JPWO2017077834A1 - Fluoropolyether group-containing polymer-modified organosilicon compound, surface treatment agent and article - Google Patents

Abstract

［Ｒｆはフルオロオキシアルキル基又はフルオロオキシアルキレン基含有ポリマー残基、Ｙは２価炭化水素基、Ｑは２価オルガノシロキサン残基、シルアルキレン基又はシルアリーレン基、Ｘは水素原子、アルキル基又はフェニル基、Ｚは水素原子、下式
−ＳｉＲ₃
（Ｒはアルキル基又はフェニル基。）
で表される基、又は下式
−Ｗ−Ｑ’−Ｘ
（Ｗは単結合又は２価炭化水素基、Ｑ’はシロキサン結合、シルアルキレン構造及びシルアリーレン構造から選ばれる構造を有する２価の基。）
で表される基、αは１又は２。］
で表されるフルオロポリエーテル基含有ポリマー変性有機ケイ素化合物。Fluoropolyether group-containing polymer-modified organosilicon compound capable of forming a water- and oil-repellent layer with excellent abrasion resistance under mild conditions, a surface treatment agent containing the compound, and a surface treatment with the treatment agent Provide goods.
The following general formula (1)

[Rf is a fluorooxyalkyl group- or fluorooxyalkylene group-containing polymer residue, Y is a divalent hydrocarbon group, Q is a divalent organosiloxane residue, silalkylene group or silarylene group, X is a hydrogen atom, alkyl group or A phenyl group, Z is a hydrogen atom, -SiR ₃
(R is an alkyl group or a phenyl group.)
Or a group represented by the following formula: -WQ'-X
(W is a single bond or a divalent hydrocarbon group, Q ′ is a divalent group having a structure selected from a siloxane bond, a silalkylene structure and a silarylene structure.)
And α is 1 or 2. ]
A fluoropolyether group-containing polymer-modified organosilicon compound represented by:

Description

  The present invention relates to a fluoropolyether group-containing polymer-modified organosilicon compound, a surface treatment agent containing the organosilicon compound, and an article surface-treated with the surface treatment agent.

  In recent years, the touch panel of the screen including the display of the mobile phone has been accelerated. However, the touch panel has a bare screen, and there are many occasions where fingers, cheeks and the like are directly attached, and it is a problem that dirt such as sebum is easily attached. Therefore, the demand for technology that makes it difficult to attach fingerprints to the surface of the display to improve the appearance and visibility, and technology that makes it easier to remove dirt is increasing year by year, and the development of materials that can meet these requirements has been developed. It is desired. In particular, since the surface of the touch panel display is likely to be contaminated with fingerprints, it is desired to provide a water / oil repellent layer. However, the conventional water / oil repellent layer has high water / oil repellency and excellent dirt wiping property, but has a problem that the antifouling performance deteriorates during use. In addition, performance may vary depending on the coating method, and adhesion may be inferior depending on the substrate to be coated. Furthermore, many of the surface treatment agents used so far show good surface properties for glass, but surface properties such as adhesion, water and oil repellency, and wear resistance are sufficient for the resin surface. There was nothing to show.

  In general, a fluoropolyether group-containing compound has very small 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 for water and oil repellent and antifouling agents such as paper and fiber, lubricants for magnetic recording media, oil repellents for precision equipment, mold release agents, cosmetics, and protective films. ing. However, the property means that it is non-adhesive and non-adhesive to other substrates at the same time, and even if it can be applied to the surface of the substrate, it was difficult to make the film adhere to it. .

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

  Therefore, by using a fluoropolyether group-containing polymer-modified silane in which a hydrolyzable silyl group is introduced into a fluoropolyether group-containing compound, it is easy to adhere to the substrate surface, and the substrate surface has water and oil repellency, resistance to water. A composition capable of forming a film having chemical properties, lubricity, releasability, antifouling properties and the like is disclosed (Patent Documents 1 to 8: JP 2003-238777 A, Patent 2860979, Patent No. 4672095, JP-T 2008-534696, JP-T 2008-537557, JP 2012-072722, JP 2012-157856, JP 2013-136833).

  When the substrate is surface-treated with the composition containing the above-mentioned fluoropolyether group-containing polymer-modified silane, a film is formed on the substrate using various coating methods. In the step of hydrolyzing and curing the film, the hydrolysis reaction is promoted by high temperature conditions such as 80 ° C. and 120 ° C. and under humidification. Moreover, a cured film can be formed by reacting gradually with moisture in the air even at room temperature. However, the curing process has a problem that it may become a rate-limiting factor (delay factor) in manufacturing, such as requiring high-temperature humidification conditions and taking time when curing at room temperature. Furthermore, a film (water / oil repellent layer) cured in a short time under a mild condition such as room temperature curing has a problem that the anti-fouling performance deteriorates during wear resistance and use.

  In Patent Document 9 (Japanese Patent Application Laid-Open No. 2008-144144), film formation is performed in a short time under mild conditions by adding fluorine-containing carboxylic acid as a curing catalyst in the coating composition to promote curing. . However, if the amount of the catalyst is reduced, the wear resistance is inferior, and if the amount of the catalyst is increased, the initial performance is lowered. In addition, there is a high possibility that a carboxyl group which is a polar group appears on the outermost surface of the film, and in that case, the performance is lowered.

  Patent Document 10 (Japanese Patent Application Laid-Open No. 2004-145283) proposes a fluoropolyalkylene ether group-containing silane. The lens treated with the fluoropolyalkylene ether group-containing silane is excellent in oil repellency and fingerprint wiping, but has insufficient wear resistance.

JP 2003-238777 A Japanese Patent No. 2860979 Japanese Patent No. 4672095 Special table 2008-534696 gazette JP 2008-537557 A JP 2012-072272 A JP 2012-157856 A JP 2013-136833 A JP 2008-144144 A JP 2004-145283 A

  The present invention has been made in view of the above circumstances, and particularly on the resin surface, a fluoropolyether group capable of forming a water- and oil-repellent layer having excellent wear resistance even in a short time under mild conditions such as room temperature. It is an object of the present invention to provide a containing polymer-modified organosilicon compound, a surface treatment agent containing the organosilicon compound, and an article surface-treated with the surface treatment agent.

  As a result of intensive studies to solve the above-mentioned object, the present inventors have found that the surface treatment agent using the fluoropolyether group-containing polymer-modified organosilicon compound represented by the general formula (1) described below has a terminal functional group. Even if it does not exist, it has been found that a water- and oil-repellent layer excellent in abrasion resistance can be formed on a resin product such as a resin film or a plastic lens even under a mild condition such as room temperature. It came to.

［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は独立に２価の炭化水素基であり、Ｑは独立に２価の直鎖状もしくは環状オルガノシロキサン残基、シルアルキレン基又はシルアリーレン基であり、Ｘは独立に水素原子、炭素数１〜４のアルキル基又はフェニル基であり、Ｚは独立に水素原子、下記式
−ＳｉＲ₃
（式中、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る。）
で表される基、又は下記式
−Ｗ−Ｑ’−Ｘ
（式中、Ｘは上記と同じであり、Ｗは単結合又は２価の炭化水素基であり、Ｑ’はシロキサン結合、シルアルキレン構造及びシルアリーレン構造から選ばれる構造を有する２価の基である。）
で表される基であり、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有機ケイ素化合物。
〔２〕
前記式（１）において、αが１であり、Ｒｆ基が下記一般式（２）で表される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有機ケイ素化合物。

（式中、ｐ、ｑ、ｒ、ｓはそれぞれ０〜２００の整数で、ｐ＋ｑ＋ｒ＋ｓ＝３〜２００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、該単位は直鎖状でも分岐状であってもよい。）
〔３〕
前記式（１）において、αが２であり、Ｒｆ基が下記一般式（３）で表される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有機ケイ素化合物。

（式中、ｐ、ｑ、ｒ、ｓはそれぞれ０〜２００の整数で、ｐ＋ｑ＋ｒ＋ｓ＝３〜２００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、該単位は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有機ケイ素化合物。
〔５〕
前記式（１）において、Ｑが、下記式で示される基から選ばれる基である〔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有機ケイ素化合物。

（式中、Ｘは上記と同じであり、Ｒ¹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、Ｒ²は炭素数１〜４のアルキレン基又は炭素数６〜１２のアリーレン基である。ｇは１〜２０の整数であり、ｊは１〜８の整数である。）
〔６〕
前記式（１）において、Ｚが、水素原子、及び下記に示す基より選ばれる基である〔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有機ケイ素化合物。

（式中、ｇ１は２〜２０の整数であり、ｅは０〜３の整数である。）
〔７〕
上記式（１）で表されるフルオロポリエーテル基含有ポリマー変性有機ケイ素化合物が、下記式のいずれかで表されるものである〔１〕〜〔６〕のいずれか１項に記載のフルオロポリエーテル基含有ポリマー変性有機ケイ素化合物。

