JP6680350B2 - Fluoropolyether group-containing polymer-modified silane, surface treatment agent and article - Google Patents

Description

  TECHNICAL FIELD 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 water and oil repellency and abrasion resistance, and the silane and / or a portion thereof. The present invention relates to a surface treatment agent containing a (hydrolysis) condensate, and an article surface-treated with the surface treatment agent (that is, having a cured coating of the surface treatment agent on the surface).

  2. Description of the Related Art In recent years, the use of touch panels for screens, including displays for mobile phones, has accelerated. However, since the screen of the touch panel is exposed, there are many opportunities for direct contact with fingers, cheeks, and the like, and there is a problem that dirt such as sebum is easily attached. Therefore, there is an increasing demand year-on-year for technologies that make it difficult to attach fingerprints to the surface of the display in order to improve the appearance and visibility, and technologies that make it easier to remove stains, and the development of materials that can meet these requirements Is desired. In particular, since fingerprint stains easily adhere to the surface of the touch panel display, it is desired to provide a water / oil repellent layer. However, the conventional water- and oil-repellent layer has high water- and oil-repellency and is excellent in stain-wipeability, but there is a problem that the antifouling performance deteriorates during use.

  In general, a fluoropolyether group-containing compound has very small surface free energy, and therefore has water / oil repellency, chemical resistance, lubricity, releasability, stain resistance, and the like. Utilizing its properties, it is widely used industrially such as water and oil repellent antifouling agents for paper and fibers, lubricants for magnetic recording media, oil repellents for precision equipment, release agents, cosmetics, protective films, etc. ing. However, its properties mean that it is non-adhesive and non-adhesive to other base materials at the same time, and although it can be applied to the base material surface, it was difficult to adhere the coating. .

  On the other hand, a silane coupling agent is well known as a material for binding the surface of a substrate such as glass or cloth to an organic compound, and is widely used as a coating agent for the surface of various substrates. 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 to form a film. The coating film becomes a durable and strong coating film because the hydrolyzable silyl group is chemically / physically bonded to the surface of glass or metal.

  Therefore, by using a fluoropolyether group-containing polymer-modified silane in which a hydrolyzable silyl group is introduced into a fluoropolyether group-containing compound, it is easy to adhere to the surface of the base material, and the surface of the base material has water and oil repellency Compositions capable of forming a coating having chemical properties, lubricity, release properties, antifouling properties, etc. have been disclosed (Patent Documents 1 to 5: Japanese Patent Publication No. 2008-534696, Japanese Patent Publication No. 2008-537557). JP, 2012-072272A, JP 2012-157856A, JP 2013-136833A).

  A cured film such as 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 has slipperiness and releasability. However, in recent years, users' demands for wear resistance are high, and they have not been able to sufficiently exhibit the performances that satisfy the demands. Further, although the performance can be more easily exhibited by coating with a thick film, cloudiness (haze) occurs on the glass surface and the visibility is impaired.

Japanese Patent Publication No. 2008-534696 Japanese Patent Publication No. 2008-537557 JP, 2012-072272, A JP, 2012-157856, A JP, 2013-136833, A

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

  As a result of intensive studies to solve the above-mentioned object, the present inventors have used a fluoropolyether group-containing polymer modified silane represented by the general formula (1) described later in the fluoropolyether group-containing polymer modified silane. According to the present invention, a surface treatment agent containing the silane and / or its partial (hydrolyzed) condensate can form a cured coating having excellent water and oil repellency, abrasion resistance and visibility, and forms the present invention. Came to.

（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、Ｑはエーテル結合を含んでいてもよい炭素数２〜５の２価の炭化水素基であり、Ｙは、ケイ素原子、シリレン基及び／又はシロキサン結合を有してもよい２〜６価の炭化水素基であり、Ｒは独立に炭素数１〜４のアルキル基であり、Ｘは独立に水酸基又は加水分解性基であり、ｎは１〜３の整数であり、γは１〜５の整数であり、ｍは１〜５の整数であり、Ｒ’は炭素数１〜４のアルキル基であり、βは１〜３の整数であり、αは１又は２である。但し、Ｙが、ケイ素原子、シリレン基及び／又はシロキサン結合を有さない２価の炭化水素基であり、かつαが１である場合、β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αが１であり、Ｒｆ基が下記一般式（２）で表される１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ることを特徴とする〔１〕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、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、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く、ｄは１〜３の整数であり、該単位（-Ｃ_dＦ_2d-）は直鎖状でも分岐状であってもよい。）
〔３〕
前記式（１）のαが２であり、Ｒｆ基が下記一般式（３）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ることを特徴とする〔１〕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、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、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く、ｄは１〜３の整数であり、該単位（-Ｃ_dＦ_2d-）はそれぞれ独立に直鎖状でも分岐状であってもよい。）
〔４〕
前記式（１）において、Ｙが、炭素数３〜１０のアルキレン基（但し、αが１の場合、βは１又は２である。）、炭素数６〜８のアリーレン基を含むアルキレン基（但し、αが１の場合、βは１又は２である。）、アルキレン基相互がケイ素原子、シリレン基、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、及びケイ素原子数２〜１０個の直鎖状又はケイ素原子数３〜１０個の分岐状もしくは環状の２〜４価のオルガノポリシロキサン残基又はケイ素原子の結合手に、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〕
Ｙが、ケイ素原子、シリレン基及び／又はシロキサン結合を有してもよい２価の炭化水素基（但し、Ｙが、ケイ素原子、シリレン基及び／又はシロキサン結合を有さない２価の炭化水素基であり、かつαが１である場合、βは１又は２である。）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、
−ＣＨ₂ＯＣＨ₂−
である〔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。
〔７〕
前記式（１）において、Ｑが、
−ＣＨ₂ＯＣＨ₂−
であり、かつ、Ｙが、ケイ素原子、シリレン基及び／又はシロキサン結合を有さない２価の炭化水素基（但し、αが１の場合、βは１又は２である。）である〔６〕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。
〔８〕
前記式（１）において、Ｘがそれぞれ、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基からなる群より選ばれる少なくとも１種である〔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。
〔９〕
式（１）で表されるポリマー変性シランが、下記式のいずれかで表されるものである〔１〕〜〔６〕及び〔８〕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の整数であり、ｐ１＋ｑ１は１０〜１０５の整数である。）
〔１０〕
〔１〕〜〔９〕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及び／又はその部分（加水分解）縮合物を含む表面処理剤。
〔１１〕
〔１０〕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 silanes, surface treatment agents and articles.
[1]
The following general formula (1)

