JP6521091B2 - Fluoropolyether group-containing polymer modified organosilicon compound, surface treating agent and article - Google Patents

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 use of touch panels on screens, including displays of mobile phones, has been accelerating. However, the touch panel is in a state where the screen is exposed, and there are many opportunities for direct adhesion of fingers and cheeks, and it is a problem that dirt such as sebum is easily attached. Therefore, there is an increasing demand for technology to make it difficult to attach fingerprints to the surface of the display and to make it easy to remove dirt in order to improve appearance and visibility, and development of materials that can meet these requirements has It is desired. In particular, fingerprint stains easily adhere to the surface of the touch panel display, and thus it is desirable to provide a water and oil repellent layer. However, although the conventional water- and oil-repellent layer has high water- and oil-repellency and is excellent in stain wiping performance, there is a problem that the antifouling performance is deteriorated during use. Moreover, depending on the method of coating, the performance may vary, and the adhesion may be poor depending on the substrate to be coated. Furthermore, many surface treatment agents so far have exhibited good surface characteristics with respect to glass, but sufficient surface characteristics such as adhesion, water / oil / oil repellency, and abrasion resistance with respect to the resin surface are sufficient. There was nothing to show.

  In general, the fluoropolyether group-containing compound has water and oil repellency, chemical resistance, lubricity, releasability, antifouling property and the like because its surface free energy is very small. Industrially, it is widely used in industrial applications such as water and oil repellent soiling agents such as paper and fiber, lubricants for magnetic recording media, oil repellent agents for precision equipment, mold release agents, cosmetics, and protective films. ing. However, its properties mean that it is at the same time non-adhesive and non-adhesive to other substrates, and even though it can be applied to the substrate surface, it was difficult to adhere the film. .

  On the other hand, silane coupling agents are well known as those for bonding a substrate surface such as glass or cloth to 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 due to moisture in the air or the like to form a film. The coating becomes a durable and durable coating by chemically and physically bonding the hydrolyzable silyl group to a surface such as glass or metal.

  Therefore, by using a fluoropolyether group-containing polymer-modified silane in which a hydrolyzable silyl group is introduced to the fluoropolyether group-containing compound, the base material easily adheres to the substrate surface, and water and oil repellency and oil resistance on the substrate surface. A composition capable of forming a film having chemical properties, lubricity, releasability, antifouling properties, etc. is disclosed (Patent Documents 1 to 8: Japanese Patent Application Laid-Open No. 2003-238577, Patent No. 2860979, Patents No. 4672095, JP-A-2008-534696, JP-A-2008-537557, JP-A-2012-072272, JP-A-2012-157856, JP-A-2013-136833).

  When surface-treating a substrate with the composition containing the fluoropolyether group-containing polymer-modified silane described above, a film is formed on the substrate using various coating methods, but after coating, the hydrolyzable silyl group is coated In the process of hydrolyzing and curing the film, the hydrolysis reaction is promoted by high temperature conditions such as 80.degree. C. and 120.degree. C. and humidified conditions. In addition, a cured film can be formed by gradually reacting with moisture in the air even at room temperature. However, the curing process requires high-temperature humidification conditions, takes a long time to cure at room temperature, and so forth, which may cause a rate-determining factor (delay factor) in manufacturing. Furthermore, the film (water and oil repellent layer) cured in a short time under mild conditions such as room temperature curing has a problem that the anti-soiling property and the antifouling performance are deteriorated during use.

  In patent document 9 (Unexamined-Japanese-Patent No. 2008-144144), it forms into a film in mild conditions and a short time by promoting hardening by adding a fluorine-containing carboxylic acid as a curing catalyst in a coating composition. . However, reducing the amount of catalyst results in inferior wear resistance, and increasing the amount of catalyst lowers the initial performance. In addition, there is a high possibility that the carboxyl group which is a polar group is exposed to the outermost surface of the film, and in that case, the performance is lowered.

  Moreover, in patent document 10 (Unexamined-Japanese-Patent No. 2004-145283), fluoropolyalkylene ether group containing silane is proposed. The lens treated with the fluoropolyalkylene ether group-containing silane is excellent in oil repellency and fingerprint wiping properties but is not sufficiently abrasion resistant.

Unexamined-Japanese-Patent No. 2003-238577 Patent No. 2860979 Patent No. 4672095 Japanese Patent Publication No. 2008-534696 Japanese Patent Application Publication No. 2008-537557 Unexamined-Japanese-Patent No. 2012-072272 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 in particular, on a resin surface, a fluoropolyether group capable of forming a water and oil repellent layer excellent in abrasion resistance even under a mild condition such as room temperature and in a short time. 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 object, the present inventors found that the surface treatment agent using a fluoropolyether group-containing polymer modified organosilicon compound represented by the general formula (1) described later has a terminal functional group. It has been found that a water and oil repellent layer having excellent abrasion resistance even in a short time even under mild conditions such as room temperature can be formed on a resin product such as a resin film or a plastic lens without having the present invention. 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は独立に下記式

