JP6642589B2 - Fluoropolyether group-containing polymer-modified silane, surface treatment agent and article - Google Patents

Description

  The present invention relates to a fluoropolyether group-containing polymer-modified silane, and more particularly, to a fluoropolyether group-containing polymer-modified silane that forms a film having excellent slipperiness, a surface treatment agent containing the silane, and the surface treatment agent (Ie, having a cured film of the surface treatment agent on the surface).

  2. Description of the Related Art In recent years, the use of touch panels on screens, including displays of mobile phones, has been accelerating. However, there is a problem that the screen of the touch panel is exposed, the finger and cheek often come into direct contact with each other, and dirt such as sebum easily adheres. Therefore, the demand for technologies that make it difficult for fingerprints to be attached to the display surface to improve the appearance and visibility and the technology that makes it easy to remove dirt are increasing year by year, and the development of materials that can meet these demands has been increasing. Is desired. In particular, it is desired to provide a water-repellent and oil-repellent layer because fingerprint stains easily adhere to the surface of the touch panel display. However, the conventional water- and oil-repellent layer has high water- and oil-repellency and is excellent in wiping off dirt, but has a problem that the antifouling performance is deteriorated during use.

  In general, a fluoropolyether group-containing compound has very low surface free energy, and thus has water and oil repellency, chemical resistance, lubricity, mold release, antifouling properties, and the like. Utilizing its properties, it is widely used industrially as a water / oil repellent / antifouling agent for paper and textiles, lubricant for magnetic recording media, oilproofing agent for precision equipment, release agent, cosmetics, protective film, etc. ing. However, its properties mean that it is non-adhesive and non-adhesive to other substrates at the same time, and even though it can be applied to the substrate surface, it was difficult to adhere the coating. .

  On the other hand, a silane coupling agent is well known as a substance that bonds an organic compound to the surface of a substrate such as glass or cloth, 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 due to moisture in the air or the like to form a film. The coating is a durable, strong coating by chemically and physically bonding the hydrolyzable silyl group to the surface of glass, metal, or the like.

  Therefore, by using a fluoropolyether group-containing polymer-modified silane in which a hydrolyzable silyl group is introduced into a fluoropolyether group-containing compound, the compound easily adheres to the substrate surface, and the substrate surface has water- and oil-repellency, resistance to water and oil. Compositions capable of forming a film having chemical properties, lubricity, release properties, antifouling properties and the like are disclosed (Patent Documents 1 to 5: JP-T-2008-534696, JP-T-2008-535557). JP-A-2012-07272, JP-A-2012-157856, JP-A-2013-136833).

  A lens or an antireflection film surface-treated with a composition containing a fluoropolyether group-containing polymer-modified silane in which a hydrolyzable silyl group is introduced into the fluoropolyether group-containing compound is excellent in abrasion resistance and releasability. , Slipperiness is not enough.

JP 2008-534696 A Japanese Patent Publication No. 2008-535557 JP-A-2012-07272 JP 2012-157856 A JP 2013-136833 A JP 2015-199906 A

（式中、Ｒｆは１価のフルオロオキシアルキル基又は２価のフルオロオキシアルキレン基含有ポリマー残基であり、Ｙはシロキサン結合及びシリレン基を有してもよい２〜６価の炭化水素基であり、Ｒは独立に炭素数１〜４のアルキル基又はフェニル基であり、Ｘは独立に加水分解性基であり、ｎは１〜３の整数であり、ｍは１〜５の整数であり、αは１又は２である。）
で表されるフルオロポリエーテル基含有ポリマー変性シランを提案しており（特許文献６：特開２０１５−１９９９０６号公報）、該フルオロポリエーテル基含有ポリマー変性シラン及び／又はその部分加水分解縮合物を含有する表面処理剤から形成される被膜は、高い撥水撥油性、耐摩耗性を示す。しかし、滑り性は依然改善されていない。The present inventors, as a fluoropolyether group-containing compound excellent in abrasion resistance, the following formula

(Wherein, Rf is a monovalent fluorooxyalkyl group or a divalent fluorooxyalkylene group-containing polymer residue, and Y is a divalent to hexavalent hydrocarbon group which may have a siloxane bond and a silylene group. R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydrolyzable group, n is an integer of 1 to 3 and m is an integer of 1 to 5 , Α is 1 or 2.)
(Patent Document 6: JP-A-2015-199906), and the fluoropolyether group-containing polymer-modified silane and / or a partially hydrolyzed condensate thereof is proposed. The coating formed from the contained surface treatment agent exhibits high water and oil repellency and abrasion resistance. However, the slip properties have not been improved.

  The present invention has been made in view of the above circumstances, and a fluoropolyether group-containing polymer-modified silane capable of forming a water- and oil-repellent layer excellent in slipperiness, a surface treatment agent containing the silane, and the surface treatment It is an object of the present invention to provide an article surface-treated with an agent (ie, having a cured film of the surface treatment agent on its surface).

  The present inventors have conducted intensive studies to solve the above-mentioned object, and as a result, in the fluoropolyether group-containing polymer-modified silane, a hydroxyl group represented by the following general formula (1) is replaced with a -QR 'group shown below. The inventors have found that the protected fluoropolyether group-containing polymer-modified silane can form a water- and oil-repellent layer having excellent slipperiness, weather resistance, and excellent storage stability, and have accomplished the present invention.

（式中、Ｒｆは、ＣＦ₃Ｏ-（ＣＦ₂Ｏ）_p1-（Ｃ₂Ｆ₄Ｏ）_p2-Ｃ_tＦ_2t-（式中、ｐ１は５〜１００の整数、ｑ１は５〜１００の整数で、ｐ１＋ｑ１は１０〜１０５の整数であり、ｔは１〜３の整数である。各繰り返し単位はランダムに結合されていてよい。）で表される１価フルオロオキシアルキレン基含有ポリマー残基又は-Ｃ_tＦ_2tＯ-（ＣＦ₂Ｏ）_p1-（Ｃ₂Ｆ₄Ｏ）_p2-Ｃ_tＦ_2t-（式中、ｐ１は５〜１００の整数、ｑ１は５〜１００の整数で、ｐ１＋ｑ１は１０〜１０５の整数であり、ｔは１〜３の整数である。各繰り返し単位はランダムに結合されていてよい。）で表される２価のフルオロオキシアルキレン基含有ポリマー残基であり、Ｙはシロキサン結合及び／又はシリレン基を有してもよい２〜６価の炭化水素基であり、Ｒは炭素数１〜４のアルキル基又はフェニル基であり、Ｘは水酸基又は加水分解性基であり、Ｑはシロキサン結合及び／又はシリレン基を有してもよい２価の有機基であり、Ｒ’は１価のフルオロアルキル基、１価のフルオロオキシアルキレン基含有ポリマー残基、炭素数１〜４のアルキル基又はフェニル基であり、ｎは１〜３の整数であり、ｍは１〜５の整数であり、αは１又は２である。）
で表されるフルオロポリエーテル基含有ポリマー変性シラン。
〔２〕
前記式（１）のＲｆ基において、ｔは１又は２である〔１〕に記載のフルオロポリエーテル基含有ポリマー変性シラン。
〔３〕
前記式（１）のＲｆ基において、ｔ＝１である〔１〕に記載のフルオロポリエーテル基含有ポリマー変性シラン。
〔４〕
前記式（１）において、Ｙが、炭素数３〜１０のアルキレン基、フェニレン基を含む炭素数８〜１６のアルキレン基、炭素数２〜１０のアルキレン基相互がシルアルキレン構造又はシルアリーレン構造を介して結合している２価の基、ケイ素原子数２〜１０個の直鎖状オルガノポリシロキサン残基の結合手に炭素数２〜１０のアルキレン基が結合している２〜４価の基、及びケイ素原子数３〜１０個の分岐状もしくは環状のオルガノポリシロキサン残基の結合手に炭素数２〜１０のアルキレン基が結合している２〜４価の基からなる群より選ばれる少なくとも１種の基である〔１〕〜〔３〕のいずれかに記載のフルオロポリエーテル基含有ポリマー変性シラン。
〔５〕
前記式（１）において、Ｘが、それぞれ独立に、水酸基、炭素数１〜１０のアルコキシ基、炭素数２〜１０のアルコキシ置換アルコキシ基、炭素数２〜１０のアシロキシ基、炭素数２〜１０のアルケニルオキシ基及びハロゲン原子からなる群より選ばれるものである〔１〕〜〔４〕のいずれかに記載のフルオロポリエーテル基含有ポリマー変性シラン。
〔６〕
前記式（１）において、Ｑが下記式（４）で表される２価の有機基であることを特徴とする〔１〕〜〔５〕のいずれかに記載のフルオロポリエーテル基含有ポリマー変性シラン。

（式中、Ｒ’’はケトン、エステル、アミド、エーテル、スルフィド、アミン、フェニレンのいずれかを有していてもよい炭素数１〜１０のアルキレン基、又はカルボニル基であり、Ｗはケイ素原子数２〜４０個の直鎖状の２価のオルガノ（ポリ）シロキサン残基、炭素数１〜４のアルキレン基を介して結合しているケイ素原子数３〜４０個のシロキサン結合を有してもよい直鎖状のシルアルキレン基、及び炭素数６〜１０のアリーレン基を介して結合しているケイ素原子数３〜４０個のシロキサン結合を有してもよい直鎖状のシルアリーレン基から選ばれる２価の基であり、オルガノ（ポリ）シロキサン残基、シルアルキレン基、シルアリーレン基はそれぞれ単一でも混合されていてもよく、βは０又は１であり、γは０又は１であり、β＋γは１又は２である。）
〔７〕
式（１）で表されるポリマー変性シランが、下記式で表されるものである〔１〕〜〔６〕のいずれかに記載のフルオロポリエーテル基含有ポリマー変性シラン。

（式中、ｐ１は５〜１００の整数、ｑ１は５〜１００の整数で、ｐ１＋ｑ１は１０〜１０５の整数である。）
〔８〕
〔１〕〜〔７〕のいずれかに記載のフルオロポリエーテル基含有ポリマー変性シランを含む表面処理剤。
〔９〕
〔８〕に記載の表面処理剤の硬化被膜を表面に有する物品。 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, CF 3 O- (CF 2 O} ) p1 - (C 2 F 4 O) p2 -C t F 2t - (In the formula, p1 5-100 integer, q1 is 5-100 In the formula, p1 + q1 is an integer of 10 to 105, and t is an integer of 1 to 3. Each repeating unit may be randomly bonded.) or _{-C t F 2t O- (CF 2} O) p1 - (C 2 F 4 O) p2 -C t F 2t - ( wherein, p1 is an integer of 5 to 100, q1 is an integer of 5 to 100, p1 + q1 is an integer of 10 to 105, and t is an integer of 1 to 3. Each repeating unit may be randomly bonded.) is a divalent fluorooxyalkylene group-containing polymer residue represented by the following formula: , Y is a divalent to hexavalent hydrocarbon group optionally having a siloxane bond and / or a silylene group, and R is An alkyl group or a phenyl group having 1 to 4 carbon atoms, X is a hydroxyl group or a hydrolyzable group, Q is a divalent organic group optionally having a siloxane bond and / or a silylene group, and R ′ Is a monovalent fluoroalkyl group, a monovalent fluorooxyalkylene group-containing polymer residue, an alkyl group having 1 to 4 carbon atoms or a phenyl group, n is an integer of 1 to 3, and m is 1 to 5 Is an integer, and α is 1 or 2.)
A fluoropolyether group-containing polymer-modified silane represented by the formula:
[2]
The fluoropolyether group-containing polymer-modified silane according to [1], wherein t is 1 or 2 in the Rf group of the formula (1).
[3]
The fluoropolyether group-containing polymer-modified silane according to [1], wherein t = 1 in the Rf group of the formula (1).
[4]
In the above formula (1), Y is an alkylene group having 3 to 10 carbon atoms, an alkylene group having 8 to 16 carbon atoms including a phenylene group, and an alkylene group having 2 to 10 carbon atoms is a silalkylene structure or a silarylene structure. Divalent group, a divalent group having 2 to 10 silicon atoms, and a divalent group having 2 to 10 carbon atoms bonded to a bond of a linear organopolysiloxane residue having 2 to 10 silicon atoms And at least one selected from the group consisting of divalent to tetravalent groups in which an alkylene group having 2 to 10 carbon atoms is bonded to a bond of a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms. The fluoropolyether group-containing polymer-modified silane according to any one of [1] to [3], which is one type of group.
[5]
In the above formula (1), X is each independently a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxy-substituted alkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, and 2 to 10 carbon atoms. The fluoropolyether group-containing polymer-modified silane according to any one of [1] to [4], which is selected from the group consisting of an alkenyloxy group and a halogen atom.
[6]
In the formula (1), Q is a divalent organic group represented by the following formula (4), wherein the fluoropolyether group-containing polymer is modified according to any one of [1] to [5]. Silane.