(In the formula, Rf is a monovalent or divalent fluorooxyalkylene group-containing polymer residue, Q is a divalent hydrocarbon group having 2 to 5 carbon atoms and optionally containing an ether bond, and Y is , A silicon atom, a silylene group and / or a divalent to hexavalent hydrocarbon group which may have a siloxane bond, R is independently an alkyl group having 1 to 4 carbon atoms, and X is independently a hydroxyl group or a hydrolyzed group. It is a decomposable group, n is an integer of 1 to 3, γ is an integer of 1 to 5, m is an integer of 1 to 5, R'is an alkyl group having 1 to 4 carbon atoms, β is an integer of 1 to 3 and α is 1 or 2. However, Y is a divalent hydrocarbon group having no silicon atom, silylene group and / or siloxane bond, and α is 1 , Then β is 1 or 2.)
Fluoropolyether group-containing polymer-modified silane represented by.
[2]
[Alpha] in the formula (1) is 1, and the Rf group is a monovalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (2). Ether group-containing polymer-modified silane.

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

(In the formula, p, q, r, and s are each an integer of 0 to 200 and are an integer of p + q + r + s = 3 to 200, and each repeating unit may be linear or branched, and each repeating unit is may be bonded randomly, d is an integer from 1 to 3, the unit (-C _d F _2d -) may be branched in each independently linear).
[4]
In the formula (1), Y is an alkylene group having 3 to 10 carbon atoms (however, when α is 1, β is 1 or 2) and an alkylene group containing an arylene group having 6 to 8 carbon atoms ( However, when α is 1, β is 1 or 2.) , alkylene groups are bonded to each other through a silicon atom, a silylene group, a silalkylene structure or a silarylene structure, and a silicon atom. number 2-10 straight or silicon divalent to tetravalent organopolysiloxane residue group or atom number 3-10 branched or cyclic in bonds of silicon atoms, alkylene group having 2 to 10 carbon atoms The fluoropolyether group-containing polymer-modified silane according to any one of [1] to [3], which is at least one group selected from the group consisting of divalent to tetravalent groups bonded to each other.
[5]
Y is a divalent hydrocarbon group which may have a silicon atom, a silylene group and / or a siloxane bond (provided that Y is a divalent hydrocarbon having no silicon atom, silylene group and / or a siloxane bond) A fluoropolyether group-containing polymer-modified silane according to any one of [1] to [4] , wherein β is 1 or 2 when α is 1 .
[6]
In the formula (1), Q is
-CH ₂ OCH ₂ -
The fluoropolyether group-containing polymer-modified silane according to any one of [1] to [5].
[7]
In the formula (1), Q is
-CH ₂ OCH ₂ -
And Y is a divalent hydrocarbon group having no silicon atom, silylene group and / or siloxane bond (provided that when α is 1, β is 1 or 2) [6. ] The fluoropolyether group-containing polymer-modified silane described above.
[8]
In the formula (1), X is a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms. And the fluoropolyether group-containing polymer-modified silane according to any one of [1] to [7], which is at least one selected from the group consisting of: and a halogen group.
[9]
The polymer-modified silane represented by the formula (1) is represented by any of the following formulas [1] to [6] and [8]. .

(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.)
[10]
A surface treating agent containing the fluoropolyether group-containing polymer-modified silane according to any one of [1] to [9] and / or a partial (hydrolyzed) condensate thereof.
[11]
An article having on its surface a cured coating of the surface treatment agent according to [10].

  Since the fluoropolyether group-containing polymer-modified silane of the present invention has a large number of reactive functional groups and ether linking groups, it has improved adhesion to a substrate and wettability, whereby the silane and / or its portion ( An article surface-treated with a surface treatment agent containing a (hydrolyzed) condensate has excellent water and oil repellency, abrasion resistance, and visibility.

（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、Ｑはエーテル結合を含んでいてもよい炭素数２〜６の２価の炭化水素基であり、Ｙはケイ素原子、シリレン基及び／又はシロキサン結合を有してもよい２〜６価の炭化水素基であり、Ｒは独立に炭素数１〜４のアルキル基であり、Ｘは独立に水酸基又は加水分解性基であり、ｎは１〜３の整数であり、γは１〜５の整数であり、ｍは１〜５の整数であり、Ｒ’は炭素数１〜４のアルキル基であり、βは１〜３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).

(In the formula, Rf is a monovalent or divalent fluorooxyalkylene group-containing polymer residue, Q is a divalent hydrocarbon group having 2 to 6 carbon atoms and optionally containing an ether bond, and Y is A silicon atom, a silylene group, and / or a divalent to hexavalent hydrocarbon group which may have a siloxane bond, R is independently an alkyl group having 1 to 4 carbon atoms, and X is independently a hydroxyl group or hydrolysis. Is a natural group, n is an integer of 1 to 3, γ is an integer of 1 to 5, m is an integer of 1 to 5, R ′ is an alkyl group having 1 to 4 carbon atoms, and β Is an integer of 1 to 3, and α is 1 or 2.)

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

（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、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く、ｄは１〜３の整数であり、該単位（−Ｃ_dＦ_2d−）は直鎖状でも分岐状であってもよい。）When α is 1, a monovalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (2) (hereinafter sometimes referred to as a monovalent fluorooxyalkyl group) is preferable as Rf. .

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

（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、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く、ｄは１〜３の整数であり、該単位（−Ｃ_dＦ_2d−）はそれぞれ独立に直鎖状でも分岐状であってもよい。）When α is 2, Rf is preferably a divalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (3) (hereinafter sometimes referred to as a divalent fluorooxyalkylene group). .

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

  In the above formulas (2) and (3), p, q, r, and s are each an integer of 0 to 200, preferably p is an integer of 5 to 100, q is an integer of 5 to 100, and r is 0 to 100. Integer, s is an integer of 0 to 100, p + q + r + s = an integer of 3 to 200, preferably an integer of 10 to 105, and each repeating unit may be linear or branched, and each repeating unit is May be randomly combined. More preferably, p + q is an integer of 10 to 105, particularly an integer of 15 to 60, and r = s = 0. When p + q + r + s is smaller than the above upper limit value, the adhesion and curability are good, and when it is larger than the above lower limit value, the characteristics of the fluoropolyether group can be sufficiently exhibited, which is preferable.

In the above formula (2), (3), d is an integer from 1 to 3, preferably 1 or 2, the unit (-C _d F _2d -) is branched in each independently represent a linear It may be.