（式中、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、Ｒ ¹ 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、Ｒ ² 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。）
で示される基から選ばれる基であり、Ｘは上記と同じであり、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、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〕〜〔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、ｇ１は２〜２０の整数であり、ｅは０〜３の整数である。）
〔６〕
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〕〜〔５〕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。）
〔７〕
〔１〕〜〔６〕のいずれかに記載のフルオロポリエーテル基含有ポリマー変性有機ケイ素化合物を含む表面処理剤。
〔８〕
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〔７〕に記載の表面処理剤。
〔９〕
〔８〕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, R f is a monovalent fluorooxyalkyl group or a divalent fluorooxyalkylene group-containing polymer residue, Y is independently a divalent hydrocarbon group, and Q is independently of the following formula

(Wherein, X is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, R ¹ is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ² is 1 carbon atom It is an alkylene group of -4 or an arylene group having 6 to 12 carbon atoms, g is an integer of 1 to 20, and j is an integer of 1 to 8.)
And X is the same as above , Z is independently a hydrogen atom, and the following formula -SiR ₃
(Wherein R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group)
Or a group represented by the following formula -W-Q'-X
(Wherein, X is the same as above, W is a single bond or a divalent hydrocarbon group, and Q ′ is a divalent group having a structure selected from a siloxane bond, a silalkylene structure and a silarylene structure) is there.)
Is a group represented by and α is 1 or 2. ]
The fluoropolyether group containing polymer modified organosilicon compound represented by these.
[2]
The fluoropolyether group-containing polymer-modified organosilicon compound according to [1], wherein in the formula (1), α is 1 and the Rf group is a group represented by the following general formula (2).

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

(Wherein p, q, r, s are integers of 0 to 200, respectively, and p + q + r + s = 3 to 200, each repeating unit may be linear or branched, and each repeating unit is random 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 in any one of [1]-[3] whose Y is a C3-C10 alkylene group in said Formula (1).
[ 5 ]
The fluoropolyether group containing polymer modified organosilicon compound in any one of [1]-[ 4 ] whose Z is a hydrogen atom and the group shown below in said Formula (1).

(Wherein, g1 is an integer of 2 to 20 and e is an integer of 0 to 3)
[ 6 ]
The fluoropolyether according to any one of [1] to [ 5 ], wherein the fluoropolyether group-containing polymer-modified organic silicon compound represented by the above formula (1) is represented by any one of the following formulas Ether group-containing polymer modified organosilicon compound.

(Wherein Z is 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. g1 is an integer of 2 to 20, e Is an integer of 0 to 3.)
[ 7 ]
The surface treating agent containing the fluoropolyether group containing polymer modified organic silicon compound in any one of [1]-[ 6 ].
[ 8 ]
The surface treatment agent further comprises the following general formula (4)

(In the formula, A is a monovalent fluorine-containing group whose end is a —CF ₃ group, and Rf ′ is a divalent fluorooxyalkylene group-containing polymer residue.)
The surface treating agent according to [ 7 ], which contains a fluoropolyether group-containing polymer represented by
[ 9 ]
[ 8 ] An article surface-treated with the surface treatment agent according to [ 8 ].

  The film formed from the surface treatment agent containing the fluoropolyether group-containing polymer modified organosilicon compound of the present invention is high in water and oil repellency, and in particular, the film formed in a short time under mild conditions such as room temperature Excellent in wear resistance. The surface treatment agent containing the fluoropolyether group-containing polymer modified organosilicon compound of the present invention has a specific adhesion to a resin surface, in particular, and therefore, treatment with the surface treatment agent results in a resin film or glasses It is possible to easily impart excellent water and oil repellency, low dynamic friction, and abrasion resistance 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, R f is a monovalent fluorooxyalkyl group or a divalent fluorooxyalkylene group-containing polymer residue, Y is independently a divalent hydrocarbon group, and Q is an independently divalent linear chain Or cyclic organosiloxane residue, a silalkylene group or a silarylene group, X independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, Z independently represents a hydrogen atom, the following formula -SiR ₃
(Wherein R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group)
Or a group represented by the following formula -W-Q'-X
(Wherein, X is the same as above, W is a single bond or a divalent hydrocarbon group, and Q ′ is a divalent group having a structure selected from a siloxane bond, a silalkylene structure and a silarylene structure) is there.)
Is a group represented by 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, a monovalent fluorooxyalkyl group represented by the following general formula (2) is preferable as Rf.

(Wherein p, q, r, s are integers of 0 to 200, respectively, and p + q + r + s = 3 to 200, each repeating unit may be linear or branched, and each repeating unit is random 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, a divalent fluorooxyalkylene group represented by the following general formula (3) is preferable as Rf.

(Wherein p, q, r, s are integers of 0 to 200, respectively, and p + q + r + s = 3 to 200, each repeating unit may be linear or branched, and each repeating unit is random 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 The integer s is an integer of 0 to 100, p + q + r + s = 3 to 200, preferably 10 to 100, and each repeating unit may be linear or branched, and each repeating unit is randomly bonded It may be done. More preferably, p + q is an integer of 10 to 105, in particular 15 to 60, and r = s = 0. If p + q + r + s is smaller than the above upper limit value, adhesion and film formation properties are good, and if 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 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 a main chain structure represented by the above formula (2) or (3) as Rf, it is possible to form a film having a low coefficient of dynamic friction.
In addition, 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 (where α is 1 and Rf is a formula (2) The monovalent fluorooxyalkyl group to be substituted is a linear polymer (a is 2 and Rf is represented by the formula (3)) containing a siloxane bond, a silphenylene bond or a silalkylene bond at both ends Excellent wear resistance can be imparted to the resulting film as compared to the fluorooxyalkylene group).

