, R is independently an alkyl group having 1 to 4 carbon atoms, and X is independently a hydroxyl group or hydrolyzed 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 carbon atoms, β Is an integer from 1 to 3, and α is 1 or 2.)

The fluoropolyether group-containing polymer-modified silane of the present invention comprises a monovalent or divalent fluorooxyalkylene group-containing polymer residue (Rf), a hydrolyzable silyl group such as an alkoxysilyl group, or a hydroxyl group-containing silyl group (—Si (R) _3-n (X) _n ) may have a hydrocarbon chain (Q) and an ether group and a silicon atom, a silylene group and / or a siloxane bond, a divalent to hexavalent hydrocarbon group (Y) It has a structure bonded via, preferably has 3 or more reactive functional groups (X) in the polymer, and has a plurality of ether linking groups to improve the adhesion to the substrate, wear resistance, visual recognition It is characterized by excellent properties.

When α is 1, a monovalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (2) (hereinafter sometimes referred to as a monovalent fluorooxyalkyl group) is preferable. .

(Wherein p, q, r and s are each an integer of 0 to 200 and p + q + r + s = an integer of 3 to 200, and each repeating unit may be linear or branched, May be randomly bonded, d is an integer of 1 to 3, and the unit (—C _d F _2d —) may be linear or branched.)

When α is 2, a divalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (3) (hereinafter sometimes referred to as a divalent fluorooxyalkylene group) is preferable. .

(Wherein p, q, r and s are each an integer of 0 to 200 and p + q + r + s = an integer of 3 to 200, and each repeating unit may be linear or branched, May be bonded at random, d is an integer of 1 to 3, and the units (—C _d F _2d —) may be each independently linear or branched.)

In the above formulas (2) and (3), 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 Integer, s is an integer of 0 to 100, p + q + r + s = an integer of 3 to 200, preferably an integer of 10 to 105, and each repeating unit may be linear or branched, May be randomly combined. More preferably, p + q is an integer of 10 to 105, particularly an integer of 15 to 60, and r = s = 0. If p + q + r + s is smaller than the above upper limit value, the adhesion and curability are good, and if p + q + r + s is larger than the above lower limit value, the characteristics of the fluoropolyether group can be sufficiently exhibited.

In the above formulas (2) and (3), d is an integer of 1 to 3, preferably 1 or 2, and the units (—C _d F _2d —) are each independently linear or branched. There may be.

Specific examples of Rf include the following.

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

In the above formula (1), Y is a divalent to hexavalent, preferably divalent to tetravalent, more preferably divalent hydrocarbon group, which may have a silicon atom, a silylene group and / or a siloxane bond, By not including a linking group having a low binding energy in the molecule, a coating film having excellent wear resistance can be provided.

Specific examples of Y include a propylene group (trimethylene group, methylethylene group), a butylene group (tetramethylene group, methylpropylene group), a C3-C10 alkylene group such as a hexamethylene group, and a carbon such as a phenylene group. An alkylene group containing an arylene group of 6 to 8 (for example, an alkylene / arylene group of 8 to 16 carbon atoms) and an alkylene group are bonded to each other via a silicon atom, a silylene group, a silalkylene structure, or a silarylene structure. Divalent group, 2 to 10 silicon atoms, preferably 2 to 5 linear, branched or cyclic divalent to hexavalent organopolysiloxane residues, or the number of carbon atoms in the bond of silicon atoms Examples thereof include divalent to hexavalent groups to which an alkylene group having 2 to 10 is bonded, and preferably an alkylene group having 3 to 10 carbon atoms and an phenylene group. A divalent group in which a ren group and an alkylene group are bonded to each other via a silalkylene structure or a silarylene structure, a linear group having 2 to 10 silicon atoms, or a branched or cyclic group having 3 to 10 silicon atoms A divalent to tetravalent organopolysiloxane residue, or a divalent to tetravalent group in which an alkylene group having 2 to 10 carbon atoms is bonded to the bond of a silicon atom, more preferably 3 to 6 carbon atoms. An alkylene group;

Here, as a silalkylene structure and a silarylene structure, what is shown below can be illustrated.

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

Examples of the linear, branched or cyclic divalent to hexavalent organopolysiloxane residues having 2 to 10, preferably 2 to 5 silicon atoms include the following.

(Wherein R ¹ is the same as above, g is an integer of 1 to 9, preferably 1 to 4, h is an integer of 2 to 6, preferably 2 to 4, and j is 0) An integer of ˜8, 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 include the following groups.

In the above formula (1), Q is a divalent hydrocarbon group having 2 to 6 carbon atoms which may contain an ether bond. Specific examples of Q include an ethylene group, a propylene group (trimethylene group, a methylethylene group), a butylene group (tetramethylene group, a methylpropylene group), a hexamethylene group and other alkylene groups having 2 to 6 carbon atoms, an ether bond Alkylene group having 2 to 6 carbon atoms such as ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), hexamethylene group, and the like, preferably ether bond Is an alkylene group having 2 or 3 carbon atoms in between.

Specific examples of Q include the following groups.

In the above formula (1), X is a hydroxyl group or a hydrolyzable group which may be different from each other. Examples of such X include hydroxyl groups, methoxy groups, ethoxy groups, propoxy groups, isopropoxy groups, butoxy groups and the like, alkoxy groups having 1 to 10 carbon atoms, methoxymethoxy groups, methoxyethoxy groups and the like having 2 to 10 carbon atoms. Examples include an alkoxy-substituted alkoxy group, an acyloxy group having 2 to 10 carbon atoms such as an acetoxy group, an alkenyloxy group having 2 to 10 carbon atoms such as an isopropenoxy group, a halogen atom such as a chloro atom, a bromo atom, and an iodo atom. Of these, a methoxy group, an ethoxy group, an isopropenoxy group, and a chloro atom are preferable.

In the above formula (1), R is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, and among them, a methyl group and an ethyl group are preferable. n is an integer of 1 to 3, preferably 2 or 3, and 3 is more preferable from the viewpoint of reactivity and adhesion to a substrate.

In the above formula (1), m is an integer of 1 to 5, and 1 or 2 is preferable from the viewpoint of obtaining raw materials. Γ is an integer of 1 to 5, and is preferably an integer of 1 to 3 from the viewpoint of easiness of synthesis, stability of the product, and the like.