（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 include the following.

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

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

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

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

Examples of the linear, branched, or cyclic divalent to hexavalent organopolysiloxane residue having 2 to 10 silicon atoms, preferably 2 to 5 silicon atoms include those shown below.

（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。）

(In the formula, 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. Is 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), Q is a divalent hydrocarbon group having 2 to 6 carbon atoms which may contain an ether bond. As Q, specifically, an alkylene group having 2 to 6 carbon atoms such as ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), and hexamethylene group, an ether bond Is an alkylene group having 2 to 6 carbon atoms such as ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), hexamethylene group, etc., preferably an ether bond Is an alkylene group having 2 or 3 carbon atoms, including

Specific examples of Q include the following groups.

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

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

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

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

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

（式中、ｐ１は５〜１００の整数、ｑ１は５〜１００の整数であり、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.)

Examples of the method for preparing the fluoropolyether group-containing polymer-modified silane represented by the above formula (1), where α is 1, include the following methods.
A fluorooxyalkyl group-containing polymer having preferably 2 or more (particularly 2 or 3) olefin moieties at one end of the molecular chain is used as a solvent, for example, a fluorine-based polymer such as 1,3-bis (trifluoromethyl) benzene. An organosilicon compound dissolved in a solvent and having a SiH group and a hydrolyzable terminal group (alkoxy group such as methoxy group) in a molecule such as trimethoxysilane, and a hydrosilylation reaction catalyst, for example, chloroplatinic acid / vinylsiloxane complex In the presence of a toluene solution of 40 to 120 ° C., preferably 60 to 100 ° C., more preferably about 80 ° C. for 1 to 48 hours, preferably 2 to 10 hours, more preferably about 5 hours, Hydrosilylation Addition reaction and aging.

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

  Incidentally, 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 As the above, an organosilicon compound which does not have a hydrolyzable terminal group and has two or more SiH groups is used. At that time, in the same manner as in the above method, a fluorooxyalkyl group-containing polymer having preferably 2 or more (particularly 2 or 3) olefin moieties at one end of the molecular chain and a hydrolyzable end group in the molecule are added. Reactant having not more than 2 or more (particularly 2 or 3) residual SiH groups at one end of a molecular chain by hydrosilylation addition reaction with an organosilicon compound having 2 or more SiH groups After the (intermediate) is produced, a residual SiH group at the polymer end of the reaction product (intermediate) and an organosilicon compound having an olefin moiety and a hydrolyzable end group in the molecule such as allyltrimethoxysilane are added. At a temperature of 40 to 120 ° C, preferably 60 to 100 ° C, more preferably about 80 ° C in the presence of a hydrosilylation reaction catalyst, for example, a toluene solution of a chloroplatinic acid / vinylsiloxane complex. 1 to 48 hours, preferably 2 to 10 hours, more preferably under conditions of about 5 hours, it is aged together to hydrosilylation addition reaction again.

（式中、Ｒｆ、Ｒ’、Ｑ、ｍ、βは上記と同じである。Ｚは２価炭化水素基である。）Here, examples of the fluorooxyalkyl group-containing polymer having an olefin moiety at one end of the molecular chain include fluorooxyalkyl group-containing polymers represented by the following general formula (4).

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

  In the above formula (4), Z is a divalent hydrocarbon group, preferably a divalent hydrocarbon group having 1 to 8 carbon atoms, particularly 1 to 4 carbon atoms. Specifically, a methylene group, an ethylene group, Propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), hexamethylene group, octamethylene group and other C1-8 alkylene groups, phenylene group and other C6-8 And an alkylene group containing an arylene group (for example, an alkylene / arylene group having 7 to 8 carbon atoms) and the like. Z is preferably a linear alkylene group having 1 to 4 carbon atoms.

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

（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。）

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

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

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

（式中、ｕ１は１〜２４の整数であり、ｒ１、ｐ１、ｑ１、ｐ１＋ｑ１は上記と同じである。）

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

The olefin-introducing agent used in the preparation of the fluorooxyalkyl group-containing polymer represented by the formula (4) is, for example, preferably 2 or more (particularly 2 or (3) olefin moieties and a sulfonic acid ester residue represented by —S (═O) ₂ O— at the other end.

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

Examples of the base used for preparing the fluorooxyalkyl group-containing polymer represented by the formula (4) include amines and alkali metal bases. Specifically, amines include triethylamine, Examples include diisopropylethylamine, pyridine, DBU, imidazole and the like. Examples of alkali metal bases include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, alkyllithium, potassium t-butoxide, lithium diisopropylamide, lithium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, potassium bis. (Trimethylsilyl) amide and the like can be mentioned.
The amount of the base used is 1 to 20 equivalents, more preferably 5 to 15 equivalents, and still more preferably about 9 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. Can be used.

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

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

  Then, the reaction is stopped, and the aqueous layer and the fluorine solvent layer are separated by liquid separation operation. By further washing the obtained fluorine solvent layer with an organic solvent and distilling off the solvent, the fluorooxyalkyl group-containing polymer represented by the formula (4) is obtained.

In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the above formula (1) and α is 1, the solvent used is preferably a fluorine-based solvent, and the fluorine-based solvent is 1,3-bis ( Trifluoromethyl) benzene, trifluoromethylbenzene, methylnonafluorobutyl ether, methylnonafluoroisobutyl ether, ethylnonafluorobutyl ether, ethylnonafluoroisobutyl ether, 1,1,1,2,3,4,4,5,5 , A hydrofluoroether (HFE) solvent such as 5-decafluoro-3-methoxy-2- (trifluoromethyl) pentane (manufactured by 3M, trade name: Novec series), composed of a completely fluorinated compound Perfluoro solvent (manufactured by 3M, trade name: Fluorinert series) ), And the like.
The amount of the solvent used is 10 to 300 parts by mass, preferably 50 to 150 parts by mass, and more preferably about 100 parts by mass with respect to 100 parts by mass of the fluorooxyalkyl group-containing polymer having an olefin moiety at one end of the molecular chain. be able to.

（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１〜５の整数、好ましくは１〜３の整数であり、ｉ＋ｊは２〜９の整数、好ましくは２〜４の整数である。）In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) and α is 1, the organosilicon compound having a SiH group and a hydrolyzable terminal group in the molecule is represented by the following general formula: The compounds represented by (5) to (8) are preferable.

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

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

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

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

（式中、Ｒ¹、Ｒ²、ｇ、ｊ、ｉ、ｉ＋ｊ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) where α is 1, 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 (9) to (11) are preferable.