（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。）Specifically as Rf, the following can be illustrated.

(Wherein p ′, q ′, r ′, s ′ are each an integer of 1 or more, and the upper limit is the same as the upper limit of the above p, q, r, s. U is 1 to 24, v is 1 to 24 and is a number satisfying u + v = r, and each repeating unit may be randomly combined.)

  In the above formula (1), Y is independently a divalent hydrocarbon group, and is a propylene group having 3 to 10 carbon atoms, particularly 3 to 8 carbon atoms (trimethylene group, methyl ethylene group), butylene group (tetramethylene group) It is preferable that it is an alkylene group such as methylpropylene group), hexamethylene group, octamethylene group and the like, and particularly preferable is trimethylene group.

  In the above formula (1), X independently represents 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 formulas .

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

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

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, and among them, a methyl group or an ethyl group is preferable.

In -W-Q'-X, W is a single bond or a divalent hydrocarbon group, and as the divalent hydrocarbon group, an ethylene group having 2 to 10 carbon atoms, particularly 2 to 8 carbon atoms, And alkylene groups such as propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), hexamethylene group, octamethylene group etc. are mentioned, and W is a single bond or trimethylene group Is preferred.
X is the same as 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 the above Q, a silalkylene structure, Those having a silarylene structure are preferred.
Specific examples of Q ′ include, for example, the following groups.

(Wherein, g 1 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。）As Z, specifically, a hydrogen atom and those shown below can be exemplified.

(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。）As a fluoropolyether group containing polymer modified organic silicon compound represented by said Formula (1), what is represented with a following formula can be illustrated. In each formula, the repeating number (or 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). 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.)

  As a method for preparing the fluoropolyether group-containing polymer-modified organosilicon compound represented by the above formula (1), for example, the following methods may be mentioned.

  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 or an amide group at the molecular chain terminal, a nucleophile, and a solvent For example, by mixing 1,3-bis (trifluoromethyl) benzene and tetrahydrofuran, 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 those shown below.

(Wherein, R f and α are the same as above)

In addition, as a nucleophile, allyl magnesium halide, 3-butenyl magnesium halide, 4-pentenyl magnesium halide, 5-hexenyl magnesium halide and the like can be used. It is also possible to use corresponding lithium reagents.
The amount of the nucleophile used is 2 to 5 equivalents, more preferably 2.5 to 3.5 equivalents, per equivalent of the reactive groups 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 fluorine 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) .

(Wherein R f and α are the same as above. U is a divalent hydrocarbon group.)

  In the above formula (a), U is a divalent hydrocarbon group, and specifically, a methylene group, an ethylene group, a propylene group (trimethylene group, methylethylene group), a butylene group (tetramethylene group, a methylpropylene group) ), Alkylene groups having 1 to 8 carbon atoms such as hexamethylene group and octamethylene group, and alkylene groups having 6 to 8 carbon atoms such as phenylene group (for example, alkylene arylene groups having 7 to 8 carbon atoms, etc.) And the like. As U, Preferably it is a C1-C4 linear alkylene group.

  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.

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

Here, as the silylating agent, for example, silyl halide or silyl triflate can be used. Specifically, trimethylsilyl chloride, triethylsilyl chloride, tert-butyldimethyl chloride, triisopropylsilyl chloride, triphenylsilyl chloride And trimethylsilyl bromide, trimethylsilyl triflate, triethylsilyl triflate, tert-butyldimethyl triflate, triisopropylsilyl triflate, etc., and when no base is used, hexamethyldisilazane, trimethylsilyldimethylamine, trimethylsilyldiethylamine, trimethylsilylimidazole are used. The amount used may be a molecule having a hydroxyl group and an olefin moiety at the end of the molecular chain represented by 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.
Moreover, as the hydrosilane, trimethylsilane, triethylsilane, tert-butyldimethylsilane, triisopropylsilane, triphenylsilane and the like can be mentioned, and the amount thereof used is a hydroxyl group and an olefin at the molecular chain terminal represented by the formula (a) It is possible to use 1 to 5 equivalents, more preferably 1.5 to 3 equivalents, still more preferably about 2 equivalents, to 1 equivalent of the 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 terminal represented by the following formula (b) Be

(Wherein, Rf, R, U and α are the same as above)

  Moreover, as a method of substituting a hydrogen atom of a hydroxyl group with a group represented by -W-Q'-X, for example, a fluoropolyether group containing a hydroxyl group and an olefin moiety at the molecular chain end represented by the formula (a) 0 to 60 ° C., preferably 15 to 35 ° C., more preferably a polymer and an organosilicon compound having an SiH group, in the presence of a dehydrogenation catalyst such as a boron catalyst, using a solvent such as a fluorinated solvent or an organic solvent The dehydrogenation reaction is carried out 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 which has SiH group, the thing shown below can be illustrated, for example.

(Wherein, 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 per equivalent of the hydroxyl group of the 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 to give an olefin moiety at the molecular chain terminal and a hydroxyl moiety represented by the following formula (c): an organosilicon compound group The fluorooxyalkyl group-containing polymer substituted by is obtained.