(Wherein, R ″ is an alkylene group having 1 to 10 carbon atoms which may have any of ketone, ester, amide, ether, sulfide, amine and phenylene, or carbonyl group, and W is a silicon atom A linear divalent organo (poly) siloxane residue having 2 to 40 carbon atoms, having a siloxane bond having 3 to 40 silicon atoms bonded through an alkylene group having 1 to 4 carbon atoms; it may also be linear silalkylene group, and silarylene group may linear, which has a bonded silicon atoms that are 3-40 amino siloxane bonds and through an arylene group having 6 to 10 carbon atoms Wherein the organo (poly) siloxane residue, the silalkylene group, and the silarylene group may each be single or mixed, β is 0 or 1, and γ is 0 or 1. And β + γ is 1 or 2.)
[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 the following formula.

(In the formula, 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 according to any one of [1] to [7].
[9]
An article having on its surface a cured film of the surface treatment agent according to [8].

  The surface treating agent of the present invention containing a fluoropolyether group-containing polymer-modified silane in which a hydroxyl group bonded to a carbon atom is sealed with the -QR 'group forms a water- and oil-repellent layer having excellent slipperiness. Can be.

（式中、Ｒｆは１価又は２価のフルオロオキシアルキレン基含有ポリマー残基であり、Ｙはシロキサン結合及び／又はシリレン基を有してもよい２〜６価の炭化水素基であり、Ｒは炭素数１〜４のアルキル基又はフェニル基であり、Ｘは水酸基又は加水分解性基であり、Ｑはシロキサン結合及び／又はシリレン基を有してもよい２価の有機基であり、Ｒ’は１価のフルオロアルキル基、１価のフルオロオキシアルキレン基含有ポリマー残基、炭素数１〜４のアルキル基又はフェニル基であり、ｎは１〜３の整数であり、ｍは１〜５の整数であり、αは１又は２である。）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, Y is a divalent to hexavalent hydrocarbon group optionally having a siloxane bond and / or a silylene group, Is an alkyl group or a phenyl group having 1 to 4 carbon atoms, X is a hydroxyl group or a hydrolyzable group, Q is a divalent organic group optionally having a siloxane bond and / or a silylene group, 'Is a monovalent fluoroalkyl group, a monovalent fluorooxyalkylene group-containing polymer residue, an alkyl group having 1 to 4 carbon atoms or a phenyl group, n is an integer of 1 to 3, and m is 1 to 5 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) and a hydrolyzable silyl group such as an alkoxysilyl group or a hydroxyl group-containing silyl group (—Si (R) _3-n (X) _n ) has a structure in which a siloxane bond and / or a divalent to hexavalent hydrocarbon chain (Y) which may have a silylene group is bonded via a carbon atom, Further, a divalent organic group (Q) which may have a siloxane bond and / or a silylene group as a linking group to a hydroxyl group bonded to a carbon atom in the polymer as an intermediate, preferably a ketone, an ester, an amide, An alkylene group or carbonyl group (R ″) having 1 to 10 carbon atoms which may have an ether, sulfide, amine or phenylene, or an organopolysiloxane residue or silalkylene A monovalent fluoroalkyl group, a monovalent fluorooxyalkylene group-containing polymer residue, an alkyl group having 1 to 4 carbon atoms or a phenyl group (R ′) via a silyl group or a silarylene group (W). Thereby, a water-repellent and oil-repellent layer having excellent slipperiness is formed.

（式中、ｐ、ｑ、ｒ、ｓはそれぞれ０〜２００の整数で、ｐ＋ｑ＋ｒ＋ｓ＝３〜２００の整数であり、ｔは１〜３の整数であり、各繰り返し単位は直鎖状でも分岐状であってもよく、各繰り返し単位同士はランダムに結合されていてよい。）In the above formula (1), when α is 1, Rf is a monovalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (2) (hereinafter sometimes referred to as fluorooxyalkyl group). Is preferred.

(Where p, q, r, and s are each an integer of 0 to 200, p + q + r + s is an integer of 3 to 200, t is an integer of 1 to 3, and each repeating unit is linear or branched. And each repeating unit may be randomly bonded.)

（式中、ｐ、ｑ、ｒ、ｓはそれぞれ０〜２００の整数で、ｐ＋ｑ＋ｒ＋ｓ＝３〜２００の整数であり、ｔは１〜３の整数であり、各繰り返し単位は直鎖状でも分岐状であってもよく、各繰り返し単位同士はランダムに結合されていてよい。）In the above formula (1), when α is 2, Rf is a divalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (3) (hereinafter sometimes referred to as fluorooxyalkylene group). Is preferred.

(Where p, q, r, and s are each an integer of 0 to 200, p + q + r + s is an integer of 3 to 200, t is an integer of 1 to 3, and each repeating unit is linear or branched. And each repeating unit may be randomly bonded.)

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 100, and each repeating unit may be linear or branched. May be randomly linked. More preferably, p + q is an integer of 10 to 105, particularly an integer of 15 to 60, and r = s = 0. When p + q + r + s is smaller than the above upper limit, adhesiveness and curability are good, and when p + q + r + s is larger than the above lower limit, the characteristics of the fluoropolyether group can be sufficiently exhibited.
Further, t is an integer of 1 to 3, preferably 1 or 2, and C _t F _2t may be linear or branched.

（式中、ｐ’、ｑ’、ｒ’、ｓ’はそれぞれ１以上の整数であり、その上限は上記ｐ、ｑ、ｒ、ｓの上限と同じである。ｕは１〜２４の整数、ｖは１〜２４の整数で、ｕ＋ｖ＝ｒを満足する数である。各繰り返し単位はランダムに結合されていてよい。）Specific examples of Rf (mono- or divalent fluorooxyalkylene group-containing polymer residue) include the following.

(In the formula, p ′, q ′, r ′, and s ′ are each an integer of 1 or more, and the upper limit is the same as the above upper limit of p, q, r, and s. U is an integer of 1 to 24; v is an integer of 1 to 24 and is a number that satisfies u + v = r. Each repeating unit may be randomly linked.)

In the above formula (1), Y may have a siloxane bond (such as a (di) organosiloxane unit) and / or a silylene group (a diorganosilylene group). It is preferably a divalent hydrocarbon group, and a coating film having excellent weather resistance and abrasion resistance can be provided by not including a linking group having low binding energy (such as an ether bond) in the molecule.
Specific examples of Y include carbon atoms such as an alkylene group having 3 to 10 carbon atoms such as a propylene group (trimethylene group and methylethylene group), a butylene group (tetramethylene group and methylpropylene group), and a hexamethylene group. An alkylene group containing an arylene group having the number of 6 to 8 (for example, an alkylene / arylene group having 8 to 16 carbon atoms), and an alkylene group having 2 to 10 carbon atoms having a silalkylene structure (both ends of the alkylene group are diorganosilylenes) A divalent group bonded via a group blocked by a group) or a silarylene structure (a structure in which both ends of an arylene group are blocked by a diorganosilylene group), preferably having 2 to 10 silicon atoms, preferably A divalent to hexavalent, preferably divalent to tetravalent group in which an alkylene group is bonded to a bond of 2 to 5 linear organopolysiloxane residues; A divalent to hexavalent, preferably divalent to tetravalent group in which an alkylene group is bonded to a bond of a branched or cyclic organopolysiloxane residue having 3 to 10, preferably 3 to 5 element atoms More preferably, an alkylene group having 3 to 10 carbon atoms, an alkylene group having 8 to 16 carbon atoms including a phenylene group, and an alkylene group having 2 to 10 carbon atoms are bonded to each other via a silalkylene structure or a silarylene structure. A divalent group having 2 to 10 silicon atoms, preferably 2 to 5 alkylene groups having 2 to 10 carbon atoms bonded to a bond of a linear organopolysiloxane residue having 2 to 2 carbon atoms. A tetravalent group, or an alkylene group having 2 to 10 carbon atoms bonded to a bond of a branched or cyclic organopolysiloxane residue having 3 to 10, preferably 3 to 5 silicon atoms. With a tetravalent group Ri, more preferably an alkylene group having 3 to 6 carbon atoms.

（式中、Ｒ¹は、メチル基、エチル基、プロピル基、ブチル基等の炭素数１〜４のアルキル基、フェニル基等の炭素数６〜１０のアリール基であり、Ｒ¹は同一でも異なっていてもよい。Ｒ²は、メチレン基、エチレン基、プロピレン基（トリメチレン基、メチルエチレン基）等の炭素数１〜４のアルキレン基、フェニレン基等の炭素数６〜１０のアリーレン基である。）Here, examples of the silalkylene structure and the silarylene structure include those shown below.

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

−（（Ｒ¹）_3-kＳｉＯ_k/2）（Ｏ_1/2Ｓｉ（Ｒ¹）₂）_k−

（式中、Ｒ¹は上記と同じである。ｇは１〜９の整数、好ましくは１〜４の整数であり、ｈは２〜６の整数、好ましくは２〜４の整数、ｊは０〜８の整数、好ましくは０又は１で、ｈ＋ｊは３〜１０の整数、好ましくは３〜５の整数であり、ｋは１〜３の整数であり、好ましくは２又は３である。）Further, a linear organopolysiloxane residue having 2 to 10, preferably 2 to 5 silicon atoms, and a branched or cyclic 2 to 3 silicon atoms, preferably 3 to 5 silicon atoms. Examples of the hexavalent organopolysiloxane residue include those shown below.

− ((R ¹ ) _3-k SiO _{k / 2} ) (O _1/2 Si (R ¹ ) ₂ ) _k −

(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 3-10, preferably an integer of 3-5, and k is an integer of 1-3, preferably 2 or 3.)

Specific examples of Y include, for example, 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 a C 1-10 alkoxy group such as a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group, and a C 2-10 carbon atom such as a methoxymethoxy group. 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, and a halogen atom such as a chloro atom, a bromo atom and an iodo atom. Among them, a methoxy group, an ethoxy group, an isopropenoxy group and a chloro atom are preferred.

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, or a phenyl group, and among them, a methyl group is 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.
m is an integer of 1 to 5, and if it is less than 1, the adhesion to the substrate is reduced. If it is 6 or more, the terminal alkoxy value is too high and adversely affects the performance. Yes, 1 is particularly preferred.

（式中、Ｒ’’はケトン、エステル、アミド、エーテル、スルフィド、アミン、フェニレンのいずれかを有していてもよい炭素数１〜１０のアルキレン基、又はカルボニル基であり、Ｗはケイ素原子数２〜４０個の直鎖状の２価のオルガノ（ポリ）シロキサン残基、炭素数１〜４のアルキレン基を介して結合しているケイ素原子数３〜４０個のシロキサン結合を有してもよい直鎖状のシルアルキレン基、及び炭素数６〜１０のアリーレン基を介して結合しているケイ素原子数３〜４０個のシロキサン結合を有してもよい直鎖状のシルアリーレン基から選ばれる２価の基であり、オルガノ（ポリ）シロキサン残基、シルアルキレン基、シルアリーレン基はそれぞれ単一でも混合されていてもよく、βは０又は１であり、γは０又は１であり、β＋γは１又は２である。）
In the above formula (1), Q is a divalent organic group which may have a siloxane bond and / or a silylene group, and is particularly preferably a divalent organic group represented by the following formula (4). .