（式中、Ｚは上記と同じであり、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。ｇ１は２〜２０の整数であり、ｅは０〜３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有機ケイ素化合物を含む表面処理剤。
〔９〕
表面処理剤が、更に下記一般式（４）

（式中、Ａは末端が−ＣＦ₃基である１価のフッ素含有基であり、Ｒｆ’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る。）
で表されるフルオロポリエーテル基含有ポリマーを含有することを特徴とする〔８〕に記載の表面処理剤。
〔１０〕
〔９〕記載の表面処理剤で表面処理された物品。Accordingly, the present invention provides the following fluoropolyether group-containing polymer-modified organosilicon compound, surface treatment agent and article.
[1]
The following general formula (1)

[Wherein Rf is a monovalent fluorooxyalkyl group or divalent fluorooxyalkylene group-containing polymer residue, Y is independently a divalent hydrocarbon group, and Q is independently a divalent linear chain. Or a cyclic organosiloxane residue, a silalkylene group or a silarylene group, X is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, Z is independently a hydrogen atom, _Three
(In the formula, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group.)
Or a group represented by the following formula -WQ'-X
Wherein X is the same as above, W is a single bond or a divalent hydrocarbon group, Q ′ is a divalent group having a structure selected from a siloxane bond, a silalkylene structure and a silarylene structure. is there.)
And α is 1 or 2. ]
A fluoropolyether group-containing polymer-modified organosilicon compound represented by:
[2]
In the formula (1), α is 1, and the Rf group is a group represented by the following general formula (2). The fluoropolyether group-containing polymer-modified organosilicon compound according to [1].

(In the formula, p, q, r, and s are each an integer of 0 to 200, and p + q + r + s = 3 to 200, each repeating unit may be linear or branched, and each repeating unit is randomly selected. And d is an integer of 1 to 3, and the unit may be linear or branched.)
[3]
In the formula (1), α is 2, and the Rf group is a group represented by the following general formula (3). The fluoropolyether group-containing polymer-modified organosilicon compound according to [1].

(In the formula, p, q, r, and s are each an integer of 0 to 200, and p + q + r + s = 3 to 200, each repeating unit may be linear or branched, and each repeating unit is randomly selected. And d is an integer of 1 to 3, and the unit may be linear or branched.)
[4]
The fluoropolyether group-containing polymer-modified organosilicon compound according to any one of [1] to [3], wherein in the formula (1), Y is an alkylene group having 3 to 10 carbon atoms.
[5]
In the formula (1), the fluoropolyether group-containing polymer-modified organosilicon compound according to any one of [1] to [4], wherein Q is a group selected from the groups represented by the following formulae.

(In the formula, X is the same as above, R ¹ is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ² is an alkylene group having 1 to 4 carbon atoms or an arylene having 6 to 12 carbon atoms. (G is an integer of 1 to 20, and j is an integer of 1 to 8.)
[6]
The fluoropolyether group-containing polymer-modified organosilicon compound according to any one of [1] to [5], wherein in the formula (1), Z is a hydrogen atom and a group selected from the following groups.

(In the formula, g1 is an integer of 2 to 20, and e is an integer of 0 to 3.)
[7]
The fluoropolyether according to any one of [1] to [6], wherein the fluoropolyether group-containing polymer-modified organosilicon compound represented by the formula (1) is represented by any of the following formulas: Ether group-containing polymer-modified organosilicon compound.

(In the formula, Z is the same as above, 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, g1 is an integer of 2 to 20, e Is an integer from 0 to 3.)
[8]
[1] A surface treatment agent comprising the fluoropolyether group-containing polymer-modified organosilicon compound according to any one of [1] to [7].
[9]
The surface treatment agent is further represented by the following general formula (4)

(In the formula, A is a monovalent fluorine-containing group whose terminal is a —CF ₃ group, and Rf ′ is a divalent fluorooxyalkylene group-containing polymer residue.)
The surface treatment agent according to [8], comprising a fluoropolyether group-containing polymer represented by the formula:
[10]
[9] An article surface-treated with the surface treatment agent according to [9].

  The film formed from the surface treatment agent containing the fluoropolyether group-containing polymer-modified organosilicon compound of the present invention has high water and oil repellency, and in particular, the film formed in a short time under mild conditions such as room temperature. Excellent wear resistance. Since the surface treatment agent containing the fluoropolyether group-containing polymer-modified organosilicon compound of the present invention has specific adhesion particularly to the resin surface, a resin film or glasses can be obtained by treating with the surface treatment agent. Excellent water and oil repellency, low dynamic friction and wear resistance can be easily imparted to resin products such as lenses in a short time.

［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は独立に２価の炭化水素基であり、Ｑは独立に２価の直鎖状もしくは環状オルガノシロキサン残基、シルアルキレン基又はシルアリーレン基であり、Ｘは独立に水素原子、炭素数１〜４のアルキル基又はフェニル基であり、Ｚは独立に水素原子、下記式
−ＳｉＲ₃
（式中、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る。）
で表される基、又は下記式
−Ｗ−Ｑ’−Ｘ
（式中、Ｘは上記と同じであり、Ｗは単結合又は２価の炭化水素基であり、Ｑ’はシロキサン結合、シルアルキレン構造及びシルアリーレン構造から選ばれる構造を有する２価の基である。）
で表される基であり、αは１又は２である。］The fluoropolyether group-containing polymer-modified organosilicon compound of the present invention is represented by the following general formula (1).

[Wherein Rf is a monovalent fluorooxyalkyl group or divalent fluorooxyalkylene group-containing polymer residue, Y is independently a divalent hydrocarbon group, and Q is independently a divalent linear chain. Or a cyclic organosiloxane residue, a silalkylene group or a silarylene group, X is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, Z is independently a hydrogen atom, _Three
(In the formula, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group.)
Or a group represented by the following formula -WQ'-X
Wherein X is the same as above, W is a single bond or a divalent hydrocarbon group, Q ′ is a divalent group having a structure selected from a siloxane bond, a silalkylene structure and a silarylene structure. is there.)
And α is 1 or 2. ]

（式中、ｐ、ｑ、ｒ、ｓはそれぞれ０〜２００の整数で、ｐ＋ｑ＋ｒ＋ｓ＝３〜２００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、該単位は直鎖状でも分岐状であってもよい。）In the above formula (1), when α is 1, Rf is preferably a monovalent fluorooxyalkyl group represented by the following general formula (2).

(In the formula, p, q, r, and s are each an integer of 0 to 200, and p + q + r + s = 3 to 200, each repeating unit may be linear or branched, and each repeating unit is randomly selected. And d is an integer of 1 to 3, and the unit 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、該単位は直鎖状でも分岐状であってもよい。）In the above formula (1), when α is 2, Rf is preferably a divalent fluorooxyalkylene group represented by the following general formula (3).

(In the formula, p, q, r, and s are each an integer of 0 to 200, and p + q + r + s = 3 to 200, each repeating unit may be linear or branched, and each repeating unit is randomly selected. And d is an integer of 1 to 3, and the unit may 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 = 3 to 200, preferably 10 to 100, each repeating unit may be linear or branched, and each repeating unit is randomly bonded May have been. More preferably, p + q is an integer of 10 to 105, particularly 15 to 60, and r = s = 0. If p + q + r + s is smaller than the above upper limit value, the adhesion and film forming properties are good, and if p + q + r + s is larger than the lower limit value, it is preferable because the characteristics of the fluoropolyether group can be sufficiently exhibited.
In the above formulas (2) and (3), d is an integer of 1 to 3, preferably 1 or 2, and the unit may be linear or branched.

By having the main chain structure represented by the above formula (2) or (3) as Rf, a film having a low dynamic friction coefficient can be formed.
Also, a linear polymer having a fluoropolyether structure in the main chain and containing a siloxane bond, a silphenylene bond or a silalkylene bond at one end of the molecular chain (α is 1, Rf is represented by the formula (2) The monovalent fluorooxyalkyl group) is a linear polymer containing a siloxane bond, a silphenylene bond or a silalkylene bond at both ends (α is 2 and Rf is represented by the formula (3)). Compared with the fluorooxyalkylene group), it is possible to impart excellent abrasion resistance to the resulting film.

（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、ｖは１〜２４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 include the following.

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

  In the above formula (1), Y is independently a divalent hydrocarbon group, and is a propylene group (trimethylene group or methylethylene group) having 3 to 10 carbon atoms, particularly 3 to 8 carbon atoms, butylene group (tetramethylene group). , A methylpropylene group), a hexamethylene group, an octamethylene group and the like are preferable, and a trimethylene group is particularly preferable.

  In the above formula (1), X is independently a hydrogen atom, an alkyl group such as a methyl group having 1 to 4 carbon atoms, an ethyl group, a propyl group, or a butyl group, or a phenyl group, preferably a hydrogen atom or a methyl group.