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

Furthermore, as an alternative method of substituting a hydrogen atom of a hydroxyl group with a group represented by -W-Q'-X, first, a hydrogen atom of a hydroxyl group is substituted with a terminal unsaturated group, and then the terminal unsaturated group ( There may be mentioned a method of reacting an olefin site) with an organosilicon compound having an SiH group together with other olefin sites.
As a method of substituting the terminal unsaturated group with a hydrogen atom of a hydroxyl group, 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) Additives such as tetrabutyl ammonium halide, alkali metal halide etc. in the presence of a base such as an alkali metal base or the like, or an additive such as a fluorine solvent or an organic solvent to improve the reactivity, such as tetrabutyl ammonium halide or alkali metal halide; 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 and the like 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 thereof used is a molecular chain represented by formula (a) It can be used in an amount of 1 to 10 equivalents, more preferably 2.5 to 6 equivalents, still more preferably about 5 equivalents based on 1 equivalent of the hydroxyl group of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the end.

（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 terminal represented by the following formula (d).

(Wherein, 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, and as the divalent hydrocarbon group, specifically, a methylene group, an ethylene group, a propylene group (trimethylene group, a methyl ethylene group An alkylene group containing an alkylene group having 1 to 8 carbon atoms such as butylene group (tetramethylene group, methylpropylene group), hexamethylene group, octamethylene group, etc., or an arylene group having 6 to 8 carbon atoms such as phenylene group (eg And an alkylene arylene group having 7 to 8 carbon atoms and the like. Preferably it is a methylene group as V.

  Then, any of the fluoropolyether group-containing polymers having an olefin moiety at the molecular chain end represented by the formulas (a) to (d) obtained above and an organosilicon compound having an SiH group in the molecule are hydrosilylated. Reaction catalyst, for example, in the presence of a solution of chloroplatinic acid / vinylsiloxane complex in toluene, 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, preferably for 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, as an organic silicon compound which has a SiH group in a molecule | numerator, the compound represented by a following formula is preferable.

(Wherein, R ¹ , R ² , X, g, 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 Is)

（式中、ｇ、ｇ１、ｅは上記と同じである。）As an organic silicon compound which has a SiH group in such a molecule | numerator, what is shown below etc. are mentioned, for example.

(Wherein, g, g1 and e are as defined 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, more preferably about 10 equivalents can be used.

  Thereafter, the solvent and the unreacted material are distilled off under reduced pressure, whereby the fluoropolyether group-containing polymer-modified organosilicon compound represented by the above formula (1) can be obtained. In addition, it is also possible to perform the reaction mentioned above independently or continuously.

  The surface treatment agent of the present invention contains the 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 comprises the following general formula (4)

(Wherein, A is a fluorine atom or a monovalent fluorine-containing group having a terminal of —CF ₃ group, and Rf ′ is a divalent fluorooxyalkylene group-containing polymer residue)
And a fluoropolyether group-containing polymer (hereinafter referred to as a nonfunctional polymer) represented by

（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 or a linear perfluoroalkyl group having 1 to 6 carbon atoms, Among them -F group, -CF ₃ group, -CF ₂ CF ₃ group, -CF ₂ CF ₂ CF ₃ group is preferred.
Further, Rf 'is a divalent fluorooxyalkylene group-containing polymer residue, and as Rf', those shown below are preferable.

(Wherein 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, t1 is 5 to 200, preferably an integer of 10 to 100, t2 is an integer of 10 to 200, preferably an integer of 20 to 100, t1 + p2 is an integer of 10 to 205, preferably an integer of 20 to 110, q2 + p2 is an integer of 10 to 205, preferably 20 to 110 Is an integer of

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

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

  The amount used in the case of blending the nonfunctional polymer represented by the formula (4) is not particularly limited, but it is preferably 0. 1 with respect to the mass of the fluoropolyether group-containing polymer modified organosilicon compound represented by the formula (1). A range of 1 to 60% by mass, particularly 10 to 40% by mass is preferable, and when the amount is too large, an adhesion problem may occur.

The surface treatment agent may contain a suitable solvent. As such solvents, fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane and the like), fluorine-modified aromatic hydrocarbon solvents (m-xylene hexafluoride (1,3-bis (trifluoro) Methyl) benzene), benzo trifluoride etc), fluorine modified ether solvents (methyl perfluoro butyl ether, ethyl perfluoro butyl ether, perfluoro (2-butyl tetrahydrofuran) etc), fluorine modified alkyl amine solvents (perfluoro tributyl amine, Perfluorotripentylamine etc., hydrocarbon solvents (petroleum benzine, mineral spirits, toluene, xylene etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone etc.) can be exemplified. Among these, fluorine-modified solvents are preferable in terms of solubility, wettability and the like, and in particular, m-xylene hexafluoride, perfluoro (2-butyltetrahydrofuran), perfluorotributylamine, ethyl perfluoro Butyl ether is preferred.
Although the said solvent may mix the 2 or more types, it is preferable to dissolve a fluoropolyether group containing polymer modified organosilicon compound uniformly. The optimum concentration of the fluorooxyalkylene group-containing polymer- modified organosilicon compound to be dissolved in the solvent varies depending on the treatment method, but it is 0.01 to 40% by mass, particularly 0.05 to 25% by mass in the surface treatment agent. Is preferred.