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

  Examples of the organosilicon compound that does not have a hydrolyzable terminal group in the molecule and has two or more SiH groups include the compounds shown below.

  In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) where α is 1, a fluorooxyalkyl group-containing polymer having an olefin moiety at one end of the molecular chain and a hydrolyzable end group in the molecule , Which does not have a hydrolyzable terminal group in the molecule when it is reacted with an organosilicon compound having two or more SiH groups, and the amount of the organosilicon compound having two or more SiH groups is It is possible to use 7 to 30 equivalents, more preferably 10 to 20 equivalents, and still more preferably about 15 equivalents to 1 equivalent of the reactive terminal group of the fluorooxyalkyl group-containing polymer having an olefin moiety at the chain end.

（式中、Ｒ、Ｘ、ｎは上記と同じである。Ｕは単結合、又は炭素数１〜６の２価炭化水素基である。）Further, in the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) and α is 1, as the organosilicon compound having an olefin moiety and a hydrolyzable terminal group in the molecule, the following general formula is used. The compound represented by (12) is preferable.

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

  In the above formula (12), U is a single bond or a divalent hydrocarbon group having 1 to 6 carbon atoms, and specific examples of the divalent hydrocarbon group having 1 to 6 carbon atoms include a methylene group and an ethylene group. Examples include propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), alkylene group such as hexamethylene group, phenylene group, and the like. U is preferably a single bond or a methylene group.

  In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) where α is 1, a fluorooxyalkyl group-containing polymer having an olefin moiety at one end of the molecular chain and a hydrolyzable end group in the molecule Which does not have an olefin moiety and a hydrolyzable end group in the molecule and a reaction product of the organosilicon compound having two or more SiH groups are reacted with each other in the molecule. The amount of the organosilicon compound having a decomposable end group is such that the fluorooxyalkyl group-containing polymer having an olefin moiety at one end of the molecular chain and the molecule does not have a hydrolyzable end group and has two or more SiH groups. 3 to 9 equivalents, more preferably 5 to 7 equivalents, and still more preferably about 6 equivalents are used with respect to 1 equivalent of the reactive terminal group of the reaction product with the organosilicon compound. Door can be.

In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) and α is 1, the hydrosilylation reaction catalyst includes platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, and platinum chloride. Platinum group metal catalysts such as tetrakis (triphenylphosphine) palladium, chlorotris (triphenylphosphine) rhodium, etc., such as complexes of acids with olefins, aldehydes, vinyl siloxanes, acetylene alcohols and the like can be mentioned. Platinum compounds such as vinyl siloxane coordination compounds are preferred.
The amount of the hydrosilylation reaction catalyst used is a fluorooxyalkyl group-containing polymer having an olefin moiety at one end of the molecular chain, or an organic polymer having two or more SiH groups without a hydrolyzable end group in the polymer and 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 mass of the reaction product with the silicon 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。

Then, the solvent and unreacted materials are distilled off under reduced pressure to obtain the target compound.
For example, as a fluorooxyalkyl group-containing polymer having an olefin moiety at one end of the molecular chain, a compound represented by the following formula

And using trimethoxysilane 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 the method for preparing the fluoropolyether group-containing polymer-modified silane represented by the above formula (1) and α being 2 include the following methods.
A fluorooxyalkylene group-containing polymer having preferably 2 or more (particularly 2 or 3) olefin moieties at both ends of the molecular chain, and a solvent such as fluorine such as 1,3-bis (trifluoromethyl) benzene. An organosilicon compound having a SiH group and a hydrolyzable terminal group in a molecule such as trimethoxysilane is dissolved in a system solvent, and a hydrosilylation reaction catalyst, for example, in the presence of a toluene solution of a chloroplatinic acid / vinyl siloxane complex, is added at 40- A hydrosilylation addition reaction and aging are carried out at a temperature of 120 ° C., preferably 60 to 100 ° C., more preferably about 80 ° C. for 1 to 48 hours, preferably 2 to 10 hours, more preferably about 5 hours. .

Further, as another method for preparing the fluoropolyether group-containing polymer-modified silane represented by the above formula (1) and α is 2, the following method may be mentioned, for example.
A fluorooxyalkylene group-containing polymer having two or more (particularly two or three) olefin moieties at both ends of the molecular chain is preferably used as a solvent, for example, fluorine such as 1,3-bis (trifluoromethyl) benzene. An organic silicon compound having a SiH group and a hydrolyzable terminal group in a molecule such as trichlorosilane is dissolved in a system solvent, and a hydrosilylation reaction catalyst, for example, 40 to 120 in the presence of a toluene solution of chloroplatinic acid / vinyl siloxane complex. C., preferably 60 to 100.degree. C., more preferably about 80.degree. C., under conditions of 1 to 48 hours, preferably 2 to 10 hours, and more preferably about 5 hours. After that, the substituent on the silyl group is converted into, for example, a methoxy group.

  Incidentally, 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 As the above, an organosilicon compound which does not have a hydrolyzable terminal group and has two or more SiH groups is used. At that time, in the same manner as in the above method, a fluorooxyalkylene group-containing polymer having two or more (particularly two or three) olefin moieties at both terminals of the molecular chain and a hydrolyzable terminal group in the molecule are preferably used. Which has 2 or more SiH groups and has a hydrosilylation addition reaction with an organosilicon compound having 2 or more SiH groups, and preferably 2 or more (particularly 2 or 3) residual SiH groups at both ends of the molecular chain. After the product (intermediate) is formed, preferably at least two (particularly, two or three) SiH groups and molecules such as allyltrimethoxysilane remaining at the polymer ends of the reaction product (intermediate). An olefinic moiety and an organosilicon compound having a hydrolyzable terminal group therein, in the presence of a hydrosilylation reaction catalyst, for example, a toluene solution of a chloroplatinic acid / vinyl siloxane complex, At 20 ° C., preferably 60 to 100 ° C., more preferably about 80 ° C., for 1 to 48 hours, preferably 2 to 10 hours, more preferably about 5 hours, a hydrosilylation addition reaction is performed again and aging is performed. Let

（式中、Ｒｆ、Ｒ’、Ｑ、ｍ、Ｚ、βは上記と同じである。）Here, examples of the fluorooxyalkylene group-containing polymer having olefin moieties at both ends of the molecular chain include fluorooxyalkylene group-containing polymers represented by the following general formula (13).

