WO2025047303A1 - Fluorine-containing ether composition, surface treatment agent, and article - Google Patents

Abstract

Provided is a fluorine-containing ether composition which contains: a fluoropolyether group-containing polymer that contains a hydrolyzable silyl group or a silanol group having a specific structure that includes CF₃O- or CF₃CF₂O- at a terminal; and/or a partial (hydrolysis) condensation product of the polymer. The fluoropolyether group-containing polymer and/or the partial (hydrolysis) condensation product of the polymer are contained at a quantity whereby the molar ratio of CF₃O- and CF₃CF₂O- (CF₃CF₂O-/CF₃O-) is 0.01-0.17. The fluorine-containing ether composition can form a cured film that exhibits water-and oil-repellency and excellent anti-fouling properties, heat resistance, surface release properties and durability against eraser abrasion.

Description

Fluorine-containing ether composition, surface treatment agent and article

The present invention relates to a fluorine-containing ether composition containing a fluoropolyether group-containing polymer (a compound having a fluoropolyether group in the molecule), and more specifically to a fluorine-containing ether composition containing a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group and/or a partial (hydrolyzed) condensate thereof, which is capable of forming a cured coating having water and oil repellency, as well as excellent stain resistance, heat resistance, surface peelability and eraser abrasion resistance, a surface treatment agent containing the fluorine-containing ether composition, and an article surface-treated with the surface treatment agent.

In recent years, the use of touch panels in displays, including smartphones, has accelerated. However, touch panels have exposed screens and are often in direct contact with fingers or cheeks, which makes them susceptible to dirt such as sebum. As a result, there is an increasing demand every year for technology that makes it difficult for fingerprints to appear on the surface of displays to improve appearance and visibility, and technology that makes it easy to remove dirt, and there is a need to develop materials that can meet these demands. In particular, since the surface of touch panel displays is prone to fingerprints, there is a demand for the provision of a water- and oil-repellent layer. However, while conventional water- and oil-repellent layers are highly water- and oil-repellent and easy to wipe off, there is a problem in that their anti-fouling performance deteriorates during use.

Generally, fluoropolyether group-containing compounds have very low surface free energy and therefore have water and oil repellency, chemical resistance, lubricity, release properties, and stain resistance. Taking advantage of these properties, they are widely used industrially as water and oil repellent and stain resistant agents for paper and textiles, lubricants for magnetic recording media, oil repellents for precision instruments, release agents, cosmetics, protective films, and more. However, these properties also mean that they are non-sticky and non-adhesive to other substrates, and although they can be applied to the surface of a substrate, it has been difficult to make the coating adhere to it.

On the other hand, silane coupling agents are well known as agents that bond organic compounds to the surfaces of substrates such as glass and cloth, and are widely used as coating agents for the surfaces of various substrates. Silane coupling agents have 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 undergoes a self-condensation reaction in the presence of moisture in the air to form a coating. The hydrolyzable silyl group chemically and physically bonds with the surface of glass, metal, etc., resulting in a strong, durable coating.

Therefore, compositions have been disclosed that use fluoropolyether group-containing polymers in which hydrolyzable silyl groups have been introduced into fluoropolyether group-containing compounds, and that can form coatings on the substrate surface that are easily adhered to the substrate surface and have water and oil repellency, chemical resistance, lubricity, releasability, and stain resistance (Patent Documents 1 to 6: JP-T-2008-534696, JP-T-2008-537557, JP-A-2012-072272, JP-A-2012-157856, JP-A-2013-136833, and JP-A-2015-199906).

In particular, as a method for forming a coating with improved heat resistance, it has been reported that an organic group containing an alicyclic structure having 3 to 13 carbon atoms is a thermally stable structure, and that a fluorine-containing ether compound containing this organic group has improved heat resistance (Patent Document 7: International Publication No. 2021/054202). However, since it is necessary to introduce a specific organic group, it becomes difficult to achieve both of these properties even if other performances are improved.
In addition to the above-mentioned documents, the following documents can be mentioned as prior art related to the present invention.