(Wherein, R ″ is an alkylene group having 1 to 10 carbon atoms which may have any of ketone, ester, amide, ether, sulfide, amine and phenylene, or carbonyl group, and W is a silicon atom A linear divalent organo (poly) siloxane residue having 2 to 40 carbon atoms, having a siloxane bond having 3 to 40 silicon atoms bonded through an alkylene group having 1 to 4 carbon atoms; it may also be linear silalkylene group, and silarylene group may linear, which has a bonded silicon atoms that are 3-40 amino siloxane bonds and through an arylene group having 6 to 10 carbon atoms Wherein the organo (poly) siloxane residue, the silalkylene group, and the silarylene group may each be single or mixed, β is 0 or 1, and γ is 0 or 1. And β + γ is 1 or 2.)

  In the above formula (4), R ″ is specifically a carbon atom such as a methylene group, ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group, hexamethylene group, etc.). 2 wherein alkylene groups having 1 to 10 carbon atoms and alkylene groups having 1 to 10 carbon atoms are bonded to each other via an arylene group such as a ketone, ester, amide, ether, sulfide, amine, or phenylene group having 6 to 8 carbon atoms. And a carbonyl group, preferably an alkylene group having 1 to 4 carbon atoms, a divalent group in which alkylene groups having 1 to 4 carbon atoms are bonded to each other via an ether, or a carbonyl group.

Specific examples of R ″ include, for example, the following groups.

（式中、Ｒ¹は、メチル基、エチル基、プロピル基、ブチル基等の炭素数１〜４のアルキル基、フェニル基等の炭素数６〜１０のアリール基であり、Ｒ¹は同一でも異なっていてもよい。Ｒ²は、メチレン基、エチレン基、プロピレン基（トリメチレン基、メチルエチレン基）等の炭素数１〜４のアルキレン基、フェニレン基等の炭素数６〜１０のアリーレン基である。）In the above formula (4), specific examples of the linear silalkylene group represented by W, the silalkylene structure in the linear silarylene group, and the silarylene structure include the following.

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

（式中、Ｒ¹は上記と同じである。ｆは１〜３９の整数であり、好ましくは２〜９の整数である。）Examples of the linear divalent organopolysiloxane residue having 2 to 40, preferably 3 to 10 silicon atoms include those shown below.

(In the formula, R ¹ is the same as above. F is an integer of ^{1 to} 39, preferably an integer of 2 to 9.)

Here, the following can be exemplified as W.

  In the above formula (1), R 'is a monovalent fluoroalkyl group (for example, a fluoroalkyl group having 1 to 6 carbon atoms), a monovalent fluorooxyalkylene group-containing polymer residue, a methyl group having 1 to 4 carbon atoms. , An ethyl group, a propyl group, an alkyl group such as a butyl group, or a phenyl group, among which a monovalent fluorooxyalkylene group-containing polymer residue and an alkyl group having 1 to 4 carbon atoms are preferable, and particularly a monovalent fluorooxy group. Alkylene group-containing polymer residues are preferred.

（式中、ｐ、ｑ、ｒ、ｓはそれぞれ０〜２００の整数で、ｐ＋ｑ＋ｒ＋ｓ＝３〜２００の整数であり、ｔは１〜３の整数であり、各繰り返し単位は直鎖状でも分岐状であってもよく、各繰り返し単位同士はランダムに結合されていてよい。）In the above formula (1), when R ′ is a monovalent fluorooxyalkylene group-containing polymer residue, R ′ is a monovalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (2). Groups are preferred.

(Where p, q, r, and s are each an integer of 0 to 200, p + q + r + s is an integer of 3 to 200, t is an integer of 1 to 3, and each repeating unit is linear or branched. And each repeating unit may be randomly bonded.)

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

（式中、ｐ１は５〜１００の整数、ｑ１は５〜１００の整数で、ｐ１＋ｑ１は１０〜１０５の整数である。）

(In the formula, 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.)

The method for preparing the fluoropolyether group-containing polymer-modified silane represented by the above formula (1) wherein α is 1 includes, for example, the following method.
A fluorooxyalkyl group-containing polymer having two olefin moieties at one end of the molecular chain (ie, a monovalent fluorooxyalkylene group-containing polymer residue and a polymer having two olefin moieties at one end of the molecular chain) is dissolved in a solvent, for example, Dissolved in a fluorinated solvent such as 1,3-bis (trifluoromethyl) benzene to convert an organosilicon compound having a SiH group and a hydrolyzable terminal group in a molecule such as trimethoxysilane into a hydrosilylation reaction catalyst such as chloride In the presence of a toluene solution of a platinate / vinylsiloxane complex, at a temperature of 40 to 120C, preferably 60 to 100C, more preferably about 80C, for 1 to 72 hours, preferably 20 to 36 hours, more preferably about 20 to 36 hours. Under the condition of 24 hours, hydrosilylation addition reaction and aging are performed.

Further, as another method for preparing the fluoropolyether group-containing polymer-modified silane represented by the above formula (1) wherein α is 1, for example, the following method can be mentioned.
A fluorooxyalkyl group-containing polymer having two olefin moieties at one end of a molecular chain is dissolved in a solvent, for example, a fluorinated solvent such as 1,3-bis (trifluoromethyl) benzene, and SiH is dissolved in a molecule such as trichlorosilane. An organosilicon compound having a group and a hydrolyzable terminal group (e.g., a halogen atom bonded to a silicon atom such as a chlorine atom) is reacted with a hydrosilylation reaction catalyst such as a chloroplatinic acid / vinylsiloxane complex in a toluene solution at 40 to 120. C., preferably 60 to 100.degree. C., more preferably about 80.degree. C., for 1 to 72 hours, preferably 20 to 36 hours, more preferably about 24 hours. And the substituents on the silyl group (eg, halogen atoms) are hydrolyzable, such as alkoxy groups such as methoxy groups. To convert to.

  In addition, instead of the organosilicon compound having a SiH group and a hydrolyzable terminal group in the molecule, a SiH group-containing organosilicon compound having no hydrolyzable terminal group can be used. In this case, the organosilicon compound may be used. Used is an organosilicon compound having no hydrolyzable terminal group in the molecule and having two or more SiH groups. At this time, a fluorooxyalkyl group-containing polymer having two olefin sites at one end of the molecular chain and an organosilicon having no hydrolyzable terminal group in the molecule and having two or more SiH groups in the same manner as described above. The compound is subjected to a hydrosilylation addition reaction in equimolar or more to form a reactant (intermediate) having two residual SiH groups at one end of the molecular chain, and then the SiH at the polymer end of the reaction product (intermediate) is produced. A group and an organosilicon compound having an olefin moiety and a hydrolyzable terminal group in a molecule such as allyltrimethoxysilane in the presence of a hydrosilylation reaction catalyst such as a toluene solution of chloroplatinic acid / vinylsiloxane complex at 40 to 120 ° C. Preferably at a temperature of 60-100 ° C, more preferably about 80 ° C, for 1-72 hours, preferably 20-36 hours, more preferably about 24 hours. In ripen causes further hydrosilation addition reaction.

（式中、Ｒｆ、Ｑ、Ｒ’は上記と同じである。Ｚは２価炭化水素基である。）Here, as the fluorooxyalkyl group-containing polymer having two olefin sites at one end of the molecular chain, a fluorooxyalkyl group-containing polymer represented by the following general formula (5) can be exemplified.

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

  In the above formula (5), Z is a divalent hydrocarbon group, preferably a divalent hydrocarbon group having 1 to 8, particularly 1 to 4 carbon atoms, specifically, a methylene group, an ethylene group, C1-C8 alkylene groups such as propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), hexamethylene group, and octamethylene 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.

（式中、ｒ１は１〜１００の整数であり、ｐ１、ｑ１、ｐ１＋ｑ１は上記と同じである。）Preferred examples of the fluorooxyalkyl group-containing polymer represented by the formula (5) include the following. In each of the formulas, the number of repetitions (or the degree of polymerization) of each of the repeating units constituting the fluorooxyalkyl group can be any number that satisfies the formula (2) in the above Rf.

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

  As a method for preparing the fluorooxyalkyl group-containing polymer represented by the above formula (5), for example, a fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of a molecular chain and having two olefin moieties (ie, a monovalent polymer) A fluorooxyalkylene group-containing polymer residue, a polymer having two olefinic moieties at one end of the molecular chain and a hydroxyl group) and hydrosilane in the presence of a dehydrogenation catalyst using a solvent at 0 to 60 ° C, preferably 15 to 35 ° C. The dehydrogenation reaction is carried out at a temperature of about 25 ° C., more preferably for about 10 minutes to 24 hours, preferably for about 30 minutes to 2 hours, more preferably for about 1 hour.

  As another method for preparing the fluorooxyalkyl group-containing polymer represented by the above formula (5), a fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of a molecular chain and having two olefin moieties (ie, A monovalent fluorooxyalkylene group-containing polymer residue, a polymer having two olefin moieties and a hydroxyl group at one end of the molecular chain) and, for example, a fluorooxyalkyl group-containing polymer having an acid fluoride at one end of the molecular chain; In the presence, using a solvent at a temperature of 0 to 100 ° C, preferably 25 to 80 ° C, more preferably 60 ° C, for 1 to 48 hours, preferably 5 to 36 hours, more preferably about 20 hours. A hydrogen halide (dehydrofluorination) reaction or the like is performed.

（式中、ｐ１、ｑ１、ｐ１＋ｑ１は上記と同じである。）Here, the fluorooxyalkyl group-containing polymer having an acid fluoride at one end of the molecular chain includes, as a group at one end of the molecular chain, other acid halides (for example, acid chloride) and acid anhydrides in addition to the acid fluoride described above. Products, esters (eg, alkyl esters such as methyl ester), carboxylic acids, and the like can also be used.
Specific examples of the perfluorooxyalkyl group-containing polymer having these groups (acid halide, acid anhydride, ester, carboxylic acid, etc.) at one terminal of the molecular chain include the following.

(In the formula, p1, q1, and p1 + q1 are the same as above.)

  The addition amount of the fluorooxyalkyl group-containing polymer having a functional group such as acid fluoride at one end of the molecular chain is based on one equivalent of the reactive terminal group (hydroxyl group) of the fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain. Thus, 0.5 to 1 equivalent, more preferably 0.8 to 1 equivalent, and still more preferably about 0.9 equivalent can be used.

As the base used for preparing the fluorooxyalkyl group-containing polymer represented by the formula (5), for example, amines and alkali metal bases can be used. Specifically, amines include triethylamine, Diisopropylethylamine, pyridine, DBU, imidazole and the like. Alkali metal bases include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, alkyl lithium, potassium t-butoxy, lithium diisopropylamide, lithium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, potassium bis (Trimethylsilyl) amide and the like.
The amount of the base used is 1 to 10 equivalents, more preferably 1 to 3 equivalents, and still more preferably about 2 equivalents, relative to 1 equivalent of the reactive terminal group of the fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain. Can be used.

In the preparation of the fluorooxyalkyl group-containing polymer represented by the above formula (5), the solvent used is preferably a fluorinated solvent, and as the fluorinated solvent, 1,3-bis (trifluoromethyl) benzene, trifluoro Methylbenzene, methylnonafluorobutylether, methylnonafluoroisobutylether, ethylnonafluorobutylether, ethylnonafluoroisobutylether, 1,1,1,2,3,4,4,5,5,5-decafluoro-3- Hydrofluoroether (HFE) -based solvents such as methoxy-2- (trifluoromethyl) pentane (manufactured by 3M, trade name: Novec series), and perfluoro-based solvents (3M manufactured by fully fluorinated compounds) (Trade name: Florinart Series).
The amount of the solvent used is 10 to 300 parts by mass, preferably 50 to 150 parts by mass, more preferably about 100 parts by mass, based on 100 parts by mass of the fluorooxyalkylene group-containing polymer having two olefin sites at one end of the molecular chain. Part 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, whereby a fluorooxyalkyl group-containing polymer represented by the formula (5) is obtained.