(In the formula, Rf, R ′, Q, m, Z and β are the same as 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 (13) include those shown below. In each formula, the repeating number (or the degree of polymerization) of each repeating unit 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.)

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

  Examples of the fluorooxyalkylene group-containing polymer having hydroxyl groups at both ends of the molecular chain used for preparing the fluorooxyalkylene group-containing polymer represented by the formula (13) include the followings.

（式中、ｖ１は１〜２４の整数であり、ｕ１、ｐ１、ｑ１、ｐ１＋ｑ１は上記と同じである。）

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

As the olefin introducing agent used for preparing the fluorooxyalkylene group-containing polymer represented by the formula (13), for example, as shown below, preferably 2 or more (particularly 2 or (3) olefin moieties and a sulfonic acid ester residue represented by —S (═O) ₂ O— at the other end.

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

Examples of the base used for preparing the fluorooxyalkylene group-containing polymer represented by the formula (13) include amines and alkali metal bases. Specifically, amines include triethylamine, Examples include diisopropylethylamine, pyridine, DBU, imidazole and the like. Examples of alkali metal bases include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, alkyllithium, potassium t-butoxide, lithium diisopropylamide, lithium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, potassium bis. (Trimethylsilyl) amide and the like can be mentioned.
The amount of the base used is 1 to 20 equivalents, more preferably 5 to 15 equivalents, still more preferably about 9 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 formula (13), tetrabutylammonium halide, alkali metal halide or the like may be used as an additive for improving reactivity or as a phase transfer catalyst. Specific examples of the additive include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydrogen sulfate, sodium iodide, potassium iodide, cesium iodide, crown ether and the like. . These additives improve the reactivity by catalytically exchanging the halogen with the olefin introducing agent in the reaction system, and improve the reactivity by coordinating the crown ether with the metal.
The additive is used in an amount of 0.005 to 0.2 equivalent, and more preferably 0.01 to 0.2, 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. 15 equivalents, more preferably about 0.1 equivalents can be used.

A solvent may be used for the preparation of the fluorooxyalkylene group-containing polymer represented by the formula (13). The solvent is not necessarily used, but as the solvent to be used, fluorine-containing solvents such as 1,3-bis (trifluoromethyl) benzene, trifluoromethylbenzene, and other fluorine-containing aromatic hydrocarbon solvents, 1,1 , 1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2- (trifluoromethyl) pentane and other hydrofluoroether (HFE) -based solvents (3M, trade name: (Novec series), a perfluorinated solvent composed of a completely fluorinated compound (3M, trade name: Fluorinert series), and the like. Furthermore, as the organic solvent, dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetonitrile, THF or the like can be used. Also, water may be used.
The amount of the solvent used is 10 to 300 parts by mass, preferably 30 to 150 parts by mass, and more preferably about 50 parts by mass, relative to 100 parts by mass of the fluorooxyalkylene group-containing polymer having hydroxyl groups at both ends of the molecular chain. Parts can be used.

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

In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the above formula (1) and α is 2, the solvent used is preferably a fluorine-based solvent, and the fluorine-based solvent is 1,3-bis ( Trifluoromethyl) benzene, trifluoromethylbenzene, methylnonafluorobutyl ether, methylnonafluoroisobutyl ether, ethylnonafluorobutyl ether, ethylnonafluoroisobutyl ether, 1,1,1,2,3,4,4,5,5 , A hydrofluoroether (HFE) solvent such as 5-decafluoro-3-methoxy-2- (trifluoromethyl) pentane (manufactured by 3M, trade name: Novec series), composed of a completely fluorinated compound Perfluoro solvent (manufactured by 3M, trade name: Fluorinert series) ), And the like.
The amount of the solvent used is 10 to 300 parts by mass, preferably 50 to 150 parts by mass, and more preferably about 100 parts by mass, relative to 100 parts by mass of the fluorooxyalkylene group-containing polymer having olefin moieties at both ends of the molecular chain. Can be used.

  In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) and α is 2, the organosilicon compound having a SiH group and a hydrolyzable terminal group in the molecule is represented by the following general formula: The compounds represented by (5) to (8) are preferable.

（式中、Ｒ、Ｘ、ｎ、Ｒ¹、Ｒ²、Ｒ³、ｇ、ｉ、ｊ、ｉ＋ｊは上記と同じである。）

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

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

  In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) where α is 2, a fluorooxyalkylene group-containing polymer having olefin moieties at both ends of the molecular chain and a SiH group and a hydrolyzate in the molecule are prepared. The amount of the organosilicon compound having a SiH group and a hydrolyzable terminal group used in the reaction with the organosilicon compound having a decomposable terminal group is the amount of the fluorooxyalkylene group having an olefin moiety at each end of the molecular chain. It is possible to use 1 to 3 equivalents, more preferably 1.5 to 2.5 equivalents, still more preferably about 2 equivalents, relative to 1 equivalent of the reactive terminal groups of the contained polymer.

  Further, in the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) and α is 2, 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 (9) to (11) are preferable.

（式中、Ｒ¹、Ｒ²、ｇ、ｊ、ｉ、ｉ＋ｊは上記と同じである。）

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

  Examples of the organosilicon compound that does not have a hydrolyzable terminal group in the molecule and has two or more SiH groups include the compounds shown below.

  In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) where α is 2, a fluorooxyalkylene group-containing polymer having olefin moieties at both terminals of the molecular chain and a hydrolyzable terminal in the molecule The amount of the organosilicon compound which does not have a hydrolyzable terminal group and has 2 or more SiH groups in the molecule when it is reacted with an organosilicon compound which does not have a group and has 2 or more SiH groups is It can be used in an amount of 7 to 30 equivalents, more preferably 10 to 20 equivalents, still more preferably about 15 equivalents, relative to 1 equivalent of the reactive terminal group of the fluorooxyalkylene group-containing polymer having olefin moieties at both ends of the molecular chain. .

（式中、Ｒ、Ｘ、Ｕ、ｎ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) and α is 2, the organic silicon compound having an olefin moiety and a hydrolyzable terminal group in the molecule is represented by the following general formula: The compound represented by (12) is preferable.