Special Publication No. 2008-534696 Special Publication No. 2008-537557 JP 2012-072272 A JP 2012-157856 A JP 2013-136833 A JP 2015-199906 A International Publication No. 2021/054202 Patent No. 6451279 Patent No. 6119656 Patent No. 6828744 Patent No. 6524955 Patent No. 6521091

The present invention has been made in consideration of the above circumstances, and aims to provide a fluorine-containing ether composition containing a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group and/or a partial (hydrolyzed) condensate thereof, capable of forming a cured coating having water and oil repellency, as well as excellent stain resistance, heat resistance, surface peelability and eraser abrasion resistance, a surface treatment agent containing the fluorine-containing ether composition, and an article surface-treated with the surface treatment agent.

In order to achieve the above object, the present inventors have newly discovered that a surface treatment agent containing a fluorine-containing composition containing a fluoropolyether group-containing polymer and/or a partial (hydrolyzed) condensate thereof in which a hydrolyzable silyl group has been introduced into a fluoropolyether group-containing compound, and/or a surface treatment agent containing a fluorine-containing composition containing a partial (hydrolyzed) condensate thereof, can form a cured coating having high performance in terms of water and oil repellency, heat resistance, and abrasion resistance, by considering the molar ratio in the composition of the fluoropolyether group contained in the fluoropolyether group-containing compound, particularly the fluorooxymethylene group and the fluorooxyethylene group adjacent to the terminal fluorooxyalkyl group.

As a result of further investigations, the present inventors have found that a surface treatment agent containing a fluorine-containing ether composition containing a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end and/or a partial (hydrolyzed) condensate thereof, which is represented by the average composition formula (1) described below, in which the molar ratio of the terminal groups fluorooxymethyl group and fluorooxyethyl group is within a specific range, can form a cured coating that is water- and oil-repellent, as well as excellent stain resistance, heat resistance, surface peelability, and eraser abrasion resistance, and have been able to complete the present invention.

［式中、ＲＦ¹はＣＦ₃Ｏ－又はＣＦ₃ＣＦ₂Ｏ－であり、ＣＦ₃Ｏ－とＣＦ₃ＣＦ₂Ｏ－のモル比（ＣＦ₃ＣＦ₂Ｏ－／ＣＦ₃Ｏ－）が０．０１以上０．１７以下である。ＲＦ²は－ＣＦ₂Ｏ－又は－ＣＦ₂ＣＦ₂Ｏ－であり、Ｒｆは下記式（２）

（式中、Ｗは１以上の水素原子を含むフルオロアルキレン基である。ｄは１～６の整数であり、ｐ、ｑ、ｒ、ｓ、ｔ、ｕ、ｖはそれぞれ０～４５０の整数で、ｐ＋ｑ＋ｒ＋ｓ＋ｔ＋ｕ＋ｖ＝１０～４５０であり、これら各単位は直鎖状であっても分岐状であってもよい。また、ｐ、ｑ、ｒ、ｓ、ｔ、ｕ、ｖが付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。）
で表される２価のフルオロポリエーテル基であり、Ｕは単結合又は２～５価の有機基であり、Ｚは独立に単結合、又は炭素原子、ケイ素原子、窒素原子、－ＳｉＲ’＝（Ｒ’は炭素数１～４のアルキル基）もしくは３～９価の有機基であり、Ｙは独立にフッ素原子、ケイ素原子及びシロキサン結合から選ばれる１種もしくは２種以上を有していてもよい２価炭化水素基であり、Ｒは独立に炭素数１～４のアルキル基又はフェニル基であり、Ｘは独立に水酸基又は加水分解性基であり、ａはケイ素原子に結合する単位毎に独立して２又は３であり、ｂは独立に１～８の整数であり、ｃは１～４の整数である。］
［２］
　前記式（１）のＲＦ²において、－ＣＦ₂Ｏ－と－ＣＦ₂ＣＦ₂Ｏ－とのモル比（－ＣＦ₂ＣＦ₂Ｏ－／－ＣＦ₂Ｏ－）が１．０５以上１．２以下である［１］に記載の含フッ素エーテル組成物。
［３］
　前記式（１）において、Ｘが、水酸基、炭素数１～１０のアルコキシ基、炭素数２～１０のアルコキシ置換アルコキシ基、炭素数２～１０のアシロキシ基、炭素数２～１０のアルケニルオキシ基及びハロゲン基からなる群より選ばれるものである［１］又は［２］に記載の含フッ素エーテル組成物。
［４］
　前記式（１）において、Ｕが、単結合、カルボニル基、アミド基、下記式で示される基、