The surface treatment agent of the present invention is subjected to surface treatment to a resin product such as a resin film or an eyeglass lens. Here, as the resin product, one made of a thermoplastic resin is preferable, and specifically, a hard coat-treated thermoplastic resin film (hard coat film), which has a pencil hardness of 4 H or more and is not provided with a hard coat A thermoplastic resin film (high hardness resin film) or a thermoplastic resin film (antireflection film) provided with an antireflection layer is preferably used.
Further, in the present invention, it is preferable to use one obtained by treating the above-mentioned resin product with SiO ₂ in advance. Here, the SiO ₂ treatment is preferable from the viewpoint of improving the adhesion between the resin product and the treating agent, which has been SiO ₂ treated by the sputtering method.

The surface treatment agent of the present invention can be applied onto a substrate by known methods such as brushing, dipping, spraying, vapor deposition and the like. The heating method at the time of vapor deposition may be either resistance heating or electron beam heating, and is not particularly limited. 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 substrate, from room temperature (25 ° C.) The temperature may be in the range of 200 ° C. for 5 minutes to 24 hours, in particular 10 minutes to 12 hours, and may be post-treated under humidification. In the present invention, in particular, 10 minutes to 24 hours, in particular 30 minutes to 12 hours, is sufficient even at room temperature. Further, the film thickness of the film is appropriately selected depending on the type of the substrate, but is usually 0.1 to 100 nm, particularly 1 to 25 nm.

  The resin products to be treated with the surface treatment agent of the present invention include car navigations, mobile phones, digital cameras, digital video cameras, PDAs, portable audio players, car audios, game machines, game lenses, eyeglass lenses, camera lenses, lens filters, Parts of products such as sunglasses, medical instruments such as stomach cameras, copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panels, protective films, hard coat films, high hardness resins, antireflective films, wearable terminals, etc. An optical article, a touch panel, an antireflective film, a quartz substrate, etc. which are used as a part or part are preferable.

  The surface treatment agent for surface-treating the resin product of the present invention can form a film on the article even in a short time under mild conditions such as room temperature, and the film is excellent in water and oil repellency and durability. In particular, it is useful as a water and oil repellent layer for glasses lenses, touch panel displays, hard coat films, high hardness resins, antireflective films, wearable terminals and the like. Here, a high hardness resin is, for example, a product that is molded as a glass substitute film and molded with a resin having a pencil hardness of 4H or more, such as Silplus manufactured by Nippon Steel Chemical Co., Ltd., and a trade name HD film manufactured by Gunze Co. In particular, it refers to a resin film formed by molding the resin, but is not particularly limited to the above-mentioned products.

Hereinafter, the present invention will be described in more detail by way of synthesis examples, examples and comparative examples, but the present invention is not limited by the following examples.
The examples and comparative examples used the compounds obtained by the following synthesis examples.

で表される化合物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 dropped. Subsequently, the following formula (A)

Compound represented by 4 . 8 × 10 ^-2 was added dropwise slowly mo l, it was heated for 4 hours at 60 ° C.. After the completion of heating, the reaction solution was cooled to room temperature and dropped into 300 g of a 1.2 M aqueous hydrochloric acid solution to stop the reaction. The lower layer fluorine compound layer was recovered by liquid separation operation and then washed with acetone. The fluorine compound layer is a lower layer after washing was recovered again under reduced pressure by distilling off the residual solvent, to obtain a fluoropolyether group containing polymer over represented by the following formula (B).

で表される化合物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）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）８Ｈ In the reaction vessel, the following formula (B)

Compound 1 represented by Put 0 × 10 ^-2 mo l, 1,3- bis dissolved in (trifluoromethyl) benzene 80 g, 2 as a toluene solution 8.0 × 10 ^-2 g (Pt alone of chloroplatinic acid / vinyl siloxane complex. Mix 1 × 10 ⁻⁶ mol) and 37 g (1.9 × 10 ⁻¹ mol) of 1,4-bis (dimethylsilyl) benzene, and age at 80 ° C. for 7 hours to obtain solvent and unreacted material The compound was evaporated under reduced pressure to obtain a fluoropolyether group-containing polymer (compound 1 ) represented by the following formula (C).

¹ H-NMR
δ 0-0.2 (-Si (C H ₃ ) ₂ ) 24 H
δ 0.4-0.6 (-CH ₂ CH ₂ C H ₂ -Si) 4 H
δ 1.3-1.6 (-CH ₂ C H ₂ CH ₂ -Si) 4 H
δ 1.6-1.9 (-C H ₂ CH ₂ CH ₂ -Si) 4 H
δ 3.6-4.2 (-Si H ) 2 H
δ 6.6-7.1 (-C ₆ H ₄ ) 8 H

で表される化合物２．７×１０^-2ｍｏｌを混合した後、トリメチルクロロシラン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)

And the compound 2 represented by After mixing the 7 × 10 ^-2 mo l, trimethylchlorosilane Sila down 5. 4 × 10 ⁻² mol was dropped. Subsequently, it was heated at 50 ° C. for 3 hours. After heating, the reaction solution was cooled to room temperature, and a hydrochloric acid aqueous solution was added dropwise. The lower layer fluorine compound layer was recovered by liquid separation operation and then washed with methanol. The fluorine compound layer is a lower layer after washing was recovered again under reduced pressure by distilling off the residual solvent, to obtain a fluoropolyether group containing polymer over represented by the following formula (D).