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

  In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) where α is 2, a fluorooxyalkylene group-containing polymer having olefin moieties at both terminals of the molecular chain and a hydrolyzable terminal in the molecule An olefin moiety in the molecule when reacting a reaction product of an organosilicon compound having no group and having two or more SiH groups with an olefin moiety in the molecule and an organosilicon compound having a hydrolyzable terminal group The amount of the organosilicon compound having a hydrolyzable terminal group is the same as that of a fluorooxyalkylene group-containing polymer having olefin moieties at both ends of the molecular chain and a SiH group having 2 hydrolyzable terminal groups in the molecule. 3 to 9 equivalents, more preferably 5 to 7 equivalents, and still more preferably 1 equivalent to 1 equivalent of the reactive terminal group of the reaction product with the organosilicon compound. Ku can be used about 6 equivalents.

In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) where α is 2, the hydrosilylation reaction catalyst includes platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, and platinum chloride. Platinum group metal catalysts such as tetrakis (triphenylphosphine) palladium, chlorotris (triphenylphosphine) rhodium, etc., such as complexes of acids with olefins, aldehydes, vinyl siloxanes, acetylene alcohols and the like can be mentioned. Platinum compounds such as vinyl siloxane coordination compounds are preferred.
The amount of the hydrosilylation reaction catalyst used is a fluorooxyalkylene group-containing polymer having olefin moieties at both ends of the molecular chain, or a polymer having no hydrolyzable terminal groups and two or more SiH groups. It is used in an amount of 0.1 to 100 ppm, and more preferably 1 to 50 ppm in terms of transition metal (mass) based on the mass of the reaction product 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。

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

And using trimethoxysilane 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 fluoropolyether group-containing polymer modified silane. The surface treatment agent is obtained by condensing a hydroxyl group of the fluoropolyether group-containing polymer modified silane or a hydroxyl group obtained by partially hydrolyzing a terminal hydrolyzable group of the fluoropolyether group-containing polymer modified silane by a known method in advance. The thus obtained partial (hydrolyzed) condensate may be contained.

As the surface treatment agent, if necessary, a hydrolysis condensation catalyst such as an organic tin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organic titanium compound (tetra n-butyl titanate, etc.), an organic acid (acetic acid, Methanesulfonic acid, fluorine-modified carboxylic acid, etc.) and inorganic acids (hydrochloric acid, sulfuric acid, etc.) may be added. Among these, acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, and fluorine-modified carboxylic acid are particularly preferable.
The addition amount of the hydrolysis-condensation catalyst is a catalytic amount, and is usually 0.01 to 5 parts by mass, especially 0 to 100 parts by mass of the fluoropolyether group-containing polymer-modified silane and / or its partial (hydrolysis) condensate. 0.1 to 1 part by mass.

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

  The solvent may be a mixture of two or more thereof, and it is preferable that the fluoropolyether group-containing polymer-modified silane and its partial (hydrolysis) condensate are uniformly dissolved. The optimum concentration of the fluoropolyether group-containing polymer-modified silane and its partial (hydrolyzed) condensate to be dissolved in a solvent varies depending on the treatment method and may be an amount that can be easily weighed, but in the case of direct coating, It is preferably 0.01 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass, relative to 100 parts by mass in total of the solvent and the fluoropolyether group-containing polymer-modified silane (and its part (hydrolysis) condensate). In the case of performing the vapor deposition treatment, the amount is 1 to 100 parts by mass, particularly 3 to 30 parts by mass based on 100 parts by mass of the solvent and the fluoropolyether group-containing polymer-modified silane (and its partial (hydrolysis) condensate). Preferably there is.

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

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

  The 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 audios, game machines, eyeglass lenses, camera lenses, lens filters, sunglasses, Examples include medical devices such as gastrocameras, copying machines, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, antireflection films, and other optical articles. The surface-treating agent of the present invention can prevent fingerprints and sebum from adhering to the article and can impart scratch resistance, and thus is particularly useful as a water / oil repellent layer for a touch panel display, an antireflection film or the like. is there.

  Further, the surface treatment agent of the present invention, a bathtub, antifouling coating of sanitary products such as wash basins, window glass or tempered glass of automobiles, trains, aircraft, etc., antifouling coating of headlamp covers, etc., building materials for outer walls. Water and oil repellent coating, coating for preventing oil stains on kitchen building materials, antifouling for telephone boxes and anti-fingerprints for paper and graffiti, anti-fingerprint coating for works such as compact discs, anti-fingerprint coating for DVDs, etc. It is also useful as a mold release agent for paints, a paint additive, a resin modifier, a fluidity modifier or dispersibility modifier of an inorganic filler, a lubricity improver for tapes, films and the like.

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

で表される化合物２．９×１０^-2ｍｏｌ、下記式（Ｂ）

で表される化合物４．３×１０^-2ｍｏｌ、テトラブチルアンモニウム硫酸水素塩０．８９ｇ（２．６×１０^-3ｍｏｌ）を混合した。続いて、３０質量％水酸化ナトリウム水溶液３５ｇ（２．６×１０^-1ｍｏｌ）を添加した後、６０℃で２０時間加熱した。加熱終了後、室温まで冷却し、塩酸水溶液を滴下した。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、残存溶剤を留去した。上記操作を再度行うことで、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。
なお、式（Ｃ）で表されるフルオロポリエーテル基含有ポリマーのＮＭＲによる分子構造の解析結果は次の通りである。 [ Reference Example 1]
In the reaction vessel, the following formula (A)

2.9 × 10 ^-2 mol of the compound represented by the following formula (B)

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

103 g of a fluoropolyether group-containing polymer represented by
The analysis results of the molecular structure of the fluoropolyether group-containing polymer represented by the formula (C) by NMR are as follows.

¹ H-NMR
_{δ3.4-3.5 (C-C H 2 -O} -CH 2 CH = CH 2) 6H
_{δ3.6-3.7 (-CF 2 -CH 2 -O-} C H 2 -C) 2H
_{δ3.7-3.8 (-CF 2 -C H 2 -O} -C H 2 -C) 2H
δ 3.8-3.9 (C-CH ₂ -O-C H ₂ CH = CH ₂ ) 6H
δ 5.0-5.2 (C-CH ₂ -O-CH ₂ CH = C H ₂ ) 6H
_{δ5.7-5.9 (C-CH 2 -O-} CH 2 C H = CH 2) 3H

で表される化合物１．５×１０^-2ｍｏｌ（即ち、末端アリルエーテル基；４．５×１０^-2ｍｏｌに相当）、１，３−ビス（トリフルオロメチル）ベンゼン５０ｇ、トリメトキシシラン１１ｇ（９．０×１０^-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５．０×１０^-2ｇ（Ｐｔ単体として１．５×１０^-7ｍｏｌを含有）を混合し、８０℃で５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５５ｇを得た。 The following formula (C) obtained above was placed in a reaction vessel.