In the above formula (1), R ′ is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group. Among them, a methyl group or an ethyl group is preferable. β is an integer of 1 to 3, and 2 or 3 is preferable from the viewpoint of reactivity and adhesion to a substrate.

Examples of the fluoropolyether group-containing polymer-modified silane represented by the above formula (1) include those represented by the following formula. In each formula, the number of repeating units (or the degree of polymerization) constituting the fluorooxyalkyl group or fluorooxyalkylene group can take any number satisfying the above formulas (2) and (3). It is.

(Wherein 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)

Examples of the method for preparing the fluoropolyether group-containing polymer-modified silane represented by the above formula (1) and α being 1 include the following methods.
A fluorooxyalkyl group-containing polymer having preferably two or more (particularly two or three) olefin moieties at one end of the molecular chain is used as a solvent, for example, a fluorine-based polymer such as 1,3-bis (trifluoromethyl) benzene. An organic silicon compound dissolved in a solvent and having a SiH group and a hydrolyzable terminal group (alkoxy group such as methoxy group) in a molecule such as trimethoxysilane, and a hydrosilylation reaction catalyst such as a chloroplatinic acid / vinylsiloxane complex In the presence of a toluene solution 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, more preferably about 5 hours, Hydrosilylation addition reaction and aging.

Moreover, as another method of preparing the fluoropolyether group-containing polymer-modified silane represented by the above formula (1) and α = 1, for example, the following method may be mentioned.
A fluorooxyalkyl group-containing polymer having preferably two or more (particularly two or three) olefin moieties at one end of the molecular chain is used as a solvent, for example, a fluorine-based polymer such as 1,3-bis (trifluoromethyl) benzene. An organosilicon compound having a SiH group and a hydrolyzable end group in a molecule such as trichlorosilane is dissolved in a solvent and a hydrosilylation reaction catalyst such as a chloroplatinic acid / vinylsiloxane complex in a toluene solution is present at 40 to 120 ° C. After the hydrosilylation addition reaction and aging at a temperature of preferably 60 to 100 ° C., more preferably about 80 ° C. for 1 to 48 hours, preferably 2 to 10 hours, more preferably about 5 hours. A hydrolyzable group such as an alkoxy group such as a methoxy group with a substituent (such as a chlorine atom bonded to a silicon atom) on a silyl group To convert.

In addition, instead of the organosilicon compound having a SiH group and a hydrolyzable end group in the molecule, a SiH group-containing organosilicon compound having no hydrolyzable end group can also be used. As an organosilicon compound having no hydrolyzable end groups in the molecule and having two or more SiH groups. At that time, in the same manner as in the above method, preferably a fluorooxyalkyl group-containing polymer having two or more (particularly two or three) olefin moieties at one end of the molecular chain and a hydrolyzable end group in the molecule. A reaction product having 2 or more (especially 2 or 3) residual SiH groups at the end of one molecular chain by hydrosilylation addition reaction with an organosilicon compound having 2 or more SiH groups After the (intermediate) is produced, a residual SiH group at the polymer end of the reaction product (intermediate) and an organosilicon compound having an olefin moiety and a hydrolyzable end group in the molecule such as allyltrimethoxysilane Hydrosilation reaction catalyst, for example, in the presence of a toluene solution of chloroplatinic 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, more preferably under conditions of about 5 hours, is aged together to hydrosilylation addition reaction again.

Here, as the fluorooxyalkyl group-containing polymer having an olefin moiety at one end of the molecular chain, a fluorooxyalkyl group-containing polymer represented by the following general formula (4) can be exemplified.

(In the formula, Rf, R ′, Q, m, and β are the same as above. 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, particularly 1 to 4 carbon atoms. Specifically, a methylene group, an ethylene group, C1-C8 alkylene group such as propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), hexamethylene group, octamethylene group, etc., and C6-C8 such as phenylene group And an alkylene group containing an arylene group (for example, an alkylene / arylene group having 7 to 8 carbon atoms). Z is preferably a linear alkylene group having 1 to 4 carbon atoms.

Preferred examples of the fluorooxyalkyl group-containing polymer represented by the formula (4) include those shown below. In each formula, the number of repeats (or the degree of polymerization) of each repeating unit constituting the fluorooxyalkyl group can be any number satisfying the formula (2) in Rf.

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

Examples of the method for preparing the fluorooxyalkyl group-containing polymer represented by the above formula (4) include, for example, a fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of a molecular chain and an olefin introducing agent in the presence of a base. Aging is carried out at 0 to 90 ° C., preferably 50 to 80 ° C., more preferably about 60 ° C. for 1 to 40 hours, preferably 10 to 30 hours, more preferably about 20 hours, if necessary using additives and solvents. To do.

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

(In the formula, u1 is an integer of 1 to 24, and r1, p1, q1, and p1 + q1 are the same as above.)

As the olefin introducing agent used for the preparation of the fluorooxyalkyl group-containing polymer represented by the formula (4), for example, preferably two or more (in particular, two or Examples include those having a sulfonic acid ester residue represented by -S (= O) ₂ O- at the other terminal and 3) olefin sites.

The olefin introducing agent can be prepared by a known method.
The amount of the olefin introducing agent used is preferably 1 to 5 equivalents as a sulfonic acid ester residue with respect to 1 equivalent of the reactive terminal group (terminal hydroxyl group) of the fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain. Can be used in an amount of 1 to 3 equivalents, more preferably about 1.5 equivalents.

As a base used for the preparation of the fluorooxyalkyl group-containing polymer represented by the formula (4), for example, amines and alkali metal bases can be used. Specifically, for amines, triethylamine, Examples include diisopropylethylamine, pyridine, DBU, and imidazole. Among alkali metal bases, sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, alkyllithium, t-butoxypotassium, lithium diisopropylamide, lithium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, potassium bis And (trimethylsilyl) amide.
The amount of the base used is 1 to 20 equivalents, more preferably 5 to 15 equivalents, and still more preferably about 9 equivalents with respect to 1 equivalent of the reactive terminal group of the polymer having a hydroxyl group at one end of the molecular chain. Can be used.

For the preparation of the fluorooxyalkyl group-containing polymer represented by the formula (4), tetrabutylammonium halide, alkali metal halide or the like may be used as an additive for improving reactivity or as a phase transfer catalyst. Specific examples of the additive include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydrogen sulfate, sodium iodide, potassium iodide, cesium iodide, crown ether and the like. . These additives improve the reactivity by catalytically exchanging halogens with the olefin introducing agent in the reaction system, and the crown ether coordinates with the metal to improve the reactivity.
The additive is used in an amount of 0.005 to 0.2 equivalent, more preferably 0.01 to 0.00, per 1 equivalent of the reactive end group of the fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain. 15 equivalents, more preferably about 0.1 equivalents can be used.