（式中、Ｘは上記と同じであり、Ｒ¹は独立に炭素数１〜４のメチル基、エチル基、プロピル基、ブチル基等のアルキル基又はフェニル基であり、Ｒ²は炭素数１〜４のメチレン基、エチレン基、プロピレン基、ブチレン基等のアルキレン基又は炭素数６〜１２のフェニレン基等のアリーレン基である。ｇは１〜２０、好ましくは１〜１０の整数であり、ｊは１〜８、好ましくは１〜３の整数である。）In the above formula (1), Q is independently a divalent linear or cyclic organosiloxane residue, a silalkylene group or a silarylene group, and is preferably a group selected from the groups represented by the following formulae. .

(Wherein X is the same as above, R ¹ is independently an alkyl group such as a methyl group having 1 to 4 carbon atoms, an ethyl group, a propyl group, or a butyl group, or a phenyl group, and R ² is 1 carbon atom) An alkylene group such as a methylene group of -4, an ethylene group, a propylene group, a butylene group, or an arylene group such as a phenylene group having 6 to 12 carbon atoms, g is an integer of 1-20, preferably 1-10, j is an integer of 1-8, preferably 1-3.

（式中、ｇ１は２〜２０、好ましくは２〜１０の整数である。）Specific examples of Q include the following groups.

(In the formula, g1 is an integer of 2 to 20, preferably 2 to 10.)

In the above formula (1), Z is independently a hydrogen atom, the following formula —SiR ₃
(In the formula, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group.)
Or a group represented by the following formula -WQ'-X
Wherein X is the same as above, W is a single bond or a divalent hydrocarbon group, Q ′ is a divalent group having a structure selected from a siloxane bond, a silalkylene structure and a silarylene structure. is there.)
It is group represented by these.

In —SiR ₃ , R is an alkyl group such as a methyl group having 1 to 4 carbon atoms, an ethyl group, a propyl group, or a butyl group, or a phenyl group. Among them, a methyl group or an ethyl group is preferable.

In -WQ'-X, W is a single bond or a divalent hydrocarbon group, and the divalent hydrocarbon group includes an ethylene group having 2 to 10 carbon atoms, particularly 2 to 8 carbon atoms, Alkylene groups such as propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), hexamethylene group, octamethylene group and the like can be mentioned, and W is a single bond or trimethylene group. Is preferred.
X is the same as described above, and is preferably a hydrogen atom or a methyl group.

（式中、ｇ１は上記と同じである。）Q ′ is a divalent group having a structure selected from a siloxane bond, a silalkylene structure and a silarylene structure, and the divalent linear or cyclic organosiloxane residue exemplified in Q above, a silalkylene structure, Those having a silarylene structure are preferred.
Specific examples of Q ′ include the following groups.

(Wherein g1 is the same as above)

（式中、ｇ１は上記と同じであり、ｅは０〜３の整数である。）Specific examples of Z include a hydrogen atom and those shown below.

(In the formula, g1 is the same as above, and e is an integer of 0 to 3.)

（式中、Ｚ、ｇ１、ｅは上記と同じであり、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。）Examples of the fluoropolyether group-containing polymer-modified organosilicon compound represented by the above formula (1) include those represented by the following formula. In each formula, the number of repeating units (or the degree of polymerization) constituting the fluorooxyalkyl group or fluorooxyalkylene group can take any number satisfying the above formulas (2) and (3). It is.

(In the formula, Z, g1, and e are the same as above, 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 organosilicon compound represented by the above formula (1) include the following methods.

  First, a fluoropolyether group-containing polymer having a reactive group such as an acid fluoride group, an acid halide group, an acid anhydride group, an ester group, a carboxylic acid group, an amide group at the molecular chain end, a nucleophile, and a solvent For example, 1,3-bis (trifluoromethyl) benzene and tetrahydrofuran are mixed, and 0 to 80 ° C., preferably 50 to 70 ° C., more preferably about 60 ° C., 1 to 6 hours, preferably 3 to 5 hours. More preferably, it is aged for about 4 hours.

（式中、Ｒｆ、αは上記と同じである。）Here, specific examples of the fluoropolyether group-containing polymer having a reactive group at the molecular chain terminal include the following.

(In the formula, Rf and α are the same as above.)

Moreover, as a nucleophile, allyl magnesium halide, 3-butenyl magnesium halide, 4-pentenyl magnesium halide, 5-hexenyl magnesium halide, etc. can be used. It is also possible to use a corresponding lithium reagent.
The amount of the nucleophile used is 2 to 5 equivalents, more preferably 2.5 to 3.5 equivalents, relative to 1 equivalent of the reactive group of the fluoropolyether group-containing polymer having a reactive group at the molecular chain end. More preferably, about 3 equivalents can be used.

（式中、Ｒｆ、αは上記と同じである。Ｕは２価の炭化水素基である。）Subsequently, the reaction is stopped, and the aqueous layer and the fluorine solvent layer are separated by a liquid separation operation. The obtained fluoro solvent layer is further washed with an organic solvent, and the solvent is distilled off to obtain a fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal represented by the following formula (a). .

(In the formula, Rf and α are the same as above. U is a divalent hydrocarbon group.)

  In the above formula (a), U is a divalent hydrocarbon group, specifically, a methylene group, an ethylene group, a propylene group (trimethylene group, methylethylene group), a butylene group (tetramethylene group, methylpropylene group). ), An alkylene group having 1 to 8 carbon atoms such as a hexamethylene group and an octamethylene group, and an alkylene group containing an arylene group having 6 to 8 carbon atoms such as a phenylene group (for example, an alkylene / arylene group having 7 to 8 carbon atoms) ) And the like. U is preferably a linear alkylene group having 1 to 4 carbon atoms.

  Next, if necessary, the hydrogen atom of the hydroxyl group of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the end of the molecular chain represented by the formula (a) obtained above is substituted with another group.

Examples of a method for substituting a hydrogen atom of a hydroxyl group with a silyl group represented by -SiR ₃ include, for example, a fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain end represented by the formula (a) and a silylating agent. And in the presence of a base such as amines or alkali metal bases, if necessary, using a solvent such as a fluorine-based solvent or an organic solvent, 0 to 80 ° C., preferably 40 to 60 ° C., more preferably about 50 ° C. Aging is carried out at a temperature for 1 to 24 hours, preferably 2 to 10 hours, more preferably about 3 hours.
As another method, the presence of a dehydrogenation catalyst such as a platinum group metal catalyst or a boron catalyst may be prepared by combining a fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain end represented by formula (a) with hydrosilane. Below, using a solvent such as a fluorine-based solvent or an organic solvent, the temperature is 0 to 60 ° C., preferably 15 to 35 ° C., more preferably about 25 ° C., 10 minutes to 24 hours, preferably 30 minutes to 2 hours, More preferably, the dehydrogenation reaction is performed for about 1 hour.

Here, as the silylating agent, for example, silyl halide, silyl triflate and the like can be used, and specifically, trimethylsilyl chloride, triethylsilyl chloride, tert-butyldimethyl chloride, triisopropylsilyl chloride, triphenylsilyl chloride. , Trimethylsilyl bromide, trimethylsilyl triflate, triethylsilyl triflate, tert-butyldimethyl triflate, triisopropylsilyl triflate The amount used may be a full amount having a hydroxyl group and an olefin moiety at the molecular chain end represented by the formula (a). On 1 equivalent of hydroxyl group of the Roporieteru group-containing polymer, 1 to 10 equivalents, more preferably 1-4 equivalents, it can be used more preferably about 2 equivalents.
Examples of the hydrosilane include trimethylsilane, triethylsilane, tert-butyldimethylsilane, triisopropylsilane, triphenylsilane, and the like. The amount used is a hydroxyl group and an olefin at the molecular chain end represented by the formula (a). 1 to 5 equivalents, more preferably 1.5 to 3 equivalents, and still more preferably about 2 equivalents can be used per 1 equivalent of hydroxyl group of the fluoropolyether group-containing polymer having a moiety.

（式中、Ｒｆ、Ｒ、Ｕ、αは上記と同じである。）Subsequently, the reaction is stopped, and the aqueous layer and the fluorine solvent layer are separated by a liquid separation operation. The obtained fluorine solvent layer is further washed with an organic solvent, and the solvent is distilled off to obtain a fluorooxyalkyl group-containing polymer having a silyl group and an olefin moiety at the molecular chain end represented by the following formula (b). It is done.

(In the formula, Rf, R, U and α are the same as above.)

  Moreover, as a method of substituting the hydrogen atom of the hydroxyl group with a group represented by -WQ'-X, for example, containing a fluoropolyether group having a hydroxyl group and an olefin moiety at the molecular chain end represented by the formula (a) A polymer and an organosilicon compound having a SiH group are mixed at 0 to 60 ° C., preferably 15 to 35 ° C., more preferably using a solvent such as a fluorine-based solvent or an organic solvent in the presence of a dehydrogenation catalyst such as a boron catalyst. The dehydrogenation reaction is performed at a temperature of about 25 ° C. for 10 minutes to 24 hours, preferably 30 minutes to 2 hours, more preferably about 1 hour.

（式中、ｇ、ｅは上記と同じであり、ｃは１〜４の整数である。）Here, as an organosilicon compound having a SiH group, for example, those shown below can be exemplified.