Compound represented by 1 . 5 × 10 ^-2 mol (i.e., terminal allyl ether group; equivalent to 4.5 × 10 ^-2 mol), 1,3- bis (trifluoromethyl) benzene 50 g, trimethoxysilane 11g (9.0 × 10 ^{- 2} mol) and 5.0 × 10 ^-2 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 1.5 × 10 ^-7 mol of Pt as a simple substance) were mixed and aged at 80 ° C. for 5 hours. . Then, the solvent and unreacted materials were distilled off under reduced pressure to obtain 55 g of a liquid product.

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

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

で表される化合物２．９×１０^-2ｍｏｌ、下記式（Ｅ）

で表される化合物４．３×１０^-2ｍｏｌ、テトラブチルアンモニウム硫酸水素塩０．８９ｇ（２．６×１０^-3ｍｏｌ）を混合した。続いて、３０質量％水酸化ナトリウム水溶液３５ｇ（２．６×１０^-1ｍｏｌ）を添加した後、６０℃で２０時間加熱した。加熱終了後、室温まで冷却し、塩酸水溶液を滴下した。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、残存溶剤を留去した。上記操作を再度行うことで、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１０１ｇを得た。
なお、式（Ｆ）で表されるフルオロポリエーテル基含有ポリマーのＮＭＲによる分子構造の解析結果は次の通りである。 [Example 1 ]
In the reaction vessel, the following formula (A)

2.9 × 10 ^-2 mol of the compound represented by the following formula (E)

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

101 g of a fluoropolyether group-containing polymer represented by
The analysis results of the molecular structure of the fluoropolyether group-containing polymer represented by the formula (F) by NMR are as follows.

¹ H-NMR
_{δ0.7-0.9 (-CH 2 C H 3)} 3H
_{δ1.3-1.5 (-C H 2 CH 3)} 2H
_{δ3.2-3.2 (C-C H 2 -O} -CH 2 CH = CH 2) 4H
_{δ3.4-3.5 (-CF 2 -CH 2 -O-} C H 2 -C) 2H
_{δ3.6-3.7 (-CF 2 -C H 2 -O} -C H 2 -C) 2H
δ 3.8-3.9 (C-CH ₂ -O-C H ₂ CH = CH ₂ ) 4H
_{δ4.9-5.2 (C-CH 2 -O-} CH 2 CH = C H 2) 4H
_{δ5.7-5.8 (C-CH 2 -O-} CH 2 C H = CH 2) 2H

で表される化合物１．５×１０^-2ｍｏｌ（即ち、末端アリルエーテル基；３．０×１０^-2ｍｏｌに相当）、１，３−ビス（トリフルオロメチル）ベンゼン５０ｇ、トリメトキシシラン７．３ｇ（６．０×１０^-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５．０×１０^-2ｇ（Ｐｔ単体として１．５×１０^-7ｍｏｌを含有）を混合し、８０℃で５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５２ｇを得た。 The following formula (F) obtained above was placed in a reaction vessel.

Compound represented by 1 . 5 × 10 ⁻² mol (that is, a terminal allyl ether group; corresponding to 3.0 × 10 ⁻² mol), 50 g of 1,3-bis (trifluoromethyl) benzene, and 7.3 g of trimethoxysilane (6.0 × 10 ⁻² mol) and 5.0 × 10 ⁻² g of toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 1.5 × 10 ⁻⁷ mol of Pt as a simple substance), and aging at 80 ° C. for 5 hours Let Then, the solvent and unreacted materials were distilled off under reduced pressure to obtain 52 g of a liquid product.

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

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

で表される化合物２．７×１０^-2ｍｏｌ（即ち、末端ヒドロキシ基；５．４×１０^-2ｍｏｌに相当）、下記式（Ｂ）

で表される化合物８．１×１０^-2ｍｏｌ、テトラブチルアンモニウム硫酸水素塩１．７ｇ（４．９×１０^-3ｍｏｌ）を混合した。続いて、３０質量％水酸化ナトリウム水溶液６５ｇ（４．９×１０^-1ｍｏｌ）を添加した後、６０℃で２０時間加熱した。加熱終了後、室温まで冷却し、塩酸水溶液を滴下した。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、残存溶剤を留去した。上記操作を再度行うことで、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１０７ｇを得た。
なお、式（Ｉ）で表されるフルオロポリエーテル基含有ポリマーのＮＭＲによる分子構造の解析結果は次の通りである。 [Example 2 ]
In the reaction vessel, the following formula (H)

2.7 × 10 ^-2 mol of the compound represented by (that is, a terminal hydroxy group; corresponding to 5.4 × 10 ^-2 mol), the following formula (B)

The compound represented by 8 × 10 ⁻² mol and tetrabutylammonium hydrogen sulfate 1.7 g (4.9 × 10 ⁻³ mol) were mixed. Subsequently, 65 g (4.9 × 10 ⁻¹ mol) of 30 mass% sodium hydroxide aqueous solution was added, and then the mixture was heated at 60 ° C. for 20 hours. After completion of heating, the mixture was cooled to room temperature and a hydrochloric acid aqueous solution was added dropwise. The lower layer, the fluorine compound layer, was recovered by a liquid separation operation, and then washed with acetone. The lower fluorine compound layer after the washing was recovered again, and the residual solvent was distilled off under reduced pressure. By repeating the above operation, the following formula (I)

107 g of a fluoropolyether group-containing polymer represented by
The analysis results of the molecular structure of the fluoropolyether group-containing polymer represented by the formula (I) by NMR are as follows.

¹ H-NMR
_{δ3.4-3.5 (C-C H 2 -O} -CH 2 CH = CH 2) 12H
_{δ3.6-3.7 (-CF 2 -CH 2 -O-} C H 2 -C) 4H
_{δ3.7-3.8 (-CF 2 -C H 2 -O} -C H 2 -C) 4H
δ 3.8-3.9 (C-CH ₂ -O-C H ₂ CH = CH ₂ ) 12H
δ 4.9-5.1 (C-CH ₂ -O-CH ₂ CH = C H ₂ ) 12H
_{δ5.7-5.9 (C-CH 2 -O-} CH 2 C H = CH 2) 6H

で表される化合物１．３３×１０^-2ｍｏｌ（即ち、末端アリルエーテル基；８．０×１０^-2ｍｏｌに相当）、１，３−ビス（トリフルオロメチル）ベンゼン５０ｇ、トリメトキシシラン２０ｇ（１．６×１０^-1ｍｏｌ）、及び塩化白金酸／ビニルシロキサン錯体のトルエン溶液５．０×１０^-2ｇ（Ｐｔ単体として１．５×１０^-7ｍｏｌを含有）を混合し、８０℃で５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６０ｇを得た。
The following formula (I) obtained above was placed in a reaction vessel.