¹ H-NMR
δ 0-0.2 (-OSi (C H ₃ ) ₃ ) 9 H
δ 2.4-2.6 (-C H ₂ CH = CH ₂ ) 4 H
δ 5.0-5.2 (-CH ₂ CH = C H ₂ ) 4 H
δ 5.7-5.9 (-CH ₂ C H = CH ₂ ) 2 H

で表される化合物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）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）６Ｈ In the reaction vessel, the following formula (D)

Compound 1 represented by Put 4 × 10 ^-2 mo l, 1,3- bis dissolved in (trifluoromethyl) benzene 50 g, toluene solution 1.5 × 10 ^-1 g of chloroplatinic acid / vinyl siloxane complex (Pt 4 as a single. and 0 × containing 10 ^-6 mol), 1,3,5,7- tetramethylcyclotetrasiloxane siloxanyl down 1. A fluoropolyether group-containing polymer (compound represented by the following formula (E) is obtained by mixing 3 × 10 ⁻¹ mol and aging at 80 ° C. for 19 hours and evaporating the solvent and the unreacted material under reduced pressure. 2 ) got.

¹ H-NMR
δ 0-0.2 (-OSi-C H ₃ , -OSi (C H ₃ ) ₃ ) 36 H
δ 0.5-0.8 (-CH ₂ CH ₂ C H ₂ -Si) 4 H
δ 1.3-2.2 (-C H ₂ C H ₂ CH ₂ -Si) 8 H
δ 4.3-5.2 (-Si H ) 6 H

で表される化合物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）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）２Ｈ Synthesis Example 3 Synthesis of Compound 3 In a reaction vessel, the following formula (B)

Compound represented by 4 . Put 0 × 10 ^-2 mo l, 1,3- bis dissolved in (trifluoromethyl) benzene 150 g, 4 as a toluene solution 8.0 × 10 ^-2 g (Pt alone of chloroplatinic acid / vinyl siloxane complex. Aged at 80 ° C. by mixing 0 × 10 ⁻⁶ mol) and 83 g (4.0 × 10 ⁻¹ mol) of 1,1,3,3,5,5,5-hexamethyltrisiloxane Then, the solvent and the unreacted material were distilled off under reduced pressure to obtain a fluoropolyether group-containing polymer (compound 3 ) represented by the following formula (F).

¹ H-NMR
δ 0-0.2 (-OSi (C H ₃ ) ₂ ) 36 H
δ 0.3-0.6 (-CH ₂ CH ₂ C H ₂ -Si) 4 H
δ 1.3-1.8 (-C H ₂ CH ₂ CH ₂ -Si, -CH ₂ C H ₂ CH ₂ -Si) 8 H
δ 3.3-3.6 (-SiH) 2 H

で表される化合物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）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）２Ｈ Synthesis Example 4 Synthesis of Compound 4 In a reaction vessel, the following formula (B)

Compound 1 represented by Put 4 × 10 ^-2 mo l, 1,3- bis dissolved in (trifluoromethyl) benzene 50 g, 1 as a toluene solution 8.0 × 10 ^-2 g (Pt alone of chloroplatinic acid / vinyl siloxane complex. Mixed with 3 × 10 ⁻⁶ mol) and 40 g (1.4 × 10 ⁻¹ mol) of 1,1,3,3,5,5,5,7,7-octamethyltetrasiloxane, After aging for 4 hours, the solvent and the unreacted material were distilled off under reduced pressure to obtain a fluoropolyether group-containing polymer (compound 4 ) represented by the following formula (G).

¹ H-NMR
δ 0-0.2 (-OSi (C H ₃ ) ₂ ) 48 H
δ 0.3-0.6 (-CH ₂ CH ₂ C H ₂ -Si) 4 H
δ 1.3-1.8 (-C H ₂ CH ₂ CH ₂ -Si, -CH ₂ C H ₂ CH ₂ -Si) 8 H
δ 3.3-3.6 (-SiH) 2 H

で表される化合物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）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）２Ｈ Synthesis Example 5 Synthesis of Compound 5 In a reaction vessel, the following formula (B)

The compound 0 represented by Put 5 × 10 ^-2 mo l, 1,3- bis dissolved in (trifluoromethyl) benzene 20 g, 0 as a toluene solution 2.0 × 10 ^-2 g (Pt alone of chloroplatinic acid / vinyl siloxane complex. 5 × 10 ^-6 mol) and the following formula (H)

In Dekashirokisa down 0 shown. The fluoropolyether group-containing polymer (compound) represented by the following formula (I) is obtained by mixing 5 × 10 ⁻¹ mol and aging for 7 hours at 80 ° C. and evaporating the solvent and the unreacted material under reduced pressure. 5 ) got.