（式中、ｒ１、ｐ１、ｑ１、ｐ１＋ｑ１は上記と同じである。）Here, as a raw material used for preparing the fluorooxyalkyl group-containing polymer represented by the formula (5), a fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of a molecular chain and having two olefin sites is specifically mentioned. Examples include the following.

(In the formula, r1, p1, q1, p1 + q1 are the same as above.)

  As a method for preparing a fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of a molecular chain and two olefin sites as the raw material, for example, an acid fluoride group (—C (＝ O) —F ), A Grignard reagent having an olefinic moiety as a nucleophile, for example, 1,3-bis (trifluoromethyl) benzene, tetrahydrofuran as a solvent, and then mixed at 0 to 80 ° C, preferably By aging at 50 to 70 ° C., more preferably about 60 ° C. for 1 to 6 hours, preferably 3 to 5 hours, and more preferably about 4 hours, a hydroxyl group is introduced together with two olefin sites at one end of the molecular chain. I do.

（式中、ｐ１、ｑ１、ｐ１＋ｑ１は上記と同じである。）Here, the perfluorooxyalkyl group-containing polymer as a raw material used for preparing the fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain and having two olefin sites is a group having at one end of the molecular chain, In addition to the acid fluoride described above, other acid halides (such as acid chloride), acid anhydrides, esters, carboxylic acids, amides, and the like can also be used.
Specific examples of the perfluorooxyalkyl group-containing polymer having these groups at one terminal of the molecular chain include the following.

(In the formula, p1, q1, and p1 + q1 are the same as above.)

Examples of the nucleophilic agent used for preparing the fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain and having two olefin sites include allyl magnesium halide, 3-butenyl magnesium halide, 4-pentenyl magnesium halide, 5-hexenyl magnesium halide and the like can be used. It is also possible to use the corresponding lithium reagent.
The nucleophile is used in an amount of 2 to 5 equivalents, more preferably 2.5 to 3.5 equivalents, and still more preferably about 3 equivalents, per equivalent of the reactive terminal group of the perfluorooxyalkyl group-containing polymer. Can be used.

Further, as a solvent used for preparing a fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain and having two olefin sites, 1,3-bis (trifluoromethyl) benzene as a fluorine-based solvent, Trifluoromethylbenzene, methylnonafluorobutylether, methylnonafluoroisobutylether, ethylnonafluorobutylether, ethylnonafluoroisobutylether, 1,1,1,2,3,4,4,5,5,5-decafluoro- Hydrofluoroether (HFE) -based solvents such as 3-methoxy-2- (trifluoromethyl) pentane (manufactured by 3M, trade name: Novec series), perfluoro-based solvents composed of fully fluorinated compounds ( 3M company, trade name: Florinert series) And the like. Further, ether solvents such as tetrahydrofuran, monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and dioxane can be used as the organic solvent.
The solvent can be used in an amount of 10 to 300 parts by mass, preferably 100 to 200 parts by mass, and more preferably about 150 parts by mass, based on 100 parts by mass of the perfluorooxyalkyl group-containing polymer.

  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, whereby the fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain is obtained.

（式中、ｐ１、ｑ１、ｐ１＋ｑ１は上記と同じである。）Examples of the hydrosilane used for preparing the fluorooxyalkyl group-containing polymer represented by the formula (5) include polydimethylsiloxane-terminated hydrosilane having 2 to 40 silicon atoms in which one of the terminal groups is blocked with an alkyl group; Examples include polydimethylsiloxane-terminated hydrosilanes having 2 to 40 silicon atoms and having one of the groups sealed with a fluoroalkyl group or a fluorooxyalkyl group.
Specific examples of the hydrosilane used for preparing the fluorooxyalkyl group-containing polymer represented by the formula (5) include the following.

(In the formula, p1, q1, and p1 + q1 are the same as above.)

  The amount of the hydrosilane used is 1 to 5 equivalents, more preferably 1 to 2 equivalents to 1 equivalent of the reactive terminal group of the fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain and having two olefin sites. Equivalents, more preferably about 1.2 equivalents.

As the dehydrogenation catalyst used for preparing the fluorooxyalkyl group-containing polymer represented by the formula (5), for example, a platinum group metal-based catalyst such as rhodium, palladium, ruthenium, or a boron catalyst can be used. Specific examples include a platinum group metal-based catalyst such as tetrakis (triphenylphosphine) palladium and chlorotris (triphenylphosphine) rhodium, and a boron catalyst such as tris (pentafluorophenyl) borane.
The amount of the dehydrogenation catalyst used is 0.01 to 0.0005 equivalent, relative to 1 equivalent of the reactive terminal group of the fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain and having two olefin sites. Preferably 0.007 to 0.001 equivalent, more preferably about 0.005 equivalent can be used.

Solvents used for preparing the fluorooxyalkyl group-containing polymer represented by the formula (5) include fluorine-containing aromatic fluorine-containing solvents such as 1,3-bis (trifluoromethyl) benzene and trifluoromethylbenzene. Hydrocarbon solvents, methyl nonafluorobutyl ether, methyl nonafluoro isobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoro isobutyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoro- Hydrofluoroether (HFE) -based solvents such as 3-methoxy-2- (trifluoromethyl) pentane (manufactured by 3M, trade name: Novec series), perfluoro-based solvents composed of fully fluorinated compounds ( 3M Company, trade name: Florinert Series). Further, ether solvents such as tetrahydrofuran, monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and dioxane can be used as the organic solvent.
The amount of the solvent to be used is 10 to 300 parts by mass, preferably 50 to 150 parts by mass, more preferably 50 parts by mass, based on 100 parts by mass of the fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain and having two olefin sites. Can be used in an amount of about 100 parts by mass.

  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, whereby a fluorooxyalkyl group-containing polymer represented by the formula (5) is obtained.

In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the above formula (1) wherein α is 1, the solvent used is preferably a fluorinated solvent, and the fluorinated solvent is 1,3-bis ( (Trifluoromethyl) benzene, trifluoromethylbenzene, methylnonafluorobutylether, methylnonafluoroisobutylether, ethylnonafluorobutylether, ethylnonafluoroisobutylether, 1,1,1,2,3,4,4,5,5 Hydrofluoroether (HFE) -based solvent (manufactured by 3M, trade name: Novec series), such as 5,5-decafluoro-3-methoxy-2- (trifluoromethyl) pentane, and a completely fluorinated compound. Perfluoro-based solvent (trade name: Fluorinert Series, manufactured by 3M) ), And the like.
The amount of the solvent used is 10 to 300 parts by mass, preferably 50 to 150 parts by mass, more preferably about 100 parts by mass, based on 100 parts by mass of the fluorooxyalkyl group-containing polymer having two olefin sites at one end of the molecular chain. Part can be used.

（式中、Ｒ、Ｘ、ｎ、Ｒ¹、Ｒ²、ｇ、ｊは上記と同じである。Ｒ³は炭素数２〜８の２価炭化水素基である。ｉは２〜９の整数、好ましくは２〜４の整数であり、ｉ＋ｊは２〜９の整数である。）In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) wherein α is 1, as the organosilicon compound having a SiH group and a hydrolyzable terminal group in the molecule, the following general formula: Compounds represented by (6) to (9) 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 2 to 9) , Preferably an integer of 2 to 4, and i + j is an integer of 2 to 9.)

Here, as the divalent hydrocarbon group having 2 to 8, preferably 2 to ³ carbon atoms for R ³ , a methylene group, an ethylene group, a propylene group (a trimethylene group, a methylethylene group), a butylene group (a 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 (such as an alkylene arylene group). And a trimethylene group are preferred.

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

  In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) wherein α is 1, a fluorooxyalkyl group-containing polymer having two olefin sites at one end of a molecular chain and a SiH group and The amount of the organosilicon compound having a SiH group and a hydrolyzable terminal group in the molecule when reacting with the organosilicon compound having a hydrolyzable terminal group is determined by the amount of the fluorooxy compound having two olefin sites at one end of the molecular chain. It can be used in an amount of 2 to 6 equivalents, more preferably 2.2 to 3.5 equivalents, and still more preferably about 3 equivalents, per equivalent of the reactive terminal group of the alkyl group-containing polymer.

（式中、Ｒ¹、Ｒ²、ｇ、ｊ、ｉは上記と同じである。）Further, in the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) wherein α is 1, an organosilicon having no hydrolyzable terminal group in the molecule and having two or more SiH groups As the compound, compounds represented by the following general formulas (10) to (12) are preferable.

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

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

  In the preparation of a fluoropolyether group-containing polymer-modified silane represented by the formula (1) wherein α is 1, a fluorooxyalkyl group-containing polymer having two olefin sites at one end of a molecular chain and a hydrolyzable compound in the molecule The amount of the organosilicon compound having no terminal group and having no hydrolyzable terminal group in the molecule when reacting with an organosilicon compound having two or more SiH groups and having two or more SiH groups is as follows: 5 to 20 equivalents, more preferably 7.5 to 12.5 equivalents, still more preferably about 1 equivalent of the reactive end group of the fluorooxyalkyl group-containing polymer having two olefin sites at one end of the molecular chain. 10 equivalents can be used.

（式中、Ｒ、Ｘ、ｎは上記と同じである。Ｖは単結合、又は炭素数１〜６の２価炭化水素基である。）In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) wherein α is 1, as the organosilicon compound having an olefin moiety and a hydrolyzable terminal group in the molecule, the following general formula: The compound represented by (13) is preferred.

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

  In the above formula (13), V is a single bond or a divalent hydrocarbon group having 1 to 6 carbon atoms, and specific examples of the divalent hydrocarbon group having 1 to 6 carbon atoms include a methylene group and an ethylene group. And 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. V 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) wherein α is 1, a fluorooxyalkyl group-containing polymer having two olefin sites at one end of a molecular chain and a hydrolyzable compound in the molecule When reacting a reaction product of an organosilicon compound having no end group and having two or more SiH groups with an olefin site in the molecule and an organosilicon compound having a hydrolyzable end group, an olefin site in the molecule is used. And the amount of the organosilicon compound having a hydrolyzable terminal group is such that the fluorooxyalkyl group-containing polymer having two olefin sites at one end of the molecular chain and the molecule having no hydrolyzable terminal group in the molecule, and having an SiH group 2 to 6 equivalents, more preferably 2.2 to 3.5 equivalents, still more preferably 1 equivalent to 1 equivalent of the reactive terminal group of the reaction product with the organosilicon compound having two or more organosilicon compounds. About 3 can be used equivalents.

In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) wherein α is 1, as the hydrosilylation reaction catalyst, platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum chloride Platinum group metal-based catalysts such as tetrakis (triphenylphosphine) palladium and chlorotris (triphenylphosphine) rhodium, such as complexes of acids with olefins, aldehydes, vinylsiloxanes, acetylene alcohols, and the like. Preferably, it is a platinum compound such as a vinylsiloxane coordination compound.
The amount of the hydrosilylation reaction catalyst used is a fluorooxyalkyl group-containing polymer having two olefinic moieties at one end of the molecular chain, or two or more SiH groups having no polymerizable hydrolyzable terminal group in the molecule. It is used in an amount of 0.1 to 100 ppm, more preferably 1 to 50 ppm in terms of transition metal (mass) based on the amount of the reactant with the organosilicon compound.

を使用し、分子中にＳｉＨ基及び加水分解性末端基を有する有機ケイ素化合物として、トリメトキシシランを使用した場合には、下記式で表される化合物が得られる。

Thereafter, the solvent and unreacted substances are distilled off under reduced pressure to obtain the desired compound.
For example, as a fluorooxyalkyl group-containing polymer having two olefin moieties 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 terminal group in the molecule, a compound represented by the following formula is obtained.