A solvent may be used for the preparation of the fluorooxyalkyl group-containing polymer represented by the formula (4). As the solvent used, fluorine-containing aromatic hydrocarbon solvents such as 1,3-bis (trifluoromethyl) benzene and trifluoromethylbenzene, 1,1,1,2,3,4, Hydrofluoroether (HFE) solvents such as 4,5,5,5-decafluoro-3-methoxy-2- (trifluoromethyl) pentane (manufactured by 3M, trade name: Novec series), fully fluorinated A perfluoro solvent composed of a compound (trade name: Fluorinert series, manufactured by 3M Co.) may be used. Further, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, THF, or the like can be used as the organic solvent. Further, water may be used.
The amount of solvent used is 10 to 300 parts by weight, preferably 30 to 150 parts by weight, more preferably about 50 parts by weight, based on 100 parts by weight of the fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain. Can be used.

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

In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the above formula (1) and α being 1, the solvent used is preferably a fluorinated solvent, and the fluorinated solvent is 1,3-bis ( 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) pentane and other hydrofluoroether (HFE) solvents (trade name: Novec series, manufactured by 3M), composed of fully fluorinated compounds Perfluoro solvent (made by 3M, trade name: Florinato Siri ), And the like.
The solvent is used in an amount of 10 to 300 parts by weight, preferably 50 to 150 parts by weight, more preferably about 100 parts by weight with respect to 100 parts by weight of the fluorooxyalkyl group-containing polymer having an olefin moiety at one end of the molecular chain. be able to.

In addition, in the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) and α is 1, an organosilicon compound having a SiH group and a hydrolyzable end group in the molecule includes the following general formula: Compounds represented by (5) to (8) are preferred.

Wherein R, X, n, R ¹ , R ² , g and j are the same as above. R ³ is a divalent hydrocarbon group having 2 to 8 carbon atoms. I is an integer of 1 to 5 (It is preferably an integer of 1 to 3, and i + j is an integer of 2 to 9, preferably an integer of 2 to 4.)

Here, the divalent hydrocarbon group having 2 to 8 carbon atoms, preferably 2 to 3 carbon atoms of R ³ includes ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group). ), An alkylene group such as a hexamethylene group and an octamethylene group, an arylene group such as a phenylene group, or a combination of two or more of these groups (an alkylene / arylene group, etc.). Among these, an ethylene group and trimethylene Groups are preferred.

Examples of the organosilicon compound having a SiH group and a hydrolyzable terminal group in the molecule include trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tributoxysilane, and triisopropenoxysilane. , Triacetoxysilane, trichlorosilane, tribromosilane, triiodosilane, and the following silanes.

In the preparation of a fluoropolyether group-containing polymer-modified silane represented by the formula (1) where α is 1, a fluorooxyalkyl group-containing polymer having an olefin moiety at one end of a molecular chain and a SiH group and hydrolysis in the molecule The amount of the organosilicon compound having a SiH group and a hydrolyzable end group in the molecule when reacting with the organosilicon compound having a functional end group is a fluorooxyalkyl group-containing polymer having an olefin moiety at one end of the molecular chain. 1 to 3 equivalents, more preferably 1.5 to 2.5 equivalents, and still more preferably about 2 equivalents to 1 equivalent of the reactive end group.

In addition, in the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) and α is 1, organosilicon having no hydrolyzable end group in the molecule and having two or more SiH groups As the compound, compounds represented by the following general formulas (9) to (11) are preferable.

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

Examples of the organosilicon compound having no hydrolyzable end group in the molecule and having two or more SiH groups include those shown below.

In the preparation of a fluoropolyether group-containing polymer-modified silane represented by the formula (1) and α = 1, a fluorooxyalkyl group-containing polymer having an olefin moiety at one end of the molecular chain and a hydrolyzable end group in the molecule The amount of the organosilicon compound having no hydrolyzable end group and having two or more SiH groups in the molecule when reacting with the organosilicon compound having two or more SiH groups is 7 to 30 equivalents, more preferably 10 to 20 equivalents, and still more preferably about 15 equivalents can be used per 1 equivalent of reactive end group of the fluorooxyalkyl group-containing polymer having an olefin moiety at the chain end.

In addition, in the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) where α is 1, an organosilicon compound having an olefin moiety and a hydrolyzable end group in the molecule includes the following general formula: The compound represented by (12) is preferred.

(In the formula, R, X and n are the same as described above. 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. Specific examples of the divalent hydrocarbon group having 1 to 6 carbon atoms include a methylene group and an ethylene group. , A propylene group (trimethylene group, methylethylene group), a butylene group (tetramethylene group, methylpropylene group), an alkylene group such as a hexamethylene group, and a phenylene group. U is preferably a single bond or a methylene group.

In the preparation of a fluoropolyether group-containing polymer-modified silane represented by the formula (1) and α = 1, a fluorooxyalkyl group-containing polymer having an olefin moiety at one end of the molecular chain and a hydrolyzable end group in the molecule In the molecule when reacting a reaction product of an organosilicon compound having 2 or more SiH groups with an organosilicon compound having an olefin moiety and a hydrolyzable end group in the molecule, The amount of the organosilicon compound having a decomposable end group is such that the polymer chain has a fluorooxyalkyl group-containing polymer having an olefin moiety at one end of the molecular chain and has no hydrolyzable end groups in the molecule and has at least two SiH groups. 3 to 9 equivalents, more preferably 5 to 7 equivalents, and even more preferably about 6 equivalents are used per 1 equivalent of the reactive end group of the reaction product with the organosilicon compound. It is possible.

In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) and α being 1, hydrosilylation reaction catalysts include platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum chloride Examples include complexes of acids with olefins, aldehydes, vinyl siloxanes, acetylene alcohols, and the like, and platinum group metal catalysts such as tetrakis (triphenylphosphine) palladium and chlorotris (triphenylphosphine) rhodium. Preferred are platinum compounds such as vinylsiloxane coordination compounds.
The amount of hydrosilylation reaction catalyst used is a fluorooxyalkyl group-containing polymer having an olefin moiety at one end of the molecular chain, or an organic compound having no hydrolyzable end groups in the polymer and molecule and having two or more SiH groups. It is used in an amount of 0.1 to 100 ppm, more preferably 1 to 50 ppm in terms of transition metal (mass) with respect to the mass of the reaction product with the silicon compound.