(In the formula, g and e are the same as above, and c is an integer of 1 to 4.)

  The amount used is 1 to 10 equivalents, more preferably 1.2 to 5 with respect to 1 equivalent of a hydroxyl group of a fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain end represented by the formula (a). An equivalent amount can be used.

（式中、Ｒｆ、Ｑ’、Ｘ、Ｕ、αは上記と同じであり、Ｗ’は単結合である。）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, thereby having an olefin moiety at the molecular chain terminal represented by the following formula (c), wherein the hydroxyl group is an organosilicon compound group. A fluorooxyalkyl group-containing polymer substituted with is obtained.

(In the formula, Rf, Q ′, X, U and α are the same as above, and W ′ is a single bond.)

Further, as another method of substituting the hydrogen atom of the hydroxyl group with a group represented by -WQ'-X, first, the hydrogen atom of the hydroxyl group is substituted with a terminal unsaturated group, and then the terminal unsaturated group ( Examples thereof include a method of reacting an olefin moiety) with an organosilicon compound having a SiH group together with other olefin moieties.
Examples of a method for substituting a hydrogen atom of a hydroxyl group with a terminal unsaturated group include, for example, a fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain end represented by the formula (a), and an olefin introducing agent. In the presence of bases such as alkenyls and alkali metal bases, additives such as tetrabutylammonium halide and alkali metal halides as necessary, and solvents such as fluorine-based solvents and organic solvents are used as necessary. C., preferably 60 to 80.degree. C., more preferably about 70.degree. C., for 1 to 25 hours, preferably 3 to 10 hours, more preferably about 6 hours.

  Here, as the olefin introducing agent, for example, allyl halide can be used. Specifically, allyl chloride, allyl bromide, allyl iodide, 4-chloro-1-butene, 4-bromo-1-butene, 4 -Iodo-1-butene, 5-chloro-1-pentene, 5-bromo-1-pentene, 5-iodo-1-pentene and the like, and the amount used is a molecular chain represented by the formula (a) It can be used in an amount of 1 to 10 equivalents, more preferably 2.5 to 6 equivalents, and even more preferably about 5 equivalents with respect to 1 equivalent of the hydroxyl group of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the terminal.

（式中、Ｒｆ、Ｕ、αは上記と同じである。Ｖは単結合又は２価の炭化水素基である。）Subsequently, the reaction is stopped, and the aqueous layer and the fluorine solvent layer are separated by a liquid separation operation. The obtained fluorine solvent layer is further washed with an organic solvent, and the solvent is distilled off to obtain a fluorooxyalkyl group-containing polymer having an olefin moiety at the molecular chain end represented by the following formula (d).

(In the formula, Rf, U, and α are the same as above. V is a single bond or a divalent hydrocarbon group.)

  In the above formula (d), V is a single bond or a divalent hydrocarbon group. Specific examples of the divalent hydrocarbon group include a methylene group, an ethylene group, and a propylene group (trimethylene group, methylethylene group). ), Butylene groups (tetramethylene group, methylpropylene group), alkylene groups having 1 to 8 carbon atoms such as hexamethylene groups and octamethylene groups, and alkylene groups having 6 to 8 carbon atoms arylene groups such as phenylene groups (for example, And an alkylene / arylene group having 7 to 8 carbon atoms). V is preferably a methylene group.

  Next, hydrosilylating one of the fluoropolyether group-containing polymer having an olefin moiety at the end of the molecular chain represented by the formulas (a) to (d) obtained above and an organosilicon compound having a SiH group in the molecule. In the presence of a chloroplatinic acid / vinylsiloxane complex toluene solution 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. Aging is carried out for a time, more preferably about 24 hours.

（式中、Ｒ¹、Ｒ²、Ｘ、ｇ、ｊは上記と同じであり、ｉは１〜６、好ましくは１〜４の整数で、ｉ＋ｊは３〜１０、好ましくは３〜５の整数である。）Here, the organosilicon compound having a SiH group in the molecule is preferably a compound represented by the following formula.

Wherein R ¹ , R ² , X, g and j are the same as above, i is an integer of 1 to 6, preferably 1 to 4, and i + j is an integer of 3 to 10, preferably 3 to 5. .)

（式中、ｇ、ｇ１、ｅは上記と同じである。）Examples of such organosilicon compounds having a SiH group in the molecule include those shown below.

(Wherein g, g1, and e are the same as above)

  The amount of the organosilicon compound having a SiH group in the molecule is 1 equivalent of the terminal unsaturated group of the fluoropolyether group-containing polymer having an olefin moiety at the molecular chain end represented by the above formulas (a) to (d). On the other hand, 5 to 20 equivalents, more preferably 7.5 to 12.5 equivalents, and still more preferably about 10 equivalents can be used.

  Then, the fluoropolyether group-containing polymer-modified organosilicon compound represented by the above formula (1) can be obtained by distilling off the solvent and unreacted substances under reduced pressure. In addition, the reaction mentioned above can be performed independently or continuously.

  The surface treating agent of the present invention contains a fluoropolyether group-containing polymer-modified organosilicon compound represented by the above formula (1).

（式中、Ａはフッ素原子又は末端が−ＣＦ₃基である１価のフッ素含有基であり、Ｒｆ’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る。）
で表されるフルオロポリエーテル基含有ポリマー（以下、無官能性ポリマーと称す）を含有してもよい。The surface treatment agent of the present invention further includes the following general formula (4).

(In the formula, A is a fluorine atom or a monovalent fluorine-containing group whose terminal is a —CF ₃ group, and Rf ′ is a divalent fluorooxyalkylene group-containing polymer residue.)
The polymer may contain a fluoropolyether group-containing polymer (hereinafter referred to as a non-functional polymer).

（式中、ｐ２は５〜２００、好ましくは１０〜１００の整数、ｑ２は５〜２００、好ましくは１０〜１００の整数、ｒ１は１０〜２００、好ましくは２０〜１００の整数、ｔ１は５〜２００、好ましくは１０〜１００の整数、ｔ２は１０〜２００、好ましくは２０〜１００の整数で、ｔ１＋ｐ２は１０〜２０５、好ましくは２０〜１１０の整数、ｑ２＋ｐ２は１０〜２０５、好ましくは２０〜１１０の整数である。）In the above formula (4), A is a fluorine atom or a monovalent fluorine-containing group whose terminal is a —CF ₃ group, preferably a fluorine atom, a linear perfluoroalkyl group having 1 to 6 carbon atoms, Among them, -F group, -CF ₃ group, -CF ₂ CF ₃ group, and -CF ₂ CF ₂ CF ₃ group are preferable.
Rf ′ is a divalent fluorooxyalkylene group-containing polymer residue, and Rf ′ is preferably the following.

(In the formula, p2 is an integer of 5 to 200, preferably 10 to 100, q2 is an integer of 5 to 200, preferably 10 to 100, r1 is an integer of 10 to 200, preferably 20 to 100, and t1 is 5 to 5. 200, preferably an integer of 10 to 100, t2 is an integer of 10 to 200, preferably 20 to 100, t1 + p2 is an integer of 10 to 205, preferably 20 to 110, q2 + p2 is 10 to 205, preferably 20 to 110 Is an integer.)

（式中、ｐ２、ｑ２、ｒ１、ｔ１、ｔ２は上記と同じである。）Examples of the non-functional polymer represented by the formula (4) include the following.

(Wherein p2, q2, r1, t1, and t2 are the same as described above.)

  Although the usage-amount in the case of mix | blending the nonfunctional polymer represented by Formula (4) is not specifically limited, It is 0.00 with respect to the mass of the fluoro polyether group containing polymer modified organosilicon compound represented by Formula (1). The range of 1-60 mass%, especially 10-40 mass% is preferable, and when too large, the problem of adhesiveness may arise.

The surface treatment agent may contain a suitable solvent. Examples of such solvents include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (m-xylene hexafluoride (1,3-bis (trifluoro) Methyl) benzene), benzotrifluoride, etc.), fluorine-modified ether solvents (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro (2-butyltetrahydrofuran), etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, Examples thereof include perfluorotripentylamine), hydrocarbon solvents (petroleum benzine, mineral spirits, toluene, xylene, etc.), and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Of these, fluorine-modified solvents are desirable in terms of solubility and wettability, and in particular, m-xylene hexafluoride, perfluoro (2-butyltetrahydrofuran), perfluorotributylamine, ethyl perfluoro Butyl ether is preferred.
Two or more of these solvents may be mixed, but it is preferable to uniformly dissolve the fluoropolyether group-containing polymer-modified organosilicon compound. In addition, although the optimal density | concentration of the fluorooxyalkylene group containing polymer dissolved in a solvent changes with processing methods, it is preferable that it is 0.01-40 mass% in a surface treating agent, especially 0.05-25 mass%.