¹ H-NMR
δ 0-0.2 (-OSi (C H ₃ ) ₂ ) 120 H
δ 0.3-0.8 (-CH ₂ CH ₂ C H ₂ -Si) 4 H
δ 1.3-1.8 (-C H ₂ CH ₂ CH ₂ -Si, -CH ₂ C H ₂ CH ₂ -Si) 8 H
δ 4.7-5.0 (-SiH) 2 H

で表される化合物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）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）８Ｈ Synthesis Example 6 Synthesis of Compound 6 In a reaction vessel, the following formula (B)

Compound 1 represented by Put 3 × 10 ^-2 mo l, 1,3- bis dissolved in (trifluoromethyl) benzene 50 g, 1 as a toluene solution 5.0 × 10 ^-2 g (Pt alone of chloroplatinic acid / vinyl siloxane complex. and 4 × containing 10 ^-6 mol), pentamethyldipropylene siloxanyl down 1. A fluoropolyether group-containing polymer (compound represented by the following formula (J) is obtained by mixing 4 × 10 ⁻¹ mol and aging for 8 hours at 80 ° C. and evaporating the solvent and the unreacted material under reduced pressure. 6 ) got.

¹ H-NMR
δ 0-0.2 (-Si-C H ₃ ) 30 H
δ 0.2-0.4 (-CH ₂ CH ₂ C H ₂ -Si) 4 H
_{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）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）８Ｈ Synthesis Example 7 Synthesis of Compound 7 In a reaction vessel, the following formula (B)

Compound 1 represented by Put 3 × 10 ^-2 mo l, 1,3- bis dissolved in (trifluoromethyl) benzene 50 g, toluene solution 1.0 × 10 ^-1 g of chloroplatinic acid / vinyl siloxane complex (Pt 2 as a unit. A mixture of 8 × 10 ^-6 mol) and 13 g (3.2 × 10 ^-2 mol) of 1-butane-decamethylpentasiloxane is aged at 80 ° C. for 20 hours, and the solvent and the unreacted material are depressurized. By distilling off, a fluoropolyether group-containing polymer (compound 7 ) represented by the following formula (K ) was obtained.

¹ H-NMR
δ 0-0.2 (-Si-C H ₃ ) 60 H
δ 0.3-0.6 (-CH ₂ CH ₂ C H ₂ -Si) 8 H
_{δ0.6-0.8 (-CH 2 CH 2 CH 2} -C H 3) 6H
δ 1.1-1.3 (-CH ₂ C H ₂ C H ₂ -C H ₃ ) 8 H
δ 1.4-1.8 (-C H ₂ C H ₂ CH ₂ -Si) 8 H

で表される化合物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）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)

The compound 0 represented by Put 7 × 10 ^-2 mo l, 1,3- bis dissolved in (trifluoromethyl) benzene 25 g, 0 as a toluene solution 2.5 × 10 ^-2 g (Pt alone of chloroplatinic acid / vinyl siloxane complex. and 7 × containing 10 ^-6 mol), bis (dimethylsilyl) methane 0. 7 × 10 ⁻¹ mol is mixed, aged at 80 ° C. for 24 hours, and a solvent and an unreacted material are distilled off under reduced pressure to obtain a fluoropolyether group-containing polymer (compound represented by the following formula (L) 8 ) got.

¹ H-NMR
δ 0-0.4 (-OSi (C ₃ H ₃ ) ₂ , -Si-C ₂ H ₂ -Si) 28 H
δ 0.4-0.8 (-CH ₂ CH ₂ C H ₂ -Si) 4 H
δ 1.2-2.0 (-C H ₂ C H ₂ CH ₂ -Si) 8 H
δ 3.8-4.2 (-SiH) 2 H

で表される化合物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 ^-1 ｍｏｌ）、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）を得た。 Synthesis Example 9 Synthesis of Compound 9 In a reaction vessel, the following formula (M)

And the compound 2 represented by 6 × 10 ^-2 mo l, 1,3- bis (trifluoromethyl) benzene 200 g, 1,1,3,3,5,5 hexamethyl trisiloxane ^{108g (5.2 × 10 -1 mol)} , and A toluene solution of chloroplatinic 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 the unreacted material were distilled off under reduced pressure. Subsequently, the remaining low boiling point components and high boiling point components were removed by a molecular distillation apparatus to obtain a liquid product (compound 9 ) .

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）４ＨIt was confirmed by ¹ H-NMR that the obtained compound 9 has a structure represented by the following formula (N).

¹ H-NMR
δ 0-0.4 (-OSi (C H ₃ ) ₂ ) 72 H
δ 0.4-0.8 (-CH ₂ CH ₂ C H ₂ -Si) 8 H
δ 1.2-2.0 (-C H ₂ C H ₂ CH ₂ -Si) 16 H
δ 3.8-4.2 (-SiH) 4 H

で表される化合物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）を得た。 Synthesis Example 10 Synthesis of Compound 10 (Comparative Product) In a reaction vessel, the following formula (B)

And the compound 2 represented by 6 × 10 ^-2 mo l, 1,3- bis (trifluoromethyl) benzene 200 g, trimethoxysilane down 1. 1 × 10 ^-1 mo l, and a toluene solution 6.0 × 10 ^-1 g of chloroplatinic acid / vinylsiloxane complex (Pt containing 1.6 × 10 ^-5 mol as a unit) were mixed, 40 at 80 ° C. Aging for time. Thereafter, the solvent and the unreacted material were distilled off under reduced pressure. Subsequently, the remaining low-boiling components and high-boiling components were removed by a molecular distillation apparatus to obtain a liquid product (compound 10 ) .