Examples of a method for preparing the fluoropolyether group-containing polymer-modified silane represented by the above formula (1) wherein α is 2 include the following methods.
A fluorooxyalkylene group-containing polymer having two olefin moieties at both ends of the molecular chain (ie, a polymer having two divalent fluorooxyalkylene group-containing polymer residues and two olefin moieties at each molecular chain end) Is dissolved in a solvent, for example, a fluorinated solvent such as 1,3-bis (trifluoromethyl) benzene, and an organosilicon compound having a SiH group and a hydrolyzable terminal group in a molecule such as trimethoxysilane is hydrosilylated. In the presence of a reaction catalyst, for example, 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, for 1 to 72 hours, preferably 20 to 36 hours. And more preferably for about 24 hours.

  Further, instead of the organosilicon compound having a SiH group and a hydrolyzable terminal group in the molecule, a SiH group-containing organosilicon compound having no hydrolyzable terminal group can be used. In this case, the organosilicon compound Used is an organosilicon compound having no hydrolyzable terminal group in the molecule and having two or more SiH groups. At this time, a fluorooxyalkylene group-containing polymer having two olefin sites at both ends of the molecular chain and an organic compound having two or more SiH groups having no hydrolyzable terminal group in the molecule in the same manner as described above. After reacting with a silicon compound in equimolar or more to form a reactant (intermediate) having two residual SiH groups at both ends of the molecular chain, a SiH group at the polymer end of the reaction product (intermediate) And an organosilicon compound having an olefin site and a hydrolyzable terminal group in a molecule such as allyltrimethoxysilane in the presence of a hydrosilylation reaction catalyst such as a toluene solution of chloroplatinic acid / vinylsiloxane complex, preferably at 40 to 120 ° C. Is aged at a temperature of 60-100 ° C., more preferably about 80 ° C., for 1-72 hours, preferably 20-36 hours, more preferably about 24 hours. .

（式中、Ｒｆ、Ｚ、Ｑ、Ｒ’は上記と同じである。）Here, as the fluorooxyalkylene group-containing polymer having two olefin moieties at both ends of the molecular chain, a fluorooxyalkylene group-containing polymer represented by the following general formula (14) can be exemplified.

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

（式中、ｐ１、ｑ１、ｐ１＋ｑ１は上記と同じである。）Preferred examples of the fluorooxyalkylene group-containing polymer represented by the formula (14) include the following. In each of the formulas, the number of repetitions (or the degree of polymerization) of each of the repeating units constituting the fluorooxyalkylene group can be any number that satisfies the formula (3) in Rf.

(In the formula, p1, q1, and p1 + q1 are the same as above.)

  Examples of the method for preparing the fluorooxyalkylene group-containing polymer represented by the above formula (14) include, for example, a fluorooxyalkylene group-containing polymer having a hydroxyl group at both molecular terminals and having two olefin sites at both molecular terminals. (I.e., a polymer having two divalent fluorooxyalkylene group-containing polymer residues and two olefin sites and hydroxyl groups at both ends of the molecular chain) and hydrosilane in the presence of a dehydrogenation catalyst using a solvent. The dehydrogenation reaction is carried out at a temperature of ６０60 ° C., preferably 15-35 ° C., more preferably about 25 ° C., for 10 minutes to 24 hours, preferably 30 minutes to 2 hours, more preferably about 1 hour.

  As another method for preparing the fluorooxyalkylene group-containing polymer represented by the above formula (14), a fluorooxyalkylene having a hydroxyl group at both ends of a molecular chain and having two olefin sites at both ends of the molecular chain. A group-containing polymer (that is, a polymer having two divalent fluorooxyalkylene group-containing polymer residues, two olefin sites at each terminal of the molecular chain, and a hydroxyl group) and, for example, an acid fluoride at one terminal of the molecular chain. In the presence of a base, a fluorooxyalkyl group-containing polymer and a solvent are used at a temperature of 0 to 100 ° C, preferably 25 to 80 ° C, more preferably 60 ° C, for 1 to 48 hours, preferably 5 to 36 hours, More preferably, a dehydrohalogenation (dehydrofluorination) reaction or the like is performed for about 20 hours.

（式中、ｐ１、ｑ１、ｐ１＋ｑ１は上記と同じである。）Here, the fluorooxyalkyl group-containing polymer having an acid fluoride at one end of the molecular chain includes, as a group having one end of the molecular chain, in addition to the acid fluoride described above, acid halides, acid anhydrides, esters, carboxylic acids, and the like. Can be used.
Specific examples of the perfluorooxyalkyl group-containing polymer having these groups (acid halide, acid anhydride, ester, carboxylic acid, etc.) at one terminal of the molecular chain include the following.

(In the formula, p1, q1, and p1 + q1 are the same as above.)

  The addition amount of the fluorooxyalkyl group-containing polymer having an acid fluoride at one end of the molecular chain is 0.1 to 1 equivalent of the reactive terminal group (hydroxyl group) of the fluorooxyalkylene group-containing polymer having a hydroxyl group at both ends of the molecular chain. 5 to 1 equivalent, more preferably 0.8 to 1 equivalent, and still more preferably about 0.9 equivalent can be used.

As the base used for preparing the fluorooxyalkylene group-containing polymer represented by the formula (14), for example, amines and alkali metal bases can be used. Specifically, amines include triethylamine, Diisopropylethylamine, pyridine, DBU, imidazole and the like. Alkali metal bases include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, alkyl lithium, potassium t-butoxy, lithium diisopropylamide, lithium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, potassium bis (Trimethylsilyl) amide and the like.
The amount of the base used is 1 to 10 equivalents, more preferably 1 to 3 equivalents, and still more preferably about 2 equivalents, relative to 1 equivalent of the reactive terminal group of the fluorooxyalkylene group-containing polymer having hydroxyl groups at both ends of the molecular chain. Can be used.

In the preparation of the fluorooxyalkylene group-containing polymer represented by the above formula (14), the solvent used is preferably a fluorinated solvent, and as the fluorinated solvent, 1,3-bis (trifluoromethyl) benzene, trifluoro Methylbenzene, methylnonafluorobutylether, methylnonafluoroisobutylether, ethylnonafluorobutylether, ethylnonafluoroisobutylether, 1,1,1,2,3,4,4,5,5,5-decafluoro-3- Hydrofluoroether (HFE) -based solvents such as methoxy-2- (trifluoromethyl) pentane (manufactured by 3M, trade name: Novec series), and perfluoro-based solvents (3M manufactured by fully fluorinated compounds) Made, trade name: Florinert series) .
The amount of the solvent to be used is 10 to 300 parts by mass, preferably 50 to 150 parts by mass, more preferably about 100 parts by mass, based on 100 parts by mass of the fluorooxyalkylene group-containing polymer having hydroxyl groups at both molecular chain terminals. Can be.

  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, whereby a fluorooxyalkylene group-containing polymer represented by the formula (14) is obtained.

（式中、ｐ１、ｑ１、ｐ１＋ｑ１は上記と同じである。）Here, as a fluorooxyalkylene group-containing polymer having a hydroxyl group at both molecular chain terminals and having two olefin sites at both molecular chain terminals, which is used for preparing the fluorooxyalkylene group-containing polymer represented by the formula (14), Specific examples include the following.

(In the formula, p1, q1, and p1 + q1 are the same as above.)

  Here, as a method for preparing a fluorooxyalkylene group-containing polymer having hydroxyl groups at both ends of the molecular chain and having two olefin sites at both ends of the molecular chain, for example, an acid fluoride group (-C A perfluorooxyalkylene group-containing polymer having (＝ O) —F), a Grignard reagent having an olefin moiety as a nucleophile, and a solvent such as 1,3-bis (trifluoromethyl) benzene and tetrahydrofuran are mixed, By aging at 80 ° C., preferably 50-70 ° C., more preferably about 60 ° C. for 1-6 hours, preferably 3-5 hours, and more preferably about 4 hours, two molecular A hydroxyl group is introduced together with the olefin moiety.

（式中、ｐ１、ｑ１、ｐ１＋ｑ１は上記と同じである。）Here, in the perfluorooxyalkylene group-containing polymer, acid halides, acid anhydrides, esters, carboxylic acids, amides, and the like can be used as the groups at both ends of the molecular chain, in addition to the acid fluorides described above.
Specific examples of the perfluorooxyalkylene group-containing polymer having these groups at both ends of the molecular chain include those shown below.

(In the formula, p1, q1, and p1 + q1 are the same as above.)

Examples of the nucleophilic agent used for preparing the fluorooxyalkylene group-containing polymer having a hydroxyl group at both ends of the molecular chain include allyl magnesium halide, 3-butenyl magnesium halide, 4-pentenyl magnesium halide, and 5-hexenyl magnesium halide. Can be used. It is also possible to use the corresponding lithium reagent.
The amount of the nucleophile to be used is 4 to 10 equivalents, more preferably 5 to 7 equivalents, and still more preferably about 6 equivalents, relative to 1 equivalent of the reactive terminal group of the perfluorooxyalkylene group-containing polymer. .

Examples of the solvent used for preparing the fluorooxyalkylene group-containing polymer having hydroxyl groups at both molecular chain terminals include 1,3-bis (trifluoromethyl) benzene, trifluoromethylbenzene, and methylnona as fluorinated solvents. Fluorobutyl ether, methylnonafluoroisobutylether, ethylnonafluorobutylether, ethylnonafluoroisobutylether, 1,1,1,2,3,4,5,5,5-decafluoro-3-methoxy-2- ( Hydrofluoroether (HFE) solvents such as (trifluoromethyl) pentane (manufactured by 3M, trade name: Novec series), and perfluoro solvents (manufactured by 3M, trade name: Novec series) composed of fully fluorinated compounds Florinart series). Further, ether solvents such as tetrahydrofuran, monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and dioxane can be used as the organic solvent.
The amount of the solvent to be used is 10 to 300 parts by mass, preferably 100 to 200 parts by mass, more preferably about 150 parts by mass, based on 100 parts by mass of the perfluorooxyalkylene group-containing polymer.

  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, whereby the fluorooxyalkylene group-containing polymer having hydroxyl groups at both molecular chain terminals is obtained.

Examples of the hydrosilane used for preparing the fluorooxyalkylene group-containing polymer represented by the formula (14) include a polydimethylsiloxane-terminated hydrosilane having 2 to 40 silicon atoms, one of the terminal groups of which is capped with an alkyl group; Examples include polydimethylsiloxane-terminated hydrosilanes having 2 to 40 silicon atoms and having one of the groups sealed with a fluoroalkyl group or a fluorooxyalkyl group.
The amount of the hydrosilane used is from 1 to 5 equivalents to 1 equivalent of the reactive end group of the fluorooxyalkylene group-containing polymer having a hydroxyl group at one end of the molecular chain and having two olefin sites at both ends of the molecular chain. Preferably 1-2 equivalents, more preferably about 1.2 equivalents can be used.

As the dehydrogenation catalyst used for preparing the fluorooxyalkylene group-containing polymer represented by the formula (14), for example, a platinum group metal-based catalyst such as rhodium, palladium, ruthenium and the like, a boron catalyst and the like can be used. Specific examples include a platinum group metal-based catalyst such as tetrakis (triphenylphosphine) palladium and chlorotris (triphenylphosphine) rhodium, and a boron catalyst such as tris (pentafluorophenyl) borane.
The amount of the dehydrogenation catalyst to be used is from 0.01 to 1 equivalent of the reactive end group of the fluorooxyalkylene group-containing polymer having hydroxyl groups at both ends of the molecular chain and having two olefin sites at both ends of the molecular chain. 0.0005 equivalents, more preferably 0.007 to 0.001 equivalents, even more preferably about 0.005 equivalents can be used.