The surface treatment agent of the present invention is used to treat a resin product such as a resin film or a spectacle lens. Here, as a resin product, what consists of a thermoplastic resin is preferable, and specifically, the thermoplastic resin film (hard coat film) by which the hard coat process was carried out, it is more than pencil hardness 4H, and the hard coat is not given. A thermoplastic resin film (high hardness resin film) or a thermoplastic resin film (antireflection film) provided with an antireflection layer is preferably used.
In the present invention, it is preferable to use the above resin product that has been treated with SiO ₂ in advance. Here, SiO ₂ process, those SiO ₂ treated by sputtering is preferred from the viewpoint of improving the adhesion between the resin product and process agent.

The surface treatment agent of the present invention can be applied onto a substrate by a known method such as brushing, dipping, spraying, or vapor deposition. The heating method during the vapor deposition process may be either a resistance heating method or an electron beam heating method, and is not particularly limited. Further, the post-treatment conditions vary depending on the post-treatment method. For example, when applied by vapor deposition or spray coating, when a resin film treated with SiO ₂ is used as a base material, from room temperature (25 ° C.) It can be 5 minutes to 24 hours, particularly 10 minutes to 12 hours in the range of 200 ° C., and may be post-treated under humidification. In particular, in the present invention, even at room temperature, 10 minutes to 24 hours, particularly 30 minutes to 12 hours are sufficient. The thickness of the coating is appropriately selected depending on the type of substrate, but is usually 0.1 to 100 nm, particularly 1 to 25 nm.

  Examples of the resin product treated with the surface treatment agent of the present invention include car navigation, mobile phone, digital camera, digital video camera, PDA, portable audio player, car audio, game device, glasses lens, camera lens, lens filter, Sunglasses, medical equipment such as stomach cameras, copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, hard coat films, high-hardness resins, antireflection films, wearable devices, etc. In addition, an optical article, a touch panel, an antireflection film, a quartz substrate, and the like used as a part are preferable.

  The surface treatment agent for surface-treating the resin product of the present invention can form a film on the article under a mild condition such as room temperature even for a short time, and the film has excellent water and oil repellency and durability. Therefore, it is particularly useful as a water / oil repellent layer for eyeglass lenses, touch panel displays, hard coat films, high-hardness resins, antireflection films, wearable terminals and the like. Here, the high-hardness resin is, for example, a product obtained by molding a resin having a pencil hardness of 4H or higher, such as a product name Sylplus manufactured by Nippon Steel Chemical Co., Ltd. and a product name HD film manufactured by Gunze Co., which is promoted as a glass substitute film. In particular, it refers to a resin film obtained by molding the resin, but is not particularly limited to the above products.

EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated in detail, this invention is not limited by the following Example.
In Examples and Comparative Examples, compounds obtained by the following synthesis examples were used.

で表される化合物３００ｇ（４．８×１０^-2ｍｏｌ）をゆっくりと滴下した後、６０℃で４時間加熱した。加熱終了後、室温まで冷却し、１．２Ｍ塩酸水溶液３００ｇ中へ溶液を滴下し、反応を停止させた。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、残存溶剤を留去することで、下記式（Ｂ）で表されるフルオロポリエーテル基含有ポリマー２９２ｇを得た。

Synthesis Example 1 Synthesis of Compound 1 In a reaction vessel, 150 g of tetrahydrofuran and 300 g of 1,3-bis (trifluoromethyl) benzene were mixed, and 160 ml of 0.7 M allylmagnesium bromide was added dropwise. Subsequently, the following formula (A)

After slowly dropping 300 g (4.8 × 10 ⁻² mol) of the compound represented by the formula, it was heated at 60 ° C. for 4 hours. After completion of the heating, the mixture was cooled to room temperature, and the solution was dropped into 300 g of 1.2 M hydrochloric acid aqueous solution to stop the reaction. The lower fluorine compound layer was recovered by a liquid separation operation and then washed with acetone. The fluorine compound layer, which is the lower layer after washing, was collected again, and the remaining solvent was distilled off under reduced pressure to obtain 292 g of a fluoropolyether group-containing polymer represented by the following formula (B).

で表される化合物８０ｇ（１．０×１０^-2ｍｏｌ）を入れ、１，３−ビス（トリフルオロメチル）ベンゼン８０ｇに溶解させ、塩化白金酸／ビニルシロキサン錯体のトルエン溶液８．０×１０^-2ｇ（Ｐｔ単体として２．１×１０^-6ｍｏｌを含有）と、１，４−ビス（ジメチルシリル）ベンゼン３７ｇ（１．９×１０^-1ｍｏｌ）を混合して、８０℃で７時間熟成し、溶剤及び未反応物を減圧留去することで、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（化合物１）７０ｇを得た。

¹Ｈ−ＮＭＲ
δ０−０．２（−Ｓｉ（ＣＨ ₃）₂）２４Ｈ
δ０．４−０．６（−ＣＨ₂ＣＨ₂ＣＨ ₂−Ｓｉ）４Ｈ
δ１．３−１．６（−ＣＨ₂ＣＨ ₂ＣＨ₂−Ｓｉ）４Ｈ
δ１．６−１．９（−ＣＨ ₂ＣＨ ₂ ＣＨ₂−Ｓｉ）４Ｈ
δ３．６−４．２（−ＳｉＨ）２Ｈ
δ６．６−７．１（−Ｃ₆ Ｈ ₄）８ＨIn the reaction vessel, the following formula (B)

80 g (1.0 × 10 ⁻² mol) of the compound represented by formula (1) is added, dissolved in 80 g of 1,3-bis (trifluoromethyl) benzene, and a toluene solution of chloroplatinic acid / vinylsiloxane complex 8.0 × 10 ^-2 g (containing 2.1 × 10 ⁻⁶ mol as a simple substance of Pt) and 37 g of 1,4-bis (dimethylsilyl) benzene (1.9 × 10 ⁻¹ mol) are mixed at 7 ° C. at 7 ° C. After aging for a while, the solvent and unreacted substances were distilled off under reduced pressure to obtain 70 g of a fluoropolyether group-containing polymer (compound 1) represented by the following formula (C).

¹ H-NMR
δ0-0.2 (-Si (C H ₃ ) ₂ ) 24H
_{δ0.4-0.6 (-CH 2 CH 2 C H} 2 -Si) 4H
_{δ1.3-1.6 (-CH 2 C H 2 CH} 2 -Si) 4H
δ1.6-1.9 (—C H ₂ CH ₂ CH ₂ —Si) 4H
δ3.6-4.2 (-Si H) 2H
δ6.6-7.1 (-C ₆ H ₄₎ 8H

で表される化合物１００ｇ（２．７×１０^-2ｍｏｌ）を混合した後、トリメチルクロロシラン５．８ｇ（５．４×１０^-2ｍｏｌ）を滴下した。続いて、５０℃で３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、メタノールで洗浄した。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（Ｄ）で表されるフルオロポリエーテル基含有ポリマー９０ｇを得た。

¹Ｈ−ＮＭＲ
δ０−０．２（−ＯＳｉ（ＣＨ ₃）₃）９Ｈ
δ２．４−２．６（−ＣＨ ₂ＣＨ＝ＣＨ₂）４Ｈ
δ５．０−５．２（−ＣＨ₂ＣＨ＝ＣＨ ₂）４Ｈ
δ５．７−５．９（−ＣＨ₂ＣＨ＝ＣＨ₂）２Ｈ[Synthesis Example 2] Synthesis of Compound 2 In a reaction vessel, 100 g of 1,3-bis (trifluoromethyl) benzene, 8.2 g (5.4 × 10 ⁻² mol) of DBU (diazabicycloundecene), the following formula (B)

After mixing 100 g (2.7 × 10 ⁻² mol) of the compound represented by formula (5), 5.8 g (5.4 × 10 ⁻² mol) of trimethylchlorosilane was added dropwise. Then, it heated at 50 degreeC for 3 hours. After completion of heating, the mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was added dropwise. After the separation of the fluorine compound layer as the lower layer by a liquid separation operation, the layer was washed with methanol. The fluorine compound layer which is the lower layer after washing was recovered again, and the residual solvent was distilled off under reduced pressure to obtain 90 g of a fluoropolyether group-containing polymer represented by the following formula (D).