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

¹ H-NMR
δ 0.2-2.2 (-C H ₂ C H ₂ C H _2- ) 12 H
δ 3.0-3.5 (-Si (OC H ₃ ) ₃ ) 18 H

Furthermore, the following compounds were used in comparative examples.
[Compound 11]

[Compound 12]

[Examples 1 to 9, Comparative Examples 1 to 3]
Preparation of surface treatment agent and formation of film The above compounds 1 to 12 were dissolved in Novec 7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20% by mass to prepare a surface treatment agent. After preparation of the surface treatment agent, the resin film (made by Taigold Corporation) is washed with plasma treatment (Ar: 10 cc, O ₂ : 80 cc, power: 250 W, time: 30 seconds), and 10 mg of the above surface treatment agent is vacuumed thereon. The film was deposited (processing conditions: pressure: 2.0 × 10 ⁻² Pa, heating temperature: 700 ° C.), and a film having a film 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 after the film surface was subjected to an acrylic hard coat treatment, the outermost surface was sputtered with SiO ₂ to a thickness of 100 nm.
The films formed using Compounds 1 to 9 are referred to as Examples 1 to 9 and the films formed using Compounds 10 to 12 are referred to as Comparative Examples 1 to 3.

  The coatings 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 50% RH.

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

According to Table 1 above, in Comparative Examples 1, 2 and 3, when the surface treatment agent is vapor deposited and coated on the surface of the substrate and the wear resistance test is performed after the post-treatment, the number of wear resistances is zero, and the wear resistance is Sex was not shown. On the other hand, in Examples 1 to 9, when the surface treatment agent was vapor-deposited and coated on the surface of the base material and the abrasion resistance test was performed after the post-treatment, excellent abrasion resistance was developed. Since Examples 1 to 9 have a siloxane bond, a silphenylene structure, or a silalkylene structure at the molecular chain end (linking group portion of the molecule), particularly the SiCH ₃ portion of these linking group portions is the SiO ₂ layer on the substrate surface Since the polymer in the surface treatment agent is easily oriented due to the interaction with the SiO ₂ -derived OH group portion of the surface treatment agent by the intermolecular force, the surface of the comparative example has no hydrolyzable group at the terminal group. It is considered that the adhesion to the substrate is improved as compared with 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 of surfaces such as spectacle lenses, sunglasses, touch panel displays, and antireflection films.

  An article surface-treated with a surface treatment agent containing the fluoropolyether group-containing polymer modified organosilicon compound of the present invention exhibits excellent abrasion durability. The resin product surface-treated with the surface treatment agent of the present invention is particularly effective as a resin product such as a touch panel display, an antireflective film, an eyeglass lens and the like in which adhesion of oil and fat is assumed.

Claims (9)

The following general formula (1)

[Wherein, R f is a monovalent fluorooxyalkyl group or a divalent fluorooxyalkylene group-containing polymer residue, Y is independently a divalent hydrocarbon group, and Q is independently of the following formula

(Wherein, X is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, R ¹ is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ² is 1 carbon atom It is an alkylene group of -4 or an arylene group having 6 to 12 carbon atoms, g is an integer of 1 to 20, and j is an integer of 1 to 8.)
And X is the same as above , Z is independently a hydrogen atom, and the following formula -SiR ₃
(Wherein R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group)
Or a group represented by the following formula -W-Q'-X
(Wherein, X is the same as above, W is a single bond or a divalent hydrocarbon group, and Q ′ is a divalent group having a structure selected from a siloxane bond, a silalkylene structure and a silarylene structure) is there.)
Is a group represented by and α is 1 or 2. ]
The fluoropolyether group containing polymer modified organosilicon compound represented by these. 2. The fluoropolyether group-containing polymer-modified organosilicon compound according to claim 1, wherein in the formula (1), α is 1 and the R f group is a group represented by the following general formula (2).

(Wherein p, q, r, s are integers of 0 to 200, respectively, and p + q + r + s = 3 to 200, each repeating unit may be linear or branched, and each repeating unit is random And d is an integer of 1 to 3, and the unit may be linear or branched.) 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).

(Wherein p, q, r, s are integers of 0 to 200, respectively, and p + q + r + s = 3 to 200, each repeating unit may be linear or branched, and each repeating unit is random And d is an integer of 1 to 3, and the unit may be linear or branched.)   The fluoropolyether group-containing polymer-modified organosilicon compound according to any one of claims 1 to 3, wherein in the formula (1), Y is an alkylene group having 3 to 10 carbon atoms. The fluoropolyether group-containing polymer-modified organosilicon compound according to any one of claims 1 to 4 , wherein Z in the formula (1) is a hydrogen atom and a group selected from the groups shown below.

(Wherein, 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 5 , wherein the fluoropolyether group-containing polymer-modified organic silicon compound represented by the above formula (1) is represented by any one of the following formulas. Containing polymer modified organosilicon compound.

(Wherein Z is 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. g1 is an integer of 2 to 20, e Is an integer of 0 to 3.) A surface treatment agent comprising the fluoropolyether group-containing polymer modified organosilicon compound according to any one of claims 1 to 6 . The surface treatment agent further comprises the following general formula (4)

(In the formula, A is a monovalent fluorine-containing group whose end is a —CF ₃ group, and Rf ′ is a divalent fluorooxyalkylene group-containing polymer residue.)
The surface treating agent according to claim 7 , containing a fluoropolyether group-containing polymer represented by An article surface-treated with the surface treatment agent according to claim 8 .