Solvents used for preparing the fluorooxyalkylene group-containing polymer represented by the formula (14) include fluorine-containing solvents such as 1,3-bis (trifluoromethyl) benzene and trifluoromethylbenzene. Hydrocarbon solvents, methyl nonafluorobutyl ether, methyl nonafluoro isobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoro isobutyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoro- Hydrofluoroether (HFE) -based solvents such as 3-methoxy-2- (trifluoromethyl) pentane (manufactured by 3M, trade name: Novec series), perfluoro-based solvents composed of fully fluorinated compounds ( 3M company, trade name: Florinert series) Further, ether solvents such as tetrahydrofuran, monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and dioxane can be used as the organic solvent.
The amount of the solvent used is 10 to 300 parts by mass, preferably 50 to 300 parts by mass, based on 100 parts by mass of a fluorooxyalkylene group-containing polymer having hydroxyl groups at both ends of the molecular chain and having two olefin sites at both ends of the molecular chain. 150 parts by weight, more preferably about 100 parts by weight 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, whereby a fluorooxyalkylene group-containing polymer represented by the formula (14) is obtained.

In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the above formula (1) wherein α is 2, the solvent used is preferably a fluorinated solvent, and the fluorinated solvent is 1,3-bis ( (Trifluoromethyl) benzene, trifluoromethylbenzene, methylnonafluorobutylether, methylnonafluoroisobutylether, ethylnonafluorobutylether, ethylnonafluoroisobutylether, 1,1,1,2,3,4,4,5,5 Hydrofluoroether (HFE) -based solvent (manufactured by 3M, trade name: Novec series), such as 5,5-decafluoro-3-methoxy-2- (trifluoromethyl) pentane, and a completely fluorinated compound. Perfluoro-based solvent (trade name: Fluorinert Series, manufactured by 3M) ), And the like.
The amount of the solvent used is 10 to 300 parts by mass, preferably 50 to 150 parts by mass, more preferably about 100 parts by mass, based on 100 parts by mass of the fluorooxyalkylene group-containing polymer having two olefin sites at both ends of the molecular chain. Parts by weight can be used.

（式中、Ｒ、Ｘ、ｎ、Ｒ¹、Ｒ²、Ｒ³、ｇ、ｉ、ｊは上記と同じである。）In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) wherein α is 2, as the organosilicon compound having a SiH group and a hydrolyzable terminal group in the molecule, the following general formula: Compounds represented by (6) to (9) are preferred.

(Wherein, R, X, n, R 1, R 2, R 3, g, i, j are as defined above.)

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

  In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) wherein α is 2, a fluorooxyalkylene group-containing polymer having two olefin sites at both ends of the molecular chain and a SiH group in the molecule The amount of the organic silicon compound having a SiH group and a hydrolyzable terminal group in the molecule when reacting with the organosilicon compound having a hydrolyzable terminal group has two olefin moieties at both ends of the molecular chain. It can be used in an amount of 2 to 6 equivalents, more preferably 2.2 to 3.5 equivalents, and still more preferably about 3 equivalents, per equivalent of the reactive terminal group of the fluorooxyalkylene group-containing polymer.

（式中、Ｒ¹、Ｒ²、ｇ、ｊ、ｉは上記と同じである。）In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) wherein α is 2, an organosilicon having no hydrolyzable terminal group in the molecule and having two or more SiH groups As the compound, compounds represented by the following general formulas (10) to (12) are preferable.

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

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

  In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) wherein α is 2, a fluorooxyalkylene group-containing polymer having two olefin sites at both ends of the molecular chain and hydrolysis in the molecule Of the organosilicon compound having no hydrolyzable terminal group and having two or more SiH groups in the molecule when reacting with an organosilicon compound having no hydrophobic end group and having two or more SiH groups Is 5 to 20 equivalents, more preferably 7.5 to 12.5 equivalents, and still more preferably 1 equivalent of the reactive end group of the fluorooxyalkylene group-containing polymer having two olefin moieties at both ends of the molecular chain. Can be used in about 10 equivalents.

（式中、Ｒ、Ｘ、Ｖ、ｎは上記と同じである。）In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) wherein α is 2, as the organosilicon compound having an olefin moiety and a hydrolyzable terminal group in the molecule, the following general formula: The compound represented by (13) is preferred.

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

  In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) wherein α is 2, a fluorooxyalkylene group-containing polymer having two olefin sites at both ends of the molecular chain and hydrolysis in the molecule When reacting a reaction product (intermediate) with an organosilicon compound having two or more SiH groups without having a hydrophilic end group and an organosilicon compound having an olefin moiety and a hydrolyzable end group in the molecule. The amount of the organosilicon compound having an olefin moiety and a hydrolyzable terminal group in the molecule is determined by using a fluorooxyalkylene group-containing polymer having two olefin moieties at both ends of the molecular chain and a hydrolyzable terminal group in the molecule. Instead, 2 to 6 equivalents, more preferably 1 equivalent to the reactive terminal group equivalent of the reaction product (intermediate) with an organosilicon compound having two or more SiH groups. Properly is 2.2 to 3.5 equivalents, can be used more preferably about 3 equivalents.

In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) wherein α is 2, the hydrosilylation reaction catalyst may be platinum black, chloroplatinic acid, an alcohol-modified chloroplatinic acid, platinum chloride Platinum group metal-based catalysts such as tetrakis (triphenylphosphine) palladium and chlorotris (triphenylphosphine) rhodium, such as complexes of acids with olefins, aldehydes, vinylsiloxanes, acetylene alcohols, and the like. Preferably, it is a platinum compound such as a vinylsiloxane coordination compound.
The amount of the hydrosilylation reaction catalyst used is a fluorooxyalkylene group-containing polymer having two olefin sites at both ends of the molecular chain, or a polymer and a polymer having no hydrolyzable terminal group and two SiH groups. The transition metal is used in an amount of 0.1 to 100 ppm, more preferably 1 to 50 ppm, in terms of transition metal (mass), based on the mass of the reaction product (intermediate) with the organosilicon compound.

を使用し、分子中にＳｉＨ基及び加水分解性末端基を有する有機ケイ素化合物として、トリメトキシシランを使用した場合には、下記式で表される化合物が得られる。

Thereafter, the solvent and unreacted substances are distilled off under reduced pressure to obtain the desired compound.
For example, as a fluorooxyalkylene group-containing polymer having two olefin moieties at both ends of the molecular chain, a compound represented by the following formula:

When trimethoxysilane is used as the organosilicon 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 fluoropolyether group-containing polymer-modified silane. The surface treating agent is obtained by partially hydrolyzing a terminal hydrolyzable group of the fluoropolyether group-containing polymer-modified silane into a hydroxyl group by a known method in advance, that is, a fluoro group represented by the above formula (1). A product obtained by hydrolyzing a part of the hydrolyzable group of X in the polyether group-containing polymer-modified silane to form a hydroxyl group can also be used.

If necessary, the surface treatment agent may include a hydrolysis-condensation catalyst such as an organic tin compound (such as dibutyltin dimethoxide and dibutyltin dilaurate), an organic titanium compound (such as tetra-n-butyl titanate), and an organic acid (acetic acid, Methanesulfonic acid, fluorine-modified carboxylic acid, etc.) and inorganic acids (hydrochloric acid, sulfuric acid, etc.) may be added. Of these, acetic acid, tetra-n-butyl titanate, dibutyl tin dilaurate, and fluorine-modified carboxylic acid are particularly desirable.
The amount of the hydrolysis-condensation catalyst to be added is a catalytic amount, and is usually 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass, per 100 parts by mass of the fluoropolyether group-containing polymer-modified silane.

  The surface treatment agent may include a suitable solvent. Examples of such a solvent include fluorine-modified aliphatic hydrocarbon solvents (such as perfluoroheptane and perfluorooctane), fluorine-modified aromatic hydrocarbon solvents (such as 1,3-bis (trifluoromethyl) benzene), and fluorine. Modified ether solvents (such as methyl perfluorobutyl ether, ethyl perfluorobutyl ether, and perfluoro (2-butyltetrahydrofuran)), fluorine-modified alkylamine solvents (such as perfluorotributylamine and perfluorotripentylamine), and hydrocarbon solvents (Eg, petroleum benzine, toluene, xylene) and ketone solvents (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone). Of these, a fluorine-modified solvent is desirable in terms of solubility, wettability, and the like, and in particular, 1,3-bis (trifluoromethyl) benzene, perfluoro (2-butyltetrahydrofuran), 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. The optimum concentration of the fluoropolyether group-containing polymer-modified silane to be dissolved in the solvent varies depending on the treatment method, and may be an amount that can be easily weighed. It is preferably 0.01 to 10% by mass, and particularly preferably 0.05 to 5% by mass, based on the total mass of the silane. It is preferably from 1 to 100% by mass, particularly preferably from 3 to 30% by mass.

  The surface treating agent of the present invention can be applied to a substrate by a known method such as brushing, dipping, spraying, and vapor deposition. The heating method at the time of the vapor deposition treatment 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, when the composition is applied by vapor deposition, a range of 20 to 200 ° C. is desirable. Moreover, you may make it harden under humidification. The thickness of the cured film is appropriately selected depending on the type of the substrate, but is usually 0.1 to 100 nm, particularly 1 to 20 nm.

The substrate to be treated with the surface treatment agent of the present invention is not particularly limited, and may be of various materials such as paper, cloth, metal and its oxide, glass, plastic, ceramic, and quartz. The surface treatment 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 glass or film treated with SiO ₂ .

  Articles 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 machines, spectacle lenses, camera lenses, lens filters, sunglasses, Examples include medical devices such as gastric cameras, copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, and optical articles such as antireflection films. Since the surface treatment agent of the present invention can prevent fingerprints and sebum from adhering to the article and further impart anti-scratching properties, it is particularly useful as a water- and oil-repellent layer for touch panel displays and anti-reflection films. is there.

  Further, the surface treatment agent of the present invention may be used as an antifouling coating for sanitary products such as bathtubs and wash basins, windowpanes or tempered glass for automobiles, trains, aircrafts, etc., antifouling coatings for headlamp covers and the like, and building materials for exterior walls. Water- and oil-repellent coating, anti-fouling coating for kitchen building materials, anti-fouling for telephone boxes and anti-fingerprint / graffiti coating, anti-fingerprint coating for fine arts, anti-fingerprint coating for compact discs, DVDs, etc. It is also useful as a mold release agent or paint additive for a mold, a resin modifier, a fluidity modifier or dispersibility modifier for an inorganic filler, and a lubricity improver for tapes and films.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

で表される化合物１１４ｇ（２．７×１０^-2ｍｏｌ）を混合し、下記式（Ｂ）

で表されるシラン１３．６ｇ（３．３×１０^-2ｍｏｌ）をゆっくりと滴下した後、２５℃で１時間撹拌した。続いて、水を添加し、分液操作により下層であるフッ素化合物層を回収後、アセトンで洗浄した。洗浄後の下層であるフッ素化合物層を再び回収し、減圧下、残存溶剤を留去することで、下記式（Ｃ）

で表されるフルオロポリエーテル基含有ポリマー１０３ｇを得た。 [Example 1]
In a reaction vessel, 100 g of 1,3-bis (trifluoromethyl) benzene, 0.01 g of tris (pentafluorophenyl) borane (2.0 × 10 ⁻⁵ mol), the following formula (A)

Is mixed with 114 g (2.7 × 10 ^-2 mol) of the compound represented by the following formula (B):

After slowly dropping 13.6 g (3.3 × 10 ^-2 mol) of the silane represented by the formula (1), the mixture was stirred at 25 ° C. for 1 hour. Subsequently, water was added, and the lower fluorine compound layer was recovered by a liquid separation operation, and then washed with acetone. The lower layer of the fluorine compound after the washing is recovered again, and the remaining solvent is distilled off under reduced pressure, whereby the following formula (C) is obtained.

103 g of a fluoropolyether group-containing polymer represented by the following formula was obtained.