¹ H-NMR
δ0-0.2 (-OSi (C H ₃ ) ₃ ) 9H
δ 2.4-2.6 (—C H ₂ CH═CH ₂ ) 4H
δ 5.0-5.2 (—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５０ｇ（１．４×１０^-2ｍｏｌ）を入れ、１，３−ビス（トリフルオロメチル）ベンゼン５０ｇに溶解させ、塩化白金酸／ビニルシロキサン錯体のトルエン溶液１．５×１０^-1ｇ（Ｐｔ単体として４．０×１０^-6ｍｏｌを含有）と、１，３，５，７−テトラメチルシクロテトラシロキサン３３ｇ（１．３×１０^-1ｍｏｌ）を混合して、８０℃で１９時間熟成し、溶剤及び未反応物を減圧留去することで、下記式（Ｅ）で表されるフルオロポリエーテル基含有ポリマー（化合物２）５６ｇを得た。

¹Ｈ−ＮＭＲ
δ０−０．２（−ＯＳｉ−ＣＨ ₃、−ＯＳｉ（ＣＨ ₃）₃）３６Ｈ
δ０．５−０．８（−ＣＨ₂ＣＨ₂ＣＨ ₂−Ｓｉ）４Ｈ
δ１．３−２．２（−ＣＨ ₂ＣＨ ₂ＣＨ₂−Ｓｉ）８Ｈ
δ４．３−５．２（−ＳｉＨ）６ＨIn the reaction vessel, the following formula (D)

Compound represented by putting 50g (1.4 × 10 ^-2 mol) in 1,3-bis dissolved in (trifluoromethyl) benzene 50 g, toluene solution 1.5 × 10 chloroplatinic acid / vinylsiloxane complex ^-1 g (containing 4.0 × 10 ⁻⁶ mol as a simple substance of Pt) and 33 g of 1,3,5,7-tetramethylcyclotetrasiloxane (1.3 × 10 ⁻¹ mol) Aging was carried out at 19 ° C. for 19 hours, and the solvent and unreacted substances were distilled off under reduced pressure to obtain 56 g of a fluoropolyether group-containing polymer (compound 2) represented by the following formula (E).

¹ H-NMR
δ0-0.2 (-OSi-C H ₃ , -OSi (C H ₃ ) ₃ ) 36H
_{δ0.5-0.8 (-CH 2 CH 2 C H} 2 -Si) 4H
δ1.3-2.2 (—C H ₂ C H ₂ CH ₂ —Si) 8H
δ4.3-5.2 (-Si H) 6H

で表される化合物１５０ｇ（４．０×１０^-2ｍｏｌ）を入れ、１，３−ビス（トリフルオロメチル）ベンゼン１５０ｇに溶解させ、塩化白金酸／ビニルシロキサン錯体のトルエン溶液８．０×１０^-2ｇ（Ｐｔ単体として４．０×１０^-6ｍｏｌを含有）と、１，１，３，３，５，５−ヘキサメチルトリシロキサン８３ｇ（４．０×１０^-1ｍｏｌ）を混合して、８０℃で２４時間熟成し、溶剤及び未反応物を減圧留去することで、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（化合物３）１５０ｇを得た。

¹Ｈ−ＮＭＲ
δ０−０．２（−ＯＳｉ（ＣＨ ₃）₂）３６Ｈ
δ０．３−０．６（−ＣＨ₂ＣＨ₂ＣＨ ₂−Ｓｉ）４Ｈ
δ１．３−１．８（−ＣＨ ₂ＣＨ₂ＣＨ₂−Ｓｉ，−ＣＨ₂ＣＨ ₂ＣＨ₂−Ｓｉ）８Ｈ
δ３．３−３．６（−ＳｉＨ）２ＨSynthesis Example 3 Synthesis of Compound 3 In a reaction vessel, the following formula (B)

150 g (4.0 × 10 ⁻² mol) of the compound represented by the formula (1) is added, dissolved in 150 g of 1,3-bis (trifluoromethyl) benzene, and a toluene solution of chloroplatinic acid / vinylsiloxane complex 8.0 × 10 ^-2 g (containing 4.0 × 10 ⁻⁶ mol as a simple substance of Pt) and 83 g of 1,1,3,3,5,5-hexamethyltrisiloxane (4.0 × 10 ⁻¹ mol) The mixture was aged at 80 ° C. for 24 hours, and the solvent and unreacted substances were distilled off under reduced pressure to obtain 150 g of a fluoropolyether group-containing polymer (compound 3) represented by the following formula (F).

¹ H-NMR
δ0-0.2 (-OSi (C H ₃ ) ₂ ) 36H
_{δ0.3-0.6 (-CH 2 CH 2 C H} 2 -Si) 4H
_{δ1.3-1.8 (-C H 2 CH 2 CH} 2 -Si, -CH 2 C H 2 CH 2 -Si) 8H
δ 3.3-3.6 (—SiH) 2 H

で表される化合物５０ｇ（１．４×１０^-2ｍｏｌ）を入れ、１，３−ビス（トリフルオロメチル）ベンゼン５０ｇに溶解させ、塩化白金酸／ビニルシロキサン錯体のトルエン溶液８．０×１０^-2ｇ（Ｐｔ単体として１．３×１０^-6ｍｏｌを含有）と、１，１，３，３，５，５，７，７−オクタメチルテトラシロキサン４０ｇ（１．４×１０^-1ｍｏｌ）を混合して、８０℃で４時間熟成し、溶剤及び未反応物を減圧留去することで、下記式（Ｇ）で表されるフルオロポリエーテル基含有ポリマー（化合物４）４１ｇを得た。

¹Ｈ−ＮＭＲ
δ０−０．２（−ＯＳｉ（ＣＨ ₃）₂）４８Ｈ
δ０．３−０．６（−ＣＨ₂ＣＨ₂ＣＨ ₂−Ｓｉ）４Ｈ
δ１．３−１．８（−ＣＨ ₂ＣＨ₂ＣＨ₂−Ｓｉ，−ＣＨ₂ＣＨ ₂ＣＨ₂−Ｓｉ）８Ｈ
δ３．３−３．６（−ＳｉＨ）２ＨSynthesis Example 4 Synthesis of Compound 4 In a reaction vessel, the following formula (B)

Compound represented by putting 50g (1.4 × 10 ^-2 mol) in 1,3-bis dissolved in (trifluoromethyl) benzene 50 g, toluene solution 8.0 × 10 chloroplatinic acid / vinylsiloxane complex ^-2 g (containing 1.3 × 10 ⁻⁶ mol as Pt alone) and 40 g (1.4 × 10 ⁻¹ mol) of 1,1,3,3,5,5,7,7-octamethyltetrasiloxane ) And aged at 80 ° C. for 4 hours, and the solvent and unreacted substances were distilled off under reduced pressure to obtain 41 g of a fluoropolyether group-containing polymer (compound 4) represented by the following formula (G). .

¹ H-NMR
δ0-0.2 (-OSi (C H ₃ ) ₂ ) 48H
_{δ0.3-0.6 (-CH 2 CH 2 C H} 2 -Si) 4H
_{δ1.3-1.8 (-C H 2 CH 2 CH} 2 -Si, -CH 2 C H 2 CH 2 -Si) 8H
δ 3.3-3.6 (—SiH) 2 H

で表される化合物２０ｇ（０．５×１０^-2ｍｏｌ）を入れ、１，３−ビス（トリフルオロメチル）ベンゼン２０ｇに溶解させ、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０．５×１０^-6ｍｏｌを含有）と、下記式（Ｈ）

で示されるデカシロキサン４０ｇ（０．５×１０^-1ｍｏｌ）を混合して、８０℃で７時間熟成し、溶剤及び未反応物を減圧留去することで、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（化合物５）１０ｇを得た。

¹Ｈ−ＮＭＲ
δ０−０．２（−ＯＳｉ（ＣＨ ₃）₂）１２０Ｈ
δ０．３−０．８（−ＣＨ₂ＣＨ₂ＣＨ ₂−Ｓｉ）４Ｈ
δ１．３−１．８（−ＣＨ ₂ＣＨ₂ＣＨ₂−Ｓｉ，−ＣＨ₂ＣＨ ₂ＣＨ₂−Ｓｉ）８Ｈ
δ４．７−５．０（−ＳｉＨ）２ＨSynthesis Example 5 Synthesis of Compound 5 In a reaction vessel, the following formula (B)

20 g (0.5 × 10 ⁻² mol) of the compound represented by formula (1) is added, dissolved in 20 g of 1,3-bis (trifluoromethyl) benzene, and a chloroplatinic acid / vinylsiloxane complex toluene solution 2.0 × 10 ^-2 g (containing 0.5 × 10 ⁻⁶ mol as a simple substance of Pt) and the following formula (H)

Is mixed with 40 g (0.5 × 10 ⁻¹ mol) of decasiloxane and aged at 80 ° C. for 7 hours, and the solvent and unreacted substances are distilled off under reduced pressure, which is represented by the following formula (I). 10 g of a fluoropolyether group-containing polymer (Compound 5) was obtained.