Then, the target compound can be obtained by depressurizingly distilling a solvent and an unreacted substance.
For example, as a fluorooxyalkyl group-containing polymer having an olefin moiety at one end of a molecular chain, a compound represented by the following formula

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

Examples of the preparation method of the fluoropolyether group-containing polymer-modified silane represented by the above formula (1) and α being 2 include the following methods.
A fluorooxyalkylene group-containing polymer having preferably two or more (particularly two or three) olefin moieties at both ends of the molecular chain and a solvent such as fluorine such as 1,3-bis (trifluoromethyl) benzene An organic silicon compound having a SiH group and a hydrolyzable end group in a molecule such as trimethoxysilane is dissolved in a system solvent, and a hydrosilylation reaction catalyst such as chloroplatinic acid / vinylsiloxane complex in the presence of a toluene solution Hydrosilylation addition reaction and aging at 120 ° C., preferably 60 to 100 ° C., more preferably about 80 ° C. for 1 to 48 hours, preferably 2 to 10 hours, more preferably about 5 hours. .

Moreover, as another method of preparing the fluoropolyether group-containing polymer-modified silane represented by the above formula (1) and α being 2, for example, the following method may be mentioned.
Preferably, a fluorooxyalkylene group-containing polymer having two or more (particularly two or three) olefin moieties at both ends of the molecular chain is used as a solvent, for example, fluorine such as 1,3-bis (trifluoromethyl) benzene. An organic silicon compound having a SiH group and a hydrolyzable end group in a molecule such as trichlorosilane is dissolved in a system solvent and a hydrosilylation reaction catalyst such as a chloroplatinic acid / vinylsiloxane complex in a toluene solution is present in an amount of 40 to 120. Hydrosilylation addition reaction and aging at a temperature of 1 ° C., preferably 60 to 100 ° C., more preferably about 80 ° C. for 1 to 48 hours, preferably 2 to 10 hours, more preferably about 5 hours. Thereafter, the substituent on the silyl group is converted to, for example, a methoxy group.

In addition, instead of the organosilicon compound having a SiH group and a hydrolyzable end group in the molecule, a SiH group-containing organosilicon compound having no hydrolyzable end group can also be used. As an organosilicon compound having no hydrolyzable end groups in the molecule and having two or more SiH groups. In this case, a fluorooxyalkylene group-containing polymer having two or more (particularly two or three) olefin moieties at both ends of the molecular chain and a hydrolyzable end group in the molecule in the same manner as described above. Reaction with an organosilicon compound having 2 or more SiH groups, and having two or more (especially 2 or 3) residual SiH groups at both ends of the molecular chain. After the product (intermediate) is formed, preferably two or more (particularly two or three) of SiH groups and allyltrimethoxysilane molecules remaining at the polymer ends of the reactant (intermediate), respectively In the presence of a hydrosilylation reaction catalyst such as a chloroplatinic acid / vinylsiloxane complex in a toluene solution, an organic silicon compound having an olefin moiety and a hydrolyzable end group in the presence of 40 to 40 The hydrosilylation addition reaction is carried out again at a temperature of 20 ° 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. Let

Here, the fluorooxyalkylene group-containing polymer having an olefin moiety at both ends of the molecular chain can be exemplified by a fluorooxyalkylene group-containing polymer represented by the following general formula (13).

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

Preferred examples of the fluorooxyalkylene group-containing polymer represented by the formula (13) include those shown below. In each formula, the number of repeating units (or the degree of polymerization) constituting the fluorooxyalkylene group can be any number satisfying the formula (3) in Rf.

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

As a method for preparing a fluorooxyalkylene group-containing polymer represented by the above formula (13), for example, a fluorooxyalkylene group-containing polymer having a hydroxyl group at both ends of a molecular chain and an olefin introducing agent in the presence of a base, Aging is carried out at 0 to 90 ° C., preferably 50 to 80 ° C., more preferably about 60 ° C. for 1 to 40 hours, preferably 10 to 30 hours, more preferably about 20 hours, if necessary using additives and solvents. To do.

Examples of 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) include the following.

(In the formula, v1 is an integer of 1 to 24, and u1, p1, q1, and p1 + q1 are the same as above.)

As the olefin introducing agent used for the preparation of the fluorooxyalkylene group-containing polymer represented by the formula (13), for example, preferably two or more (particularly two or Examples include those having a sulfonic acid ester residue represented by -S (= O) ₂ O- at the other terminal and 3) olefin sites.

The olefin introducing agent can be prepared by a known method.
The amount of the olefin introducing agent used is preferably 1 to 5 equivalents as a sulfonic acid ester residue with respect to 1 equivalent of the reactive end group (terminal hydroxyl group) of the fluorooxyalkylene group-containing polymer having hydroxyl groups at both ends of the molecular chain. Can be used in an amount of 1 to 3 equivalents, more preferably about 1.5 equivalents.

Examples of the base used for the preparation of the fluorooxyalkylene group-containing polymer represented by the formula (13) include amines and alkali metal bases. Specific examples of amines include triethylamine, Examples include diisopropylethylamine, pyridine, DBU, and imidazole. Among alkali metal bases, sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, alkyllithium, t-butoxypotassium, lithium diisopropylamide, lithium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, potassium bis And (trimethylsilyl) amide.
The amount of the base used is 1 to 20 equivalents, more preferably 5 to 15 equivalents, and even more preferably about 9 equivalents with respect to 1 equivalent of the reactive end group of the fluorooxyalkylene group-containing polymer having hydroxyl groups at both ends of the molecular chain. Can be used.

For the preparation of the fluorooxyalkylene group-containing polymer represented by the formula (13), tetrabutylammonium halide, alkali metal halide or the like may be used as an additive for improving reactivity or as a phase transfer catalyst. Specific examples of the additive include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydrogen sulfate, sodium iodide, potassium iodide, cesium iodide, crown ether and the like. . These additives improve the reactivity by catalytically exchanging halogens with the olefin introducing agent in the reaction system, and the crown ether coordinates with the metal to improve the reactivity.
The additive is used in an amount of 0.005 to 0.2 equivalent, more preferably 0.01 to 0.000, based on 1 equivalent of the reactive end group of the fluorooxyalkylene group-containing polymer having hydroxyl groups at both ends of the molecular chain. 15 equivalents, more preferably about 0.1 equivalents can be used.