¹ H-NMR
_{δ0-0.2 (-OSi (C H 3)} 3) 24H
_{δ0.5-0.7 (-SiC H 2 CH 2 CH} 2 CH 3) 2H
_{δ0.8-1.0 (-SiCH 2 CH 2 CH 2} C H 3) 3H
_{δ1.2-1.4 (-SiCH 2 C H 2 C} H 2 CH 3) 4H
_{δ2.4-2.6 (-C H 2 CH = CH} 2) 4H
_{δ4.9-5.1 (-CH 2 CH = C H} 2) 4H
_{δ5.7-5.9 (-CH 2 C H = CH} 2) 2H

で表される化合物１１１ｇ（２．４×１０^-2ｍｏｌ）、１，３−ビス（トリフルオロメチル）ベンゼン９０ｇ、トリメトキシシラン９ｇ（７．４×１０^-2ｍｏｌ）、及び塩化白金酸／ビニルシロキサン錯体のトルエン溶液９．０×１０^-2ｇ（Ｐｔ単体として２．４×１０^-6ｍｏｌを含有）を混合し、８０℃で２４時間熟成させた。その後、溶剤及び未反応物を減圧留去し、液状の生成物８８ｇを得た。 In a reaction vessel, the following formula (C)

111 g (2.4 × 10 ^-2 mol), 90 g of 1,3-bis (trifluoromethyl) benzene, 9 g (7.4 × 10 ^-2 mol) of trimethoxysilane, and chloroplatinic acid 9.0 × 10 ⁻² g of toluene solution of vinyl / vinylsiloxane complex (containing 2.4 × 10 ⁻⁶ mol as Pt alone) and aged at 80 ° C. for 24 hours. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain 88 g of a liquid product.

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

¹ H-NMR
_{δ0-0.2 (-OSi (C H 3)} 3) 24H
_{δ0.5-0.7 (-SiC H 2 CH 2 CH} 2 CH 3, -CH 2 CH 2 C H 2 -Si (OCH 3) 3) 6H
_{δ0.8-1.0 (-SiCH 2 CH 2 CH 2} C H 3) 3H
_{δ1.3-1.4 (-SiCH 2 C H 2 C} H 2 CH 3) 4H
_{δ1.5-1.9 (-CH 2 C H 2 CH} 2 -Si (OCH 3) 3, -C H 2 CH 2 CH 2 -Si (OCH 3) 3) 8H
_{δ3.4-3.7 (-Si (OC H 3)} 3) 18H

で表される化合物１１４ｇ（２．７×１０^-2ｍｏｌ）を混合し、下記式（Ｅ）

で表されるシラン２５．８ｇ（３．３×１０^-2ｍｏｌ）をゆっくりと滴下した後、２５℃で１時間撹拌した。続いて、水を添加し、分液操作により下層であるフッ素化合物層を回収後、アセトンで洗浄した。洗浄後の下層であるフッ素化合物層を再び回収し、減圧下、残存溶剤を留去することで、下記式（Ｆ）

で表されるフルオロポリエーテル基含有ポリマー１２５ｇを得た。 [Example 2]
In a reaction vessel, 100 g of 1,3-bis (trifluoromethyl) benzene, 0.01 g of tris (pentafluorophenyl) borane (2.0 × 10 ⁻⁵ mol), the following formula (A)

Is mixed with 114 g (2.7 × 10 ^-2 mol) of the compound represented by the following formula (E):

After slowly dropping 25.8 g (3.3 × 10 ^-2 mol) of the silane represented by the formula (1), the mixture was stirred at 25 ° C. for 1 hour. Subsequently, water was added, and the lower fluorine compound layer was recovered by a liquid separation operation, and then washed with acetone. The lower layer of the fluorine compound after the washing is recovered again, and the remaining solvent is distilled off under reduced pressure to obtain the following formula (F)

125 g of a fluoropolyether group-containing polymer represented by the following formula was obtained.

¹ H-NMR
_{δ0-0.2 (-OSi (C H 3)} 3) 60H
_{δ0.5-0.7 (-SiC H 2 CH 2 CH} 2 CH 3) 2H
_{δ0.8-1.0 (-SiCH 2 CH 2 CH 2} C H 3) 3H
_{δ1.2-1.4 (-SiCH 2 C H 2 C} H 2 CH 3) 4H
_{δ2.4-2.6 (-C H 2 CH = CH} 2) 4H
_{δ4.9-5.1 (-CH 2 CH = C H} 2) 4H
_{δ5.7-5.9 (-CH 2 C H = CH} 2) 2H

で表される化合物１２０ｇ（２．４×１０^-2ｍｏｌ）、１，３−ビス（トリフルオロメチル）ベンゼン９０ｇ、トリメトキシシラン９ｇ（７．４×１０^-2ｍｏｌ）、及び塩化白金酸／ビニルシロキサン錯体のトルエン溶液９．０×１０^-2ｇ（Ｐｔ単体として２．４×１０^-6ｍｏｌを含有）を混合し、８０℃で２４時間熟成させた。その後、溶剤及び未反応物を減圧留去し、液状の生成物７６ｇを得た。 The following formula (F) is added to the reaction vessel.

120 g (2.4 × 10 ⁻² mol), 90 g of 1,3-bis (trifluoromethyl) benzene, 9 g of trimethoxysilane (7.4 × 10 ⁻² mol), and chloroplatinic acid 9.0 × 10 ⁻² g of toluene solution of vinyl / vinylsiloxane complex (containing 2.4 × 10 ⁻⁶ mol as Pt alone) and aged at 80 ° C. for 24 hours. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain 76 g of a liquid product.

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

¹ H-NMR
_{δ0-0.2 (-OSi (C H 3)} 3) 60H
_{δ0.5-0.7 (-SiC H 2 CH 2 CH} 2 CH 3, -CH 2 CH 2 C H 2 -Si (OCH 3) 3) 6H
_{δ0.8-1.0 (-SiCH 2 CH 2 CH 2} C H 3) 3H
_{δ1.3-1.4 (-SiCH 2 C H 2 C} H 2 CH 3) 4H
_{δ1.5-1.9 (-CH 2 C H 2 CH} 2 -Si (OCH 3) 3, -C H 2 CH 2 CH 2 -Si (OCH 3) 3) 8H
_{δ3.4-3.7 (-Si (OC H 3)} 3) 18H

で表される化合物１１２．２ｇ（２．６×１０^-2ｍｏｌ）を混合し、下記式（Ｂ）

で表されるシラン２７．２ｇ（６．６×１０^-2ｍｏｌ）をゆっくりと滴下した後、２５℃で１時間撹拌した。続いて、水を添加し、分液操作により下層であるフッ素化合物層を回収後、アセトンで洗浄した。洗浄後の下層であるフッ素化合物層を再び回収し、減圧下、残存溶剤を留去することで、下記式（Ｉ）

で表されるフルオロポリエーテル基含有ポリマー１０５ｇを得た。 [Example 3]
In a reaction vessel, 100 g of 1,3-bis (trifluoromethyl) benzene, 0.01 g (2.0 × 10 ⁻⁵ mol) of tris (pentafluorophenyl) borane, the following formula (H)

Is mixed with 112.2 g (2.6 × 10 ^-2 mol) of the compound represented by the following formula (B):

After slowly adding dropwise 27.2 g (6.6 × 10 ^-2 mol) of the silane represented by the formula, the mixture was stirred at 25 ° C. for 1 hour. Subsequently, water was added, and the lower fluorine compound layer was recovered by a liquid separation operation, and then washed with acetone. The lower layer of the fluorine compound after the washing is recovered again, and the remaining solvent is distilled off under reduced pressure to obtain the following formula (I)

105 g of a fluoropolyether group-containing polymer represented by the formula was obtained.

¹ H-NMR
_{δ0-0.2 (-OSi (C H 3)} 3) 48H
_{δ0.5-0.7 (-SiC H 2 CH 2 CH} 2 CH 3) 4H
_{δ0.8-1.0 (-SiCH 2 CH 2 CH 2} C H 3) 6H
_{δ1.2-1.4 (-SiCH 2 C H 2 C} H 2 CH 3) 8H
_{δ2.4-2.6 (-C H 2 CH = CH} 2) 8H
_{δ4.9-5.1 (-CH 2 CH = C H} 2) 8H
_{δ5.7-5.9 (-CH 2 C H = CH} 2) 4H

で表される化合物９０ｇ（１．７５×１０^-2ｍｏｌ）、１，３−ビス（トリフルオロメチル）ベンゼン９０ｇ、トリメトキシシラン１２．８ｇ（１０．５×１０^-2ｍｏｌ）、及び塩化白金酸／ビニルシロキサン錯体のトルエン溶液８．４×１０^-2ｇ（Ｐｔ単体として２．３×１０^-6ｍｏｌを含有）を混合し、８０℃で２４時間熟成させた。その後、溶剤及び未反応物を減圧留去し、液状の生成物９３ｇを得た。 In a reaction vessel, the following formula (I)

90 g ( 1.75 × 10 ⁻² mol) of the compound represented by the formula, 90 g of 1,3-bis (trifluoromethyl) benzene, 12.8 g ( 10.5 × 10 ⁻² mol) of trimethoxysilane, and chloride 8.4 × 10 ⁻² g (containing 2.3 × 10 ⁻⁶ mol of Pt alone) of a toluene solution of a platinate / vinylsiloxane complex was mixed and aged at 80 ° C. for 24 hours. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain 93 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
_{δ0-0.2 (-OSi (C H 3)} 3) 48H
_{δ0.5-0.7 (-SiC H 2 CH 2 CH} 2 CH 3, -CH 2 CH 2 C H 2 -Si (OCH 3) 3) 12H
_{δ0.8-1.0 (-SiCH 2 CH 2 CH 2} C H 3) 6H
_{δ1.3-1.4 (-SiCH 2 C H 2 C} H 2 CH 3) 8H
_{δ1.5-1.9 (-CH 2 C H 2 CH} 2 -Si (OCH 3) 3, -C H 2 CH 2 CH 2 -Si (OCH 3) 3) 16H
_{δ3.4-3.7 (-Si (OC H 3)} 3) 36H

で表される化合物３０ｇ（７．２×１０^-3ｍｏｌ）をゆっくりと滴下した後、２５℃で１時間撹拌した。その後、溶剤及び未反応物を減圧留去し、液状の生成物３１ｇを得た。 [Example 4]
30 g of 1,3-bis (trifluoromethyl) benzene, 3.0 × 10 ⁻² g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 8.2 × 10 ⁻⁷ mol as Pt alone) in a reaction vessel, 6.0 g (4.5 × 10 ^-2 mol) of tetramethyldisiloxane was mixed, and the following formula (K) was mixed.

After slowly adding dropwise 30 g ( 7.2 × 10 ⁻³ mol) of the compound represented by the formula, the mixture was stirred at 25 ° C. for 1 hour. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain 31 g of a liquid product.

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

¹ H-NMR
_{δ0-0.2 (-OSi (C H 3)} 3) 12H
_{δ0.5-0.7 (-OCH 2 CH 2 C H} 2 -Si) 2H
_{δ1.6-1.8 (-OCH 2 C H 2 CH} 2 -Si) 2H
_{δ3.5-3.6 (-OC H 2 CH 2 CH} 2 -Si) 2H
_{δ3.7-3.8 (-C 2 F 2 C H} 2 O-) 2H
δ4.7-4.8 (-Si- H ) 1H

で表される化合物１１．４ｇ（２．７×１０^-3ｍｏｌ）を混合し、下記式（Ｌ）

で表される化合物１１．７ｇ（２．７×１０^-3ｍｏｌ）をゆっくりと滴下した後、２５℃で１時間撹拌した。続いて、水を添加し、分液操作により下層であるフッ素化合物層を回収後、アセトンで洗浄した。洗浄後の下層であるフッ素化合物層を再び回収し、減圧下、残存溶剤を留去することで、下記式（Ｍ）

で表されるフルオロポリエーテル基含有ポリマー２０ｇを得た。 In a reaction vessel, 10 g of 1,3-bis (trifluoromethyl) benzene, 2.8 × 10 ⁻³ g of tris (pentafluorophenyl) borane ( 5.5 × 10 ⁻⁶ mol), and the following formula (A)

Is mixed with 11.4 g (2.7 × 10 ⁻³ mol) of the compound represented by the following formula (L)

After slowly adding dropwise 11.7 g (2.7 × 10 ⁻³ mol) of the compound represented by the formula, the mixture was stirred at 25 ° C. for 1 hour. Subsequently, water was added, and the lower fluorine compound layer was recovered by a liquid separation operation, and then washed with acetone. The lower layer of the fluorine compound after the washing is recovered again, and the remaining solvent is distilled off under reduced pressure, whereby the following formula (M) is obtained.