¹ H-NMR
δ0-0.2 (-OSi (C H ₃ ) ₂ ) 120H
_{δ0.3-0.8 (-CH 2 CH 2 C H} 2 -Si) 4H
_{δ1.3-1.8 (-C H 2 CH 2 CH} 2 -Si, -CH 2 C H 2 CH 2 -Si) 8H
δ4.7-5.0 (-SiH) 2H

で表される化合物５０ｇ（１．３×１０^-2ｍｏｌ）を入れ、１，３−ビス（トリフルオロメチル）ベンゼン５０ｇに溶解させ、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１．４×１０^-6ｍｏｌを含有）と、ペンタメチルジシロキサン２０ｇ（１．４×１０^-1ｍｏｌ）を混合して、８０℃で８時間熟成し、溶剤及び未反応物を減圧留去することで、下記式（Ｊ）で表されるフルオロポリエーテル基含有ポリマー（化合物６）５４ｇを得た。

¹Ｈ−ＮＭＲ
δ０−０．２（−Ｓｉ−ＣＨ ₃）３０Ｈ
δ０．２−０．４（−ＣＨ₂ＣＨ₂ＣＨ ₂−Ｓｉ）４Ｈ
δ１．０−１．６（−ＣＨ ₂ＣＨ₂ＣＨ₂−Ｓｉ，−ＣＨ₂ＣＨ ₂ＣＨ₂−Ｓｉ）８ＨSynthesis Example 6 Synthesis of Compound 6 In a reaction vessel, the following formula (B)

Compound represented by putting 50g (1.3 × 10 ^-2 mol) in 1,3-bis dissolved in (trifluoromethyl) benzene 50 g, toluene solution of chloroplatinic acid / vinyl siloxane complex 5.0 × 10 ^-2 g (containing 1.4 × 10 ⁻⁶ mol as a simple substance of Pt) and 20 g (1.4 × 10 ⁻¹ mol) of pentamethyldisiloxane are mixed and aged at 80 ° C. for 8 hours. Unreacted substances were distilled off under reduced pressure to obtain 54 g of a fluoropolyether group-containing polymer (compound 6) represented by the following formula (J).

¹ H-NMR
δ0-0.2 (-Si-C H ₃ ) 30H
_{δ0.2-0.4 (-CH 2 CH 2 C H} 2 -Si) 4H
_{δ1.0-1.6 (-C H 2 CH 2 CH} 2 -Si, -CH 2 C H 2 CH 2 -Si) 8H

で表される化合物５０ｇ（１．３×１０^-2ｍｏｌ）を入れ、１，３−ビス（トリフルオロメチル）ベンゼン５０ｇに溶解させ、塩化白金酸／ビニルシロキサン錯体のトルエン溶液１．０×１０^-1ｇ（Ｐｔ単体として２．８×１０^-6ｍｏｌを含有）と、１−ブタン−デカメチルペンタシロキサン１３ｇ（３．２×１０^-2ｍｏｌ）を混合して、８０℃で２０時間熟成し、溶剤及び未反応物を減圧留去することで、下記式（Ｋ）で表されるフルオロポリエーテル基含有ポリマー（化合物７）５４ｇを得た。

¹Ｈ−ＮＭＲ
δ０−０．２（−Ｓｉ−ＣＨ ₃）６０Ｈ
δ０．３−０．６（−ＣＨ₂ＣＨ₂ＣＨ ₂−Ｓｉ）８Ｈ
δ０．６−０．８（−ＣＨ₂ＣＨ₂ＣＨ₂−ＣＨ ₃）６Ｈ
δ１．１−１．３（−ＣＨ₂ＣＨ ₂ＣＨ ₂−ＣＨ ₃）８Ｈ
δ１．４−１．８（−ＣＨ ₂ＣＨ ₂ＣＨ₂−Ｓｉ）８ＨSynthesis Example 7 Synthesis of Compound 7 In a reaction vessel, the following formula (B)

Compound represented by putting 50g (1.3 × 10 ^-2 mol) in 1,3-bis dissolved in (trifluoromethyl) benzene 50 g, toluene solution 1.0 × 10 chloroplatinic acid / vinylsiloxane complex ^-1 g (containing 2.8 × 10 ⁻⁶ mol of Pt alone) and 13 g of 1-butane-decamethylpentasiloxane (3.2 × 10 ⁻² mol), and aged at 80 ° C. for 20 hours Then, 54 g of a fluoropolyether group-containing polymer (compound 7) represented by the following formula (K) was obtained by distilling off the solvent and unreacted substances under reduced pressure.

¹ H-NMR
δ0-0.2 (-Si-C H ₃ ) 60H
_{δ0.3-0.6 (-CH 2 CH 2 C H} 2 -Si) 8H
_{δ0.6-0.8 (-CH 2 CH 2 CH 2} -C H 3) 6H
_{δ1.1-1.3 (-CH 2 C H 2 C} H 2 -C H 3) 8H
δ1.4-1.8 (—C H ₂ C H ₂ CH ₂ —Si) 8H

で表される化合物２５ｇ（０．７×１０^-2ｍｏｌ）を入れ、１，３−ビス（トリフルオロメチル）ベンゼン２５ｇに溶解させ、塩化白金酸／ビニルシロキサン錯体のトルエン溶液２．５×１０^-2ｇ（Ｐｔ単体として０．７×１０^-6ｍｏｌを含有）と、ビス（ジメチルシリル）メタン８．９ｇ（０．７×１０^-1ｍｏｌ）を混合して、８０℃で２４時間熟成し、溶剤及び未反応物を減圧留去することで、下記式（Ｌ）で表されるフルオロポリエーテル基含有ポリマー（化合物８）１０ｇを得た。

¹Ｈ−ＮＭＲ
δ０−０．４（−ＯＳｉ（ＣＨ ₃）₂，−Ｓｉ−ＣＨ ₂−Ｓｉ）２８Ｈ
δ０．４−０．８（−ＣＨ₂ＣＨ₂ＣＨ ₂−Ｓｉ）４Ｈ
δ１．２−２．０（−ＣＨ ₂ＣＨ ₂ＣＨ₂−Ｓｉ）８Ｈ
δ３．８−４．２（−ＳｉＨ）２Ｈ[Synthesis Example 8] Synthesis of Compound 8 In a reaction vessel, the following formula (B)

25 g (0.7 × 10 ⁻² mol) of the compound represented by formula (1) is added, dissolved in 25 g of 1,3-bis (trifluoromethyl) benzene, and a toluene solution of chloroplatinic acid / vinylsiloxane complex 2.5 × 10 ^-2 g (containing 0.7 × 10 ⁻⁶ mol as a simple substance of Pt) and 8.9 g (0.7 × 10 ⁻¹ mol) of bis (dimethylsilyl) methane are mixed and aged at 80 ° C. for 24 hours. Then, 10 g of a fluoropolyether group-containing polymer (compound 8) represented by the following formula (L) was obtained by distilling off the solvent and unreacted substances under reduced pressure.

¹ H-NMR
δ0-0.4 (-OSi (C H ₃ ) ₂ , -Si-C H ₂ -Si) 28H
_{δ0.4-0.8 (-CH 2 CH 2 C H} 2 -Si) 4H
δ 1.2-2.0 (—C H ₂ C H ₂ CH ₂ —Si) 8H
δ3.8-4.2 (-SiH) 2H

で表される化合物２００ｇ（２．６×１０^-2ｍｏｌ）、１，３−ビス（トリフルオロメチル）ベンゼン２００ｇ、１，１，３，３，５，５−ヘキサメチルトリシロキサン１０８ｇ（５．２×１０^-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６．０×１０^-1ｇ（Ｐｔ単体として１．６×１０^-5ｍｏｌを含有）を混合し、８０℃で４０時間熟成させた。その後、溶剤及び未反応物を減圧留去した。続いて、分子蒸留装置により残存する低沸点成分、高沸点成分を取り除いたところ、液状の生成物（化合物９）２００ｇを得た。Synthesis Example 9 Synthesis of Compound 9 In a reaction vessel, the following formula (M)

200 g (2.6 × 10 ⁻² mol) of the compound represented by the formula, 200 g of 1,3-bis (trifluoromethyl) benzene, 108 g of 1,1,3,3,5,5-hexamethyltrisiloxane (5. 2 × 10 ⁻³ mol) and 6.0 × 10 ⁻¹ g of a chloroplatinic acid / vinylsiloxane complex toluene solution (containing 1.6 × 10 ⁻⁵ mol as a simple substance of Pt) and mixed at 40 ° C. at 40 ° C. Aged for hours. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure. Subsequently, when the remaining low-boiling components and high-boiling components were removed by a molecular distillation apparatus, 200 g of a liquid product (Compound 9) was obtained.

¹Ｈ−ＮＭＲ
δ０−０．４（−ＯＳｉ（ＣＨ ₃）₂）７２Ｈ
δ０．４−０．８（−ＣＨ₂ＣＨ₂ＣＨ ₂−Ｓｉ）８Ｈ
δ１．２−２．０（−ＣＨ ₂ＣＨ ₂ＣＨ₂−Ｓｉ）１６Ｈ
δ３．８−４．２（−ＳｉＨ）４ＨThe obtained compound 9 was confirmed by ¹ H-NMR to have a structure represented by the following formula (N).