A solvent may be used for the preparation of the fluorooxyalkylene group-containing polymer represented by the formula (13). Although it is not always necessary to use a solvent, examples of the solvent used include fluorine-containing aromatic hydrocarbon solvents such as 1,3-bis (trifluoromethyl) benzene and trifluoromethylbenzene, , 1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2- (trifluoromethyl) pentane and other hydrofluoroether (HFE) solvents (manufactured by 3M, trade name: Novec series), perfluoro solvents (made by 3M, trade name: Fluorinert series) composed of fully fluorinated compounds. Further, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, THF, or the like can be used as the organic solvent. Further, water may be used.
The amount of the solvent used is 10 to 300 parts by weight, preferably 30 to 150 parts by weight, more preferably about 50 parts by weight with respect to 100 parts by weight of the fluorooxyalkylene group-containing polymer having hydroxyl groups at both ends of the molecular chain. Can be used.

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

In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the above formula (1) and α being 2, the solvent used is preferably a fluorinated solvent, and the fluorinated solvent is 1,3-bis ( 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) pentane and other hydrofluoroether (HFE) solvents (trade name: Novec series, manufactured by 3M), composed of fully fluorinated compounds Perfluoro solvent (made by 3M, trade name: Florinato Siri ), And the like.
The solvent is used in an amount of 10 to 300 parts by weight, preferably 50 to 150 parts by weight, more preferably about 100 parts by weight, based on 100 parts by weight of the fluorooxyalkylene group-containing polymer having olefin moieties at both ends of the molecular chain. Can be used.

In addition, in the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) and α being 2, an organosilicon compound having a SiH group and a hydrolyzable end group in the molecule includes the following general formula: Compounds represented by (5) to (8) are preferred.

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

In the preparation of a fluoropolyether group-containing polymer-modified silane represented by the formula (1) and α is 2, a fluorooxyalkylene group-containing polymer having olefin sites at both ends of the molecular chain and SiH groups and hydro The amount of the organosilicon compound having a SiH group and a hydrolyzable end group in the molecule when reacting with the organosilicon compound having a decomposable end group is a fluorooxyalkylene group having an olefin moiety at both ends of the molecular chain. 1 to 3 equivalents, more preferably 1.5 to 2.5 equivalents, and still more preferably about 2 equivalents can be used per 1 equivalent of reactive end groups of the containing polymer.

In addition, in the preparation of a fluoropolyether group-containing polymer-modified silane represented by formula (1) and α is 2, organosilicon having no hydrolyzable end groups in the molecule and having two or more SiH groups As the compound, compounds represented by the following general formulas (9) to (11) are preferable.

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

In the preparation of a fluoropolyether group-containing polymer-modified silane represented by the formula (1) and α is 2, a fluorooxyalkylene group-containing polymer having an olefin moiety at both ends of the molecular chain and a hydrolyzable end in the molecule The amount of the organosilicon compound having no hydrolyzable end group in the molecule and having two or more SiH groups in the molecule when reacting with an organosilicon compound having two or more SiH groups without having a group is: It can be used in an amount of 7 to 30 equivalents, more preferably 10 to 20 equivalents, and even more preferably about 15 equivalents per 1 equivalent of the reactive end group of the fluorooxyalkylene group-containing polymer having olefin moieties at both ends of the molecular chain. .

In addition, in the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) where α is 2, the organosilicon compound having an olefin moiety and a hydrolyzable end group in the molecule includes the following general formula: The compound represented by (12) is preferred.

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

In the preparation of a fluoropolyether group-containing polymer-modified silane represented by the formula (1) and α is 2, a fluorooxyalkylene group-containing polymer having an olefin moiety at both ends of the molecular chain and a hydrolyzable end in the molecule An olefin moiety in the molecule when reacting a reaction product of an organosilicon compound having two or more SiH groups with no olefin group and an organosilicon compound having an olefin moiety and a hydrolyzable end group in the molecule; The amount of the organosilicon compound having a hydrolyzable end group is a fluorooxyalkylene group-containing polymer having an olefin moiety at both ends of the molecular chain and two SiH groups without hydrolyzable end groups in the molecule. 3 to 9 equivalents, more preferably 5 to 7 equivalents, and even more preferably 1 equivalent of the reactive end group of the reaction product with the organosilicon compound. Properly it can be used about 6 equivalents.

In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) and α is 2, the hydrosilylation reaction catalyst may be platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum chloride Examples include complexes of acids with olefins, aldehydes, vinyl siloxanes, acetylene alcohols, and the like, and platinum group metal catalysts such as tetrakis (triphenylphosphine) palladium and chlorotris (triphenylphosphine) rhodium. Preferred are platinum compounds such as vinylsiloxane coordination compounds.
The amount of the hydrosilylation catalyst used is a fluorooxyalkylene group-containing polymer having olefin moieties at both ends of the molecular chain, or this polymer and the molecule do not have hydrolyzable end groups and have at least two SiH groups. It is used in an amount of 0.1 to 100 ppm, more preferably 1 to 50 ppm in terms of transition metal (mass) with respect to the mass of the reaction product with the organosilicon compound.

Then, the target compound can be obtained by depressurizingly distilling a solvent and an unreacted substance.
For example, as a fluorooxyalkylene group-containing polymer having an olefin moiety at both ends of the molecular chain, a compound represented by the following formula

The present invention further provides a surface treatment agent containing the fluoropolyether group-containing polymer-modified silane. The surface treatment agent condenses a hydroxyl group of the fluoropolyether group-containing polymer-modified silane or a hydroxyl group obtained by partially hydrolyzing a terminal hydrolyzable group of the fluoropolyether group-containing polymer-modified silane in advance by a known method. It may contain a partial (hydrolysis) condensate obtained in this way.

As necessary, the surface treatment agent may be a hydrolysis-condensation catalyst such as an organic tin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organic titanium compound (tetran-butyl titanate, etc.), an organic acid (acetic acid, Methanesulfonic acid, fluorine-modified carboxylic acid, etc.) and inorganic acid (hydrochloric acid, sulfuric acid, etc.) may be added. Of 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 a catalytic amount, and is usually 0.01 to 5 parts by mass, particularly 0, relative to 100 parts by mass of the fluoropolyether group-containing polymer-modified silane and / or its partial (hydrolysis) condensate. .1 to 1 part by mass.