20 g of a fluoropolyether group-containing polymer represented by the formula was obtained.

¹ H-NMR
_{δ0-0.2 (-OSi (C H 3)} 2) 12H
_{δ0.5-0.7 (-OCH 2 CH 2 C H} 2 -Si) 2H
_{δ1.6-1.8 (-OCH 2 C H 2 CH} 2 -Si) 2H
_{δ2.5-2.7 (-C H 2 CH = CH} 2) 4H
_{δ3.4-3.6 (-OC H 2 CH 2 CH} 2 -Si) 2H
_{δ3.6-3.8 (-C 2 F 2 C H} 2 O-) 2H
_{δ5.0-5.2 (-CH 2 CH = C H} 2) 4H
_{δ5.7-5.9 (-CH 2 C H = CH} 2) 2H

で表される化合物１７．１ｇ（２．０×１０^-3ｍｏｌ）、１，３−ビス（トリフルオロメチル）ベンゼン１５ｇ、トリメトキシシラン０．７３ｇ（６．０×１０^-3ｍｏｌ）、及び塩化白金酸／ビニルシロキサン錯体のトルエン溶液２．０×１０^-2ｇ（Ｐｔ単体として５．３×１０^-7ｍｏｌを含有）を混合し、８０℃で２４時間熟成させた。その後、溶剤及び未反応物を減圧留去し、液状の生成物１４ｇを得た。 In a reaction vessel, the following formula (M)

17.1 g (2.0 × 10 ⁻³ mol) of the compound represented by the following formula, 15 g of 1,3-bis (trifluoromethyl) benzene, 0.73 g (6.0 × 10 ⁻³ mol) of trimethoxysilane, And 2.0 × 10 ⁻² g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 5.3 × 10 ⁻⁷ mol as Pt alone) and aged at 80 ° C. for 24 hours. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain 14 g of a liquid product.

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

¹ H-NMR
_{δ0-0.2 (-OSi (C H 3)} 2) 12H
_{δ0.5-0.7 (-OCH 2 CH 2 C H} 2 -Si, -CH 2 CH 2 C H 2 -Si (OCH 3) 3) 6H
_{δ1.4-2.0 (-OCH 2 C H 2 CH} 2 -Si, -C H 2 C H 2 CH 2 -Si (OCH 3) 3) 10H
_{δ3.3-3.8 (-C 2 F 2 C H} 2 O -, - OC H 2 CH 2 CH 2 -Si, -Si (OC H 3) 3) 22H

で表される化合物１０．１ｇ（２．４×１０^-3ｍｏｌ）を混合し、下記式（Ｏ）

で表される化合物１０．０ｇ（２．４×１０^-3ｍｏｌ）をゆっくりと滴下した後、６０℃で２０時間撹拌した。続いて、塩酸を添加し、分液操作により下層であるフッ素化合物層を回収後、アセトンで洗浄した。洗浄後の下層であるフッ素化合物層を再び回収し、減圧下、残存溶剤を留去することで、下記式（Ｐ）

で表されるフルオロポリエーテル基含有ポリマー１７ｇを得た。 [Example 5]
In a reaction vessel, 10 g of 1,3-bis (trifluoromethyl) benzene, 0.54 g (5.4 × 10 ⁻³ mol) of triethylamine, the following formula (A)

Is mixed with 10.1 g ( 2.4 × 10 ⁻³ mol) of the compound represented by the following formula (O)

After slowly adding dropwise 10.0 g (2.4 × 10 ⁻³ mol) of the compound represented by the formula, the mixture was stirred at 60 ° C. for 20 hours. Subsequently, hydrochloric acid was added, and the lower fluorine compound layer was recovered by a liquid separation operation, followed by washing with acetone. The lower layer of the fluorine compound after the washing is recovered again, and the remaining solvent is distilled off under reduced pressure to obtain the following formula (P)

17 g of a fluoropolyether group-containing polymer represented by the formula: was obtained.

¹ H-NMR
_{δ2.7-3.0 (-C H 2 CH = CH} 2) 4H
_{δ4.9-5.1 (-CH 2 CH = C H} 2) 4H
_{δ5.6-5.8 (-CH 2 C H = CH} 2) 2H

で表される化合物１６．７ｇ（２．０×１０^-3ｍｏｌ）、１，３−ビス（トリフルオロメチル）ベンゼン１５ｇ、トリメトキシシラン０．７３ｇ（６．０×１０^-3ｍｏｌ）、及び塩化白金酸／ビニルシロキサン錯体のトルエン溶液２．０×１０^-2ｇ（Ｐｔ単体として５．３×１０^-7ｍｏｌを含有）を混合し、８０℃で２４時間熟成させた。その後、溶剤及び未反応物を減圧留去し、液状の生成物１３ｇを得た。
In a reaction vessel, the following formula (P)

16.7 g (2.0 × 10 ⁻³ mol) of a compound represented by the following formula, 15 g of 1,3-bis (trifluoromethyl) benzene, 0.73 g (6.0 × 10 ⁻³ mol) of trimethoxysilane, And 2.0 × 10 ⁻² g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 5.3 × 10 ⁻⁷ mol as Pt alone) and aged at 80 ° C. for 24 hours. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain 13 g of a liquid product.

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

¹ H-NMR
_{δ0.5-0.7 (-OCH 2 CH 2 C H} 2 -Si) 4H
_{δ1.7-2.1 (-OCH 2 C H 2 CH} 2 -Si, -OC H 2 CH 2 CH 2 -Si) 8H
_{δ3.4-3.7 (-Si (OC H 3)} 3) 18H

[Comparative Example 1]
The following polymers were used as comparative examples.

Preparation of Surface Treatment Agent and Formation of Cured Film The fluoropolyether group-containing polymer-modified silane obtained in Examples 1, 2, and 4 and the polymer of Comparative Example 1 were adjusted to Novec 7200 (3M Co., Ltd.) so that the concentration became 20% by mass. In ethyl perfluorobutyl ether) to prepare a surface treating agent. 7 mg of each surface treating agent was vacuum-deposited on glass (Gorilla, manufactured by Corning) having 10 nm of SiO ₂ treated on the outermost surface (processing conditions: pressure: 2.0 × 10 ⁻² Pa, heating temperature: 700 ° C.), The composition was cured for 24 hours in an atmosphere at 25 ° C. and a humidity of 40% to form a cured film having a thickness of 10 nm.

Evaluation of water repellency [ Evaluation of initial water repellency]
The contact angle (water repellency) of the cured film to water was measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) for the glass having the cured film formed as described above. Initially, it showed good water repellency. Table 1 shows the results.

[Evaluation of dynamic friction coefficient]
The dynamic friction coefficient with respect to Bencott (made by Asahi Kasei Corporation) of the glass formed with the cured film prepared above was measured using a surface property tester 14FW (made by Shinto Kagaku) under the following conditions. Table 1 shows the results.
Contact area: 10mm x 35mm
Load: 100g

[Evaluation of slipperiness]
Ten panelists touched the glass on which the cured film formed as described above was formed with fingers, and the feeling of use was evaluated according to the following criteria, and the evaluation with the largest number of persons was evaluated as the slipperiness. Table 1 shows the results.
◎: Very good ○ +: Good ○: Normal ×: Poor

  In Examples 1, 2, and 4 in which a siloxane group or a fluoropolyether group was further introduced into the fluoropolyether group-containing polymer molecule, the kinetic friction coefficient was reduced as compared with Comparative Example 1 having a single chain, and the slipperiness was improved. You can check.

Claims (9)

The following general formula (1)

(Wherein, Rf _{is, CF 3 O- (CF 2 O} ) p1 - (C 2 F 4 O) p2 -C t F 2t - (In the formula, p1 5-100 integer, q1 is 5-100 In the formula, p1 + q1 is an integer of 10 to 105, and t is an integer of 1 to 3. Each repeating unit may be randomly bonded.) or _{-C t F 2t O- (CF 2} O) p1 - (C 2 F 4 O) p2 -C t F 2t - ( wherein, p1 is an integer of 5 to 100, q1 is an integer of 5 to 100, p1 + q1 is an integer of 10 to 105, and t is an integer of 1 to 3. Each repeating unit may be randomly bonded.) is a divalent fluorooxyalkylene group-containing polymer residue represented by the following formula: , Y is a divalent to hexavalent hydrocarbon group optionally having a siloxane bond and / or a silylene group, and R is An alkyl group or a phenyl group having 1 to 4 carbon atoms, X is a hydroxyl group or a hydrolyzable group, Q is a divalent organic group optionally having a siloxane bond and / or a silylene group, and R ′ Is a monovalent fluoroalkyl group, a monovalent fluorooxyalkylene group-containing polymer residue, an alkyl group having 1 to 4 carbon atoms or a phenyl group, n is an integer of 1 to 3, and m is 1 to 5 Is an integer, and α is 1 or 2.)
A fluoropolyether group-containing polymer-modified silane represented by the formula:   The fluoropolyether group-containing polymer-modified silane according to claim 1, wherein t is 1 or 2 in the Rf group of the formula (1).   The fluoropolyether group-containing polymer-modified silane according to claim 1, wherein t = 1 in the Rf group of the formula (1).   In the above formula (1), Y is an alkylene group having 3 to 10 carbon atoms, an alkylene group having 8 to 16 carbon atoms including a phenylene group, and an alkylene group having 2 to 10 carbon atoms is a silalkylene structure or a silarylene structure. Divalent group, a divalent group having 2 to 10 silicon atoms, and a divalent group having 2 to 10 carbon atoms bonded to a bond of a linear organopolysiloxane residue having 2 to 10 silicon atoms And at least one selected from the group consisting of divalent to tetravalent groups in which an alkylene group having 2 to 10 carbon atoms is bonded to a bond of a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms. The fluoropolyether group-containing polymer-modified silane according to any one of claims 1 to 3, which is one type of group.   In the above formula (1), X is each independently a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxy-substituted alkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, and 2 to 10 carbon atoms. The fluoropolyether group-containing polymer-modified silane according to any one of claims 1 to 4, wherein the silane is selected from the group consisting of an alkenyloxy group and a halogen atom. In the formula (1), Q is a divalent organic group represented by the following formula (4), wherein the fluoropolyether group-containing polymer is modified according to any one of claims 1 to 5. Silane.

(Wherein, R ″ is an alkylene group having 1 to 10 carbon atoms which may have any of ketone, ester, amide, ether, sulfide, amine and phenylene, or carbonyl group, and W is a silicon atom A linear divalent organo (poly) siloxane residue having 2 to 40 carbon atoms, having a siloxane bond having 3 to 40 silicon atoms bonded through an alkylene group having 1 to 4 carbon atoms; it may also be linear silalkylene group, and silarylene group may linear, which has a bonded silicon atoms that are 3-40 amino siloxane bonds and through an arylene group having 6 to 10 carbon atoms Wherein the organo (poly) siloxane residue, the silalkylene group, and the silarylene group may each be single or mixed, β is 0 or 1, and γ is 0 or 1. And β + γ is 1 or 2.) 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 the following formula.

(In the formula, 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 treatment agent comprising the fluoropolyether group-containing polymer-modified silane according to claim 1.   An article having a cured film of the surface treatment agent according to claim 8 on the surface.