Compound represented by 1 . 33 × 10 ⁻² mol (that is, corresponding to a terminal allyl ether group; 8.0 × 10 ⁻² mol), 50 g of 1,3-bis (trifluoromethyl) benzene, 20 g of trimethoxysilane (1.6 × 10 ^{− 1} mol) and 5.0 × 10 ⁻² g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 1.5 × 10 ⁻⁷ mol as a Pt simple substance) were mixed and aged at 80 ° C. for 5 hours. . Then, the solvent and unreacted materials were distilled off under reduced pressure to obtain 60 g of a liquid product.

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

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

[Comparative Example 1]
As Comparative Example 1, the following polymers were used.

[Comparative Example 2]
As Comparative Example 2, the following polymers were used.

Preparation of surface treatment agent and formation of cured film
Among the fluoropolyether group-containing polymer-modified silanes obtained in Reference Example 1 and Examples 1 and 2 , the fluoropolyether group-containing polymer-modified silanes obtained in Reference Example 1 and Example 1 were used. Was subjected to the following evaluation. Namely, Reference Example 1, a fluoropolyether group containing polymer-modified silanes and polymers of Comparative Examples 1 and 2 obtained in Example 1, Novec to a concentration of 20 mass% 7200 (3M Co., ethyl perfluorobutyl ether ) Was dissolved in the solution to prepare a surface treatment agent.

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

[Thick film coating]
10 mg of each surface treatment agent was vacuum-deposited on a glass (Gorilla manufactured by Corning Co., Ltd.) whose surface was treated with 10 nm of SiO ₂ (treatment condition: pressure: 2.0 × 10 ⁻² Pa, heating temperature: 700 ° C.), It was cured for 12 hours in an atmosphere of 25 ° C. and a humidity of 40% to form a cured film having a film thickness of 14 nm.

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

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

[Evaluation of haze value]
For the glass (for haze value evaluation) on which a cured film was formed by thin film coating and thick film coating as described above, a haze meter (NDH-5000) (manufactured by Nippon Denshoku Industries Co., Ltd.) was used in accordance with JIS K 7136: 2000. And the haze value was measured. The results (haze value) are shown in Tables 1 and 2. Haze is 0.3 or more, and haze is visually confirmed. At the time of coating a thin film (7 nm), the haze value was as low as 0.3 or less in all of the reference examples, examples and comparative examples. On the other hand, at the time of thick film (14 nm) coating of Reference Example 1, the compound of Example 1, the wettability of the substrate by having a plurality of ether linking group is a polar group in the molecule is improved, reference It was confirmed that the cured film of the surface treatment agent using the compounds of Examples 1 and 1 had a haze value of 0.3 or less as compared with the comparative example, and the visibility was improved.

Claims (11)

The following general formula (1)

(In the formula, Rf is a monovalent or divalent fluorooxyalkylene group-containing polymer residue, Q is a divalent hydrocarbon group having 2 to 5 carbon atoms and optionally containing an ether bond, and Y is , A silicon atom, a silylene group and / or a divalent to hexavalent hydrocarbon group which may have a siloxane bond, R is independently an alkyl group having 1 to 4 carbon atoms, and X is independently a hydroxyl group or a hydrolyzed group. It is a decomposable group, n is an integer of 1 to 3, γ is an integer of 1 to 5, m is an integer of 1 to 5, R'is an alkyl group having 1 to 4 carbon atoms, β is an integer of 1 to 3 and α is 1 or 2. However, Y is a divalent hydrocarbon group having no silicon atom, silylene group and / or siloxane bond, and α is 1 , Then β is 1 or 2.)
Fluoropolyether group-containing polymer-modified silane represented by. The α in the formula (1) is 1, and the Rf group is a monovalent fluorooxyalkylene group-containing polymer residue represented by the following general formula (2). Ether group-containing polymer-modified silane.

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

(In the formula, p, q, r, and s are each an integer of 0 to 200 and are an integer of p + q + r + s = 3 to 200, and each repeating unit may be linear or branched, and each repeating unit is may be bonded randomly, d is an integer from 1 to 3, the unit (-C _d F _2d -) may be branched in each independently linear). In the formula (1), Y is an alkylene group having 3 to 10 carbon atoms (however, when α is 1, β is 1 or 2) and an alkylene group containing an arylene group having 6 to 8 carbon atoms ( However, when α is 1, β is 1 or 2.) , alkylene groups are bonded to each other through a silicon atom, a silylene group, a silalkylene structure or a silarylene structure, and a silicon atom. number 2-10 straight or silicon divalent to tetravalent organopolysiloxane residue group or atom number 3-10 branched or cyclic in bonds of silicon atoms, alkylene group having 2 to 10 carbon atoms The fluoropolyether group-containing polymer-modified silane according to any one of claims 1 to 3, which is at least one kind of group selected from the group consisting of divalent to tetravalent groups bonded to each other. Y is a divalent hydrocarbon group which may have a silicon atom, a silylene group and / or a siloxane bond (provided that Y is a divalent hydrocarbon having no silicon atom, silylene group and / or a siloxane bond) Is a group, and when α is 1, β is 1 or 2.) The fluoropolyether group-containing polymer-modified silane according to any one of claims 1 to 4. In the formula (1), Q is
-CH ₂ OCH ₂ -
The fluoropolyether group-containing polymer-modified silane according to any one of claims 1 to 5. In the formula (1), Q is
-CH ₂ OCH ₂ -
And Y is a divalent hydrocarbon group having no silicon atom, silylene group and / or siloxane bond (provided that when α is 1, β is 1 or 2). The fluoropolyether group-containing polymer-modified silane according to item 6.   In the above formula (1), X is a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms. And at least one selected from the group consisting of: and a halogen group, The fluoropolyether group-containing polymer-modified silane according to any one of claims 1 to 7. The fluoropolyether group-containing polymer-modified silane according to any one of claims 1 to 6 and 8, wherein the polymer-modified silane represented by the formula (1) is represented by any of the following formulas.

(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 any one of claims 1 to 9 and / or a partial (hydrolysis) condensate thereof.   An article having on its surface a cured coating of the surface treatment agent according to claim 10.