The surface treatment agent may contain a suitable solvent. Such solvents include fluorine-modified aliphatic hydrocarbon solvents (such as perfluoroheptane and perfluorooctane), fluorine-modified aromatic hydrocarbon solvents (such as 1,3-bis (trifluoromethyl) benzene), fluorine Modified ether solvents (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro (2-butyltetrahydrofuran), etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (Petroleum benzine, toluene, xylene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) can be exemplified. Among these, fluorine-modified solvents are desirable in terms of solubility, wettability, and the like, and in particular, 1,3-bis (trifluoromethyl) benzene, perfluoro (2-butyltetrahydrofuran), perfluorotrimethyl. Butylamine and ethyl perfluorobutyl ether are preferred.

Two or more of the above solvents may be mixed, and it is preferable to uniformly dissolve the fluoropolyether group-containing polymer-modified silane and its partial (hydrolyzed) condensate. In addition, the optimal concentration of the fluoropolyether group-containing polymer-modified silane to be dissolved in the solvent and its partial (hydrolyzed) condensate varies depending on the treatment method, and may be an amount that can be easily weighed. The amount is preferably 0.01 to 10 parts by weight, particularly 0.05 to 5 parts by weight, based on 100 parts by weight in total of the solvent and the fluoropolyether group-containing polymer-modified silane (and its part (hydrolyzed) condensate). In the case of vapor deposition treatment, 1 to 100 parts by mass, particularly 3 to 30 parts by mass, with respect to 100 parts by mass in total of the solvent and fluoropolyether group-containing polymer-modified silane (and its partial (hydrolyzed) condensate) Preferably there is.

The surface treatment agent of the present invention can be applied to a substrate by a known method such as brushing, dipping, spraying, or vapor deposition. The heating method during the vapor deposition process may be either a resistance heating method or an electron beam heating method, and is not particularly limited. The curing temperature varies depending on the curing method. For example, in the case of direct coating (brush coating, dipping, spraying, etc.), 25 to 200 ° C., particularly 25 to 80 ° C., 30 minutes to 36 hours, especially 1 It is preferably set to ˜24 hours. Further, when it is applied by vapor deposition, it is preferably in the range of 20 to 200 ° C. Moreover, you may make it harden | cure under humidification. The thickness of the cured coating is appropriately selected depending on the type of substrate, but is usually 0.1 to 100 nm, particularly 1 to 20 nm. Further, for example, in spray coating, if the coating is diluted with a fluorine-based solvent to which moisture has been added in advance to generate hydrolysis, that is, Si—OH, and then spray coating is performed, curing after coating is fast.

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

Articles to be treated with the surface treatment agent of the present invention include car navigation, mobile phones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game equipment, spectacle lenses, camera lenses, lens filters, sunglasses, Optical articles such as medical devices such as gastric cameras, copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, and antireflection films. Since the surface treatment agent of the present invention can prevent fingerprints and sebum from adhering to the article and can further provide scratch resistance, it is particularly useful as a water / oil repellent layer for touch panel displays, antireflection films and the like. is there.

Further, the surface treatment agent of the present invention is an antifouling coating for sanitary products such as bathtubs and washstands, window glass or tempered glass for automobiles, trains, airplanes, etc., antifouling coating for headlamp covers, etc. Water- and oil-repellent coating, anti-stain coating for kitchen building materials, anti-fouling and anti-fouling coating for phone boxes, anti-fingerprint coating for artworks, anti-fingerprint coating for compact discs, DVDs, etc. It is also useful as a lubricity improver for molds such as mold release agents or paint additives, resin modifiers, inorganic filler fluidity modifiers or dispersibility modifiers, tapes and films.

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated in detail, this invention is not limited by the following Example.

[Example 1]
In the reaction vessel, the following formula (A)

100 g (2.9 × 10 ⁻² mol) of the compound represented by the formula (B)

37 g (4.3 × 10 ⁻² mol) represented by the following formula was mixed with 0.89 g (2.6 × 10 ⁻³ mol) of tetrabutylammonium hydrogen sulfate. Subsequently, 35 g (2.6 × 10 ⁻¹ mol) of a 30% by mass aqueous sodium hydroxide solution was added, followed by heating at 60 ° C. for 20 hours. After completion of heating, the mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was added dropwise. The lower fluorine compound layer was recovered by a liquid separation operation and then washed with acetone. The fluorine compound layer as the lower layer after washing was collected again, and the remaining solvent was distilled off under reduced pressure. By performing the above operation again, the following formula (C)

103 g of a fluoropolyether group-containing polymer represented by the formula:
In addition, the analysis result of the molecular structure by NMR of the fluoropolyether group-containing polymer represented by the formula (C) is as follows.

¹ H-NMR
δ 3.4-3.5 (C—C H ₂ —O—CH ₂ CH═CH ₂ ) 6H
δ3.6-3.7 (—CF ₂ —CH ₂ —O—C H ₂ —C) 2H
δ3.7-3.8 (—CF ₂ —C H ₂ —O—C H ₂ —C) 2H
δ3.8-3.9 (C—CH ₂ —O—C H ₂ CH═CH ₂ ) 6H
δ 5.0-5.2 (C—CH ₂ —O—CH ₂ CH═C H ₂ ) 6H
_{δ5.7-5.9 (C-CH 2 -O-} CH 2 C H = CH 2) 3H

In the reaction vessel, the following formula (C) obtained above

50 g (1.5 × 10 ⁻² mol, ie, terminal allyl ether group; corresponding to 4.5 × 10 ⁻² mol), 1,3-bis (trifluoromethyl) benzene 50 g, trimethoxy 11 g (9.0 × 10 ⁻² mol) of silane and 5.0 × 10 ⁻² g of toluene solution of chloroplatinic acid / vinylsiloxane complex were mixed (containing 1.5 × 10 ⁻⁷ mol as a simple substance of Pt). Aged at 80 ° C. for 5 hours. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain 55 g of a liquid product.

It was confirmed by NMR that the obtained compound had a structure represented by the following formula (D).