¹ H-NMR
δ0-0.4 (-OSi (C H ₃ ) ₂ ) 72H
_{δ0.4-0.8 (-CH 2 CH 2 C H} 2 -Si) 8H
_{δ1.2-2.0 (-C H 2 C H 2} CH 2 -Si) 16H
δ3.8-4.2 (-SiH) 4H

で表される化合物２００ｇ（２．６×１０^-2ｍｏｌ）、１，３−ビス（トリフルオロメチル）ベンゼン２００ｇ、トリメトキシシラン１２．７ｇ（１．１×１０^-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６．０×１０^-1ｇ（Ｐｔ単体として１．６×１０^-5ｍｏｌを含有）を混合し、８０℃で４０時間熟成させた。その後、溶剤及び未反応物を減圧留去した。続いて、分子蒸留装置により残存する低沸点成分、高沸点成分を取り除いたところ、液状の生成物（化合物１０）２０１ｇを得た。Synthesis Example 10 Synthesis of Compound 10 (Comparative Product) In a reaction vessel, the following formula (B)

200 g (2.6 × 10 ⁻² mol), 1,3-bis (trifluoromethyl) benzene 200 g, trimethoxysilane 12.7 g (1.1 × 10 ⁻¹ mol), and platinum chloride A toluene solution of acid / vinylsiloxane complex 6.0 × 10 ⁻¹ g (containing 1.6 × 10 ⁻⁵ mol as a simple substance of Pt) was mixed and aged at 80 ° C. for 40 hours. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure. Then, when the low boiling component and the high boiling component which remain | survive with a molecular distillation apparatus were removed, 201 g of liquid products (compound 10) were obtained.

¹Ｈ−ＮＭＲ
δ０．２−２．２（−ＣＨ ₂ ＣＨ ₂ ＣＨ ₂ −）１２Ｈ
δ３．０−３．５（−Ｓｉ（ＯＣＨ ₃ ）₃）１８ＨThe obtained compound 10 was confirmed by ¹ H-NMR to have a structure represented by the following formula (O).

¹ H-NMR
_{δ0.2-2.2 (-C H 2 C H 2} C H 2 -) 12H
_{δ3.0-3.5 (-Si (OC H 3)} 3) 18H

Furthermore, the following compounds were used for the comparative example.
[Compound 11]

[Compound 12]

[Examples 1-9, Comparative Examples 1-3]
Preparation of surface treatment agent and formation of coating film The above-mentioned compounds 1 to 12 were dissolved in Novec 7200 (3M, ethyl perfluorobutyl ether) to a concentration of 20% by mass to prepare a surface treatment agent. After the preparation of the surface treatment agent, the resin film (manufactured by Tygold) is washed by plasma treatment (Ar: 10 cc, O ₂ : 80 cc, output: 250 W, time: 30 seconds), and 10 mg of the surface treatment agent is vacuumed thereon. Vapor deposition was performed (processing conditions were pressure: 2.0 × 10 ⁻² Pa, heating temperature: 700 ° C.), and a film having a thickness of 15 nm was formed after 24 hours in an atmosphere of 25 ° C. and humidity 50% RH. The resin film was made of polyethylene terephthalate, and the surface of the film was subjected to an acrylic hard coat treatment, and then the outermost surface was subjected to sputtering treatment with SiO ₂ with a thickness of 100 nm.
Films formed using Compounds 1 to 9 were Examples 1 to 9, and films formed using Compounds 10 to 12 were Comparative Examples 1 to 3.

  The coating films of Examples 1 to 9 and Comparative Examples 1 to 3 were evaluated by the following methods. All tests were performed at 25 ° C. and humidity 50% RH.

[Evaluation of wear resistance]
In the obtained coating, the abrasion resistance with respect to the cloth (Bencot) was measured using Tribogear TYPE: 30S (manufactured by Shinto Kagaku Co.).
The test was terminated when the water contact angle was less than 100 ° under the following conditions. The abrasion resistance was evaluated based on the number of wears that maintained a water contact angle of 100 ° or more.
Contact area: 10mm x 30mm
Load: 1.5kg
Cloth wear resistance Cloth: BEMCOT M-3II (Asahi Kasei Co., Ltd.)
Travel distance (one way) 20mm
Movement speed 1,800 mm / min Load: 0.5 kg / cm ²
Moreover, the contact angle with respect to the water (droplet: 2 microliters) of a film was measured for the water contact angle using the contact angle meter DropMaster (made by Kyowa Interface Science Co., Ltd.). The water contact angle was measured 1 second after a 2 μl droplet was deposited on the sample surface.

According to Table 1 above, in Comparative Examples 1, 2, and 3, when the surface treatment agent was vapor-deposited on the substrate surface and the wear resistance test was performed after the post-treatment, the number of wear resistance was 0, and the wear durability No sex was shown. On the other hand, in Examples 1 to 9, when the surface treatment agent was vapor-deposited on the surface of the base material and subjected to an abrasion resistance test after the post-treatment, excellent abrasion resistance was expressed. Examples 1 to 9 have a siloxane bond, a silphenylene structure, or a silalkylene structure at the end of the molecular chain (the linking group portion of the molecule), so that the SiCH ₃ portion of the linking group portion is the SiO ₂ layer on the substrate surface. Since the polymer in the surface treating agent interacts with the OH group part derived from SiO ₂ by the intermolecular force, the surface of the comparative example does not have a hydrolyzable group at the end group. It seems that the adhesion to the substrate is improved compared to the treatment agent.

  The resin in which the antifouling surface layer is formed by the surface treatment agent containing the fluoropolyether group-containing polymer-modified organosilicon compound of the present invention can exhibit excellent wear durability. The resin in which the antifouling surface layer is formed by the surface treatment agent of the present invention can be suitably used particularly for applications requiring antifouling treatment on the surface, such as eyeglass lenses, sunglasses, touch panel displays, and antireflection films.

  The article surface-treated with the surface treatment agent containing the fluoropolyether group-containing polymer-modified organosilicon compound of the present invention exhibits excellent wear durability. The resin product surface-treated with the surface treatment agent of the present invention is particularly effective as a resin product that is assumed to be attached with oils and fats, such as a touch panel display, an antireflection film, and a spectacle lens.

Claims (10)

The following general formula (1)

[Wherein Rf is a monovalent fluorooxyalkyl group or divalent fluorooxyalkylene group-containing polymer residue, Y is independently a divalent hydrocarbon group, and Q is independently a divalent linear chain. Or a cyclic organosiloxane residue, a silalkylene group or a silarylene group, X is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, Z is independently a hydrogen atom, _Three
(In the formula, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group.)
Or a group represented by the following formula -WQ'-X
Wherein X is the same as above, W is a single bond or a divalent hydrocarbon group, Q ′ is a divalent group having a structure selected from a siloxane bond, a silalkylene structure and a silarylene structure. is there.)
And α is 1 or 2. ]
A fluoropolyether group-containing polymer-modified organosilicon compound represented by: 2. The fluoropolyether group-containing polymer-modified organosilicon compound according to claim 1, wherein in the formula (1), α is 1 and the Rf group is a group represented by the following general formula (2).

(In the formula, p, q, r, and s are each an integer of 0 to 200, and p + q + r + s = 3 to 200, each repeating unit may be linear or branched, and each repeating unit is randomly selected. And d is an integer of 1 to 3, and the unit may be linear or branched.) 2. The fluoropolyether group-containing polymer-modified organosilicon compound according to claim 1, wherein in the formula (1), α is 2 and the Rf group is a group represented by the following general formula (3).

(In the formula, p, q, r, and s are each an integer of 0 to 200, and p + q + r + s = 3 to 200, each repeating unit may be linear or branched, and each repeating unit is randomly selected. And d is an integer of 1 to 3, and the unit may be linear or branched.)   In the said Formula (1), Y is a C3-C10 alkylene group, The fluoro polyether group containing polymer modified organosilicon compound of any one of Claims 1-3. The fluoropolyether group-containing polymer-modified organosilicon compound according to any one of claims 1 to 4, wherein in the formula (1), Q is a group selected from the groups represented by the following formulae.

(In the formula, X is the same as above, R ¹ is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ² is an alkylene group having 1 to 4 carbon atoms or an arylene having 6 to 12 carbon atoms. (G is an integer of 1 to 20, and j is an integer of 1 to 8.) The fluoropolyether group-containing polymer-modified organosilicon compound according to any one of claims 1 to 5, wherein, in the formula (1), Z is a group selected from a hydrogen atom and a group shown below.

(In the formula, g1 is an integer of 2 to 20, and e is an integer of 0 to 3.) The fluoropolyether group according to any one of claims 1 to 6, wherein the fluoropolyether group-containing polymer-modified organosilicon compound represented by the formula (1) is represented by any one of the following formulas: Containing polymer-modified organosilicon compound.

(In the formula, Z is the same as above, 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, g1 is an integer of 2 to 20, e Is an integer from 0 to 3.)   A surface treatment agent comprising the fluoropolyether group-containing polymer-modified organosilicon compound according to any one of claims 1 to 7. The surface treatment agent is further represented by the following general formula (4)

(In the formula, A is a monovalent fluorine-containing group whose terminal is a —CF ₃ group, and Rf ′ is a divalent fluorooxyalkylene group-containing polymer residue.)
The surface treating agent according to claim 8, comprising a fluoropolyether group-containing polymer represented by the formula:   An article surface-treated with the surface treating agent according to claim 9.