¹ H-NMR
_{_{δ0.4-0.6 (-CH 2 CH 2 C H}} 2 -Si) 6H
_{_{δ1.4-1.6 (-CH 2 C H 2 CH}} 2 -Si) 6H
δ3.1-3.7 (—Si (OC H ₃ ) ₃ , —C H ₂ CH ₂ CH ₂ —Si, C—C H ₂ —O—CH ₂ CH ₂ CH ₂ —Si, —CF ₂ —CH ₂ —O—C H ₂ —C, —CF ₂ —C H ₂ —O—CH ₂ —C) 43H

[Example 2]
In the reaction vessel, the following formula (A)

100 g (2.9 × 10 ⁻² mol) of the compound represented by the formula (E)

Embedded image 26 g (4.3 × 10 ⁻¹ mol) and tetrabutylammonium hydrogen sulfate 0.89 g (2.6 × 10 ⁻³ mol) were mixed. Subsequently, 35 g (2.6 × 10 ⁻¹ mol) of a 30% by mass aqueous sodium hydroxide solution was added, followed by heating at 60 ° C. for 20 hours. After completion of heating, the mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was added dropwise. The lower fluorine compound layer was recovered by a liquid separation operation and then washed with acetone. The fluorine compound layer as the lower layer after washing was collected again, and the remaining solvent was distilled off under reduced pressure. By performing the above operation again, the following formula (F)

101 g of a fluoropolyether group-containing polymer represented by the formula:
In addition, the analysis result of the molecular structure by NMR of the fluoropolyether group-containing polymer represented by the formula (F) is as follows.

¹ H-NMR
_{_{δ0.7-0.9 (-CH 2 C H 3)}} 3H
δ1.3-1.5 (-C H ₂ CH ₃ ) 2H
δ 3.2-3.2 (C—C H ₂ —O—CH ₂ CH═CH ₂ ) 4H
δ 3.4-3.5 (—CF ₂ —CH ₂ —O—C H ₂ —C) 2H
δ3.6-3.7 (—CF ₂ —C H ₂ —O—C H ₂ —C) 2H
δ3.8-3.9 (C—CH ₂ —O—C H ₂ CH═CH ₂ ) 4H
δ4.9-5.2 (C—CH ₂ —O—CH ₂ CH═C H ₂ ) 4H
_{δ5.7-5.8 (C-CH 2 -O-} CH 2 C H = CH 2) 2H

In the reaction vessel, the following formula (F) obtained above

50 g (1.5 × 10 ⁻² mol, ie, terminal allyl ether group; corresponding to 3.0 × 10 ⁻² mol), 1,3-bis (trifluoromethyl) benzene 50 g, trimethoxy 7.3 g (6.0 × 10 ⁻² mol) of silane and 5.0 × 10 ⁻² g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 1.5 × 10 ⁻⁷ mol as Pt alone) Mixed and aged at 80 ° C. for 5 hours. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain 52 g of a liquid product.

It was confirmed by NMR that the obtained compound had a structure represented by the following formula (G).

¹ H-NMR
_{_{δ0.4-0.6 (-CH 2 CH 2 C H}} 2 -Si) 4H
_{_{δ0.6-0.8 (-CH 2 C H 3)}} 3H
δ1.2-1.4 (-C H ₂ CH ₃ ) 2H
_{_{δ1.5-1.7 (-CH 2 C H 2 CH}} 2 -Si) 4H
δ3.1-3.7 (—Si (OC H ₃ ) ₃ , —C H ₂ CH ₂ CH ₂ —Si, C—C H ₂ —O—CH ₂ CH ₂ CH ₂ —Si, —CF ₂ —CH ₂ —O—C H ₂ —C, —CF ₂ —C H ₂ —O—CH ₂ —C) 30H

[Example 3]
In the reaction vessel, the following formula (H)

100 g of the compound represented by formula (2.7 × 10 ⁻² mol, ie, terminal hydroxy group; corresponding to 5.4 × 10 ⁻² mol), the following formula (B)

69 g (8.1 × 10 ⁻² mol) and 1.7 g (4.9 × 10 ⁻³ mol) of tetrabutylammonium hydrogen sulfate were mixed. Subsequently, 65 g (4.9 × 10 ⁻¹ mol) of a 30% by mass aqueous sodium hydroxide solution was added, followed by heating at 60 ° C. for 20 hours. After completion of heating, the mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was added dropwise. The lower fluorine compound layer was recovered by a liquid separation operation and then washed with acetone. The fluorine compound layer as the lower layer after washing was collected again, and the remaining solvent was distilled off under reduced pressure. By performing the above operation again, the following formula (I)

107 g of a fluoropolyether group-containing polymer represented by the formula:
In addition, the analysis result of the molecular structure by NMR of the fluoropolyether group-containing polymer represented by the formula (I) is as follows.

¹ H-NMR
δ 3.4-3.5 (C—C H ₂ —O—CH ₂ CH═CH ₂ ) 12H
δ3.6-3.7 (—CF ₂ —CH ₂ —O—C H ₂ —C) 4H
δ3.7-3.8 (—CF ₂ —C H ₂ —O—C H ₂ —C) 4H
δ3.8-3.9 (C—CH ₂ —O—C H ₂ CH═CH ₂ ) 12H
_{δ4.9-5.1 (C-CH 2 -O-} CH 2 CH = C H 2) 12H
_{δ5.7-5.9 (C-CH 2 -O-} CH 2 C H = CH 2) 6H

In a reaction vessel, the following formula (I) obtained above

50 g (1.33 × 10 ⁻² mol, ie, terminal allyl ether group; corresponding to 8.0 × 10 ⁻² mol), 1,3-bis (trifluoromethyl) benzene 50 g, trimethoxy Silane 20 g (1.6 × 10 ⁻¹ mol) and chloroplatinic acid / vinylsiloxane complex toluene solution 5.0 × 10 ⁻² g (containing 1.5 × 10 ⁻⁷ mol as Pt alone) were mixed. Aged at 80 ° C. for 5 hours. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain 60 g of a liquid product.

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

¹ H-NMR
_{_{δ0.4-0.7 (-CH 2 CH 2 C H}} 2 -Si) 12H
_{_{δ1.4-1.7 (-CH 2 C H 2 CH}} 2 -Si) 12H
δ3.1-3.8 (—Si (OC H ₃ ) ₃ , —C H ₂ CH ₂ CH ₂ —Si, C—C H ₂ —O—CH ₂ CH ₂ CH ₂ —Si, —CF ₂ —CH ₂ —O—C H ₂ —C, —CF ₂ —C H ₂ —O—CH ₂ —C) 86H

[Comparative Example 1]
As Comparative Example 1, the following polymer was used.

[Comparative Example 2]
As Comparative Example 2, the following polymer was used.

Preparation of surface treatment agent and formation of cured film Of the fluoropolyether group-containing polymer-modified silanes obtained in Examples 1 to 3, the fluoropolyether group-containing polymer-modified silanes obtained in Examples 1 and 2 were used. The surface treatment agent was subjected to the following evaluation. That is, the fluoropolyether group-containing polymer-modified silane obtained in Examples 1 and 2 and the polymers of Comparative Examples 1 and 2 were added to Novec 7200 (3M, ethyl perfluorobutyl ether) to a concentration of 20% by mass. A surface treatment agent was prepared by dissolution.

[Thin film coating]
6 mg of each surface treatment agent was vacuum-deposited on glass (Gorilla manufactured by Corning) with a SiO ₂ treatment of 10 nm on the outermost surface (treatment conditions: pressure: 2.0 × 10 ⁻² Pa, heating temperature: 700 ° C.) A cured film having a thickness of 7 nm was formed by curing for 12 hours in an atmosphere of 25 ° C. and a humidity of 40%.

[Thick film coating]
10 mg of each surface treatment agent was vacuum-deposited on a glass (Gorilla made by Corning) with 10 nm of SiO ₂ treated on the outermost surface (treatment conditions: pressure: 2.0 × 10 ⁻² Pa, heating temperature: 700 ° C.) A cured film having a film thickness of 14 nm was formed by curing for 12 hours in an atmosphere of 25 ° C. and a humidity of 40%.

Evaluation of water repellency [ Evaluation of initial water repellency]
Using the contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.), the contact angle (water repellency) of the cured coating to water was measured for the glass on which the cured coating was formed by thin film coating as described above (droplet: 2 μl). , Temperature: 25 ° C., humidity: 40%). The results (initial water contact angle) are shown in Table 1.
In the initial stage, both the examples and the comparative examples showed good water repellency.

[Evaluation of wear resistance]
About the glass (for abrasion resistance evaluation) which formed the hardened film by thin film coating above, the water of the hardened film after rubbing 10,000 times on the following conditions using a rubbing tester (made by Shinto Kagaku). The contact angle (water repellency) with respect to was measured in the same manner as described above to evaluate wear resistance. The test environmental conditions are 25 ° C. and humidity 40%. The results (water contact angle after wear) are shown in Table 1.
Steel wool wear resistance <br/> Steel wool: BONSTAR # 0000 (made by Nippon Steel Wool Co., Ltd.)
Contact area: 10mmφ
Travel distance (one way) 30mm
Movement speed 1,800 mm / min Load: 1 kg / cm ²
Since the compounds of Examples 1 and 2 have a plurality of ether linking groups in the molecule, the adhesion to the base material is improved, so the cured film of the surface treatment agent using the compounds of Examples 1 and 2 is a comparative example. Compared with, the contact angle was 100 ° or more and good wear resistance was exhibited.

[Evaluation of haze value]
Using the haze meter (NDH-5000) (manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS K 7136: 2000 for the glass (for haze value evaluation) on which a hard coating is formed by thin film coating and thick film coating as described above. The haze value was measured. The results (haze values) are shown in Tables 1 and 2. Haze is visually confirmed from 0.3 or more. At the time of thin film (7 nm) coating, the haze value was as low as 0.3 or less in both Examples and Comparative Examples. On the other hand, when the thick film (14 nm) was applied, the compounds of Examples 1 and 2 had a plurality of ether linking groups which are polar groups in the molecule, thereby improving the wettability with the substrate. The cured film of the surface treatment agent using the compounds No. 1 and No. 2 was confirmed to have an improved visibility with a haze value of 0.3 or less as compared with the comparative example.

Claims

The following general formula (1)

(Wherein Rf is a monovalent or divalent fluorooxyalkylene group-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, a silylene group and / or a divalent to hexavalent hydrocarbon group optionally having a siloxane bond, R is independently an alkyl group having 1 to 4 carbon atoms, and X is independently a hydroxyl group or hydrolyzed 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 carbon atoms, β Is an integer from 1 to 3, and α is 1 or 2.)
A fluoropolyether group-containing polymer-modified silane represented by:
2. The fluoropolyester according to claim 1, wherein α in the formula (1) is 1, and the Rf group is a monovalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (2). Ether group-containing polymer-modified silane.

(Wherein p, q, r and s are each an integer of 0 to 200 and p + q + r + s = an integer of 3 to 200, and each repeating unit may be linear or branched, May be bonded randomly, d is an integer of 1 to 3, and the unit (—C d F 2d —) may be linear or branched.)
2. The fluoropolyester according to claim 1, wherein α in the formula (1) is 2, and the Rf group is a divalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (3). Ether group-containing polymer-modified silane.

(Wherein p, q, r and s are each an integer of 0 to 200 and p + q + r + s = an integer of 3 to 200, and each repeating unit may be linear or branched, May be bonded randomly, d is an integer of 1 to 3, and each of the units (—C d F 2d —) may be independently linear or branched.)
In the above formula (1), Y represents an alkylene group having 3 to 10 carbon atoms, an alkylene group containing an arylene group having 6 to 8 carbon atoms, an alkylene group having a silicon atom, a silylene group, a silalkylene structure, or a silarylene structure. A divalent group bonded via each other and a linear or branched or cyclic divalent to tetravalent organopolysiloxane residue having 2 to 10 silicon atoms or a silicon atom having 3 to 10 silicon atoms, or silicon 4. The at least one group selected from the group consisting of divalent to tetravalent groups in which an alkylene group having 2 to 10 carbon atoms is bonded to an atom bond. Fluoropolyether group-containing polymer-modified silane.
In the formula (1), Q is
—CH 2 OCH 2 —
The fluoropolyether group-containing polymer-modified silane according to any one of claims 1 to 4, wherein
In the formula (1), each X is a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms. The fluoropolyether group-containing polymer-modified silane according to any one of claims 1 to 5, which is at least one selected from the group consisting of a halogen group.
The fluoropolyether group-containing polymer-modified silane according to any one of claims 1 to 6, wherein the polymer-modified silane represented by the formula (1) is represented by any one of the following formulas.

(Wherein 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)
A surface treating agent comprising the fluoropolyether group-containing polymer-modified silane and / or a partial (hydrolyzed) condensate thereof according to any one of claims 1 to 7.
An article having a cured coating of the surface treatment agent according to claim 8 on the surface.