（式中、Ｂは水素原子、炭素数１～２０の１価炭化水素基又は１価のポリエーテル基であり、Ｂ’は水素原子又は炭素数１～２０の１価炭化水素基である。）
又は酸素原子、硫黄原子、水酸基、ポリエーテル基、ジオルガノシリレン基、ケイ素原子数２～１００個の直鎖状の２価のオルガノポリシロキサン残基、シルアルキレン基、シルアリーレン基、２級アミノ基、３級アミノ基、エーテル基、カルボニル基、アミド基、及びエステル基から選ばれる１種又は２種以上の原子又は基を含んでいてもよい炭素数１～２０の２～５価の炭化水素基である［１］～［３］のいずれかに記載の含フッ素エーテル組成物。
［５］
　前記式（１）において、Ｚが、単結合、炭素原子、ケイ素原子、窒素原子、ケイ素原子数３～１３個の直鎖状、分岐状もしくは環状の３～８価のオルガノポリシロキサン残基、３価のイソシアヌル基、又は３価のトリアジン環含有基である［１］～［４］のいずれかに記載の含フッ素エーテル組成物。
［６］
　前記式（１）において、Ｙが、炭素数１～１０のアルキレン基、フッ素原子を含む炭素数１～１０のアルキレン基、炭素数６～８のアリーレン基を含む炭素数１～１０のアルキレン基、炭素数１～１０のアルキレン基相互がシルアルキレン構造又はシルアリーレン構造を介して結合している２価の基、及びケイ素原子数２～１０個の直鎖状又はケイ素原子数３～１０個の分岐状もしくは環状の２価のオルガノポリシロキサン残基の結合手に炭素数２～１０のアルキレン基が結合している２価の基からなる群より選ばれる基である［１］～［５］のいずれかに記載の含フッ素エーテル組成物。
［７］
　更に、下記一般式（３）で表される両末端にシラノール基又は加水分解性シリル基を有するフルオロポリエーテル基含有ポリマー及び／又はその部分（加水分解）縮合物を、該組成物中に２５質量％以下含有するものである［１］～［６］のいずれかに記載の含フッ素エーテル組成物。

［式中、Ｕ、Ｚ、Ｙ、Ｒ、Ｘ、ａ、ｂ、ｃは独立に上記と同じであり、Ｒｆ’は下記式（４）

（式中、Ｗ、ｄ、ｐ、ｑ、ｒ、ｓ、ｔ、ｕ、ｖ、ｐ＋ｑ＋ｒ＋ｓ＋ｔ＋ｕ＋ｖは上記と同じである。ｄ’は１～６の整数である。これら各単位は直鎖状であっても分岐状であってもよい。また、ｐ、ｑ、ｒ、ｓ、ｔ、ｕ、ｖが付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。）
で表される２価のフルオロポリエーテル基である。）］
［８］
　更に、下記一般式（５）で表されるフルオロポリエーテル基含有ポリマーを、該組成物中に３０質量％以下含有するものである［１］～［７］のいずれかに記載の含フッ素エーテル組成物。
　　Ａ－Ｒｆ’－Ａ　　　　　（５）
［式中、Ａは独立に、フッ素原子、水素原子、又は末端がＣＦ₃－、ＣＦ₂Ｈ－、ＣＦ₃ＣＦ₂－、もしくはＣＦ₃ＣＦＨ－であり酸素原子を含んでいてもよい１価のフッ素含有炭化水素基である。Ｒｆ’は下記式（４）

（式中、Ｗ、ｄ、ｐ、ｑ、ｒ、ｓ、ｔ、ｕ、ｖ、ｐ＋ｑ＋ｒ＋ｓ＋ｔ＋ｕ＋ｖは上記と同じである。ｄ’は１～６の整数である。これら各単位は直鎖状であっても分岐状であってもよい。また、ｐ、ｑ、ｒ、ｓ、ｔ、ｕ、ｖが付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。）
で表される２価のフルオロポリエーテル基である。］
［９］
　前記式（１）で表される片末端にシラノール基又は加水分解性シリル基を有するフルオロポリエーテル基含有ポリマーが、下記式で表されるものから選ばれる少なくとも１種である［１］～［８］のいずれかに記載の含フッ素エーテル組成物。

（式中、ＲＦ¹、ＲＦ²は上記と同じであり、ｐ１は５～４４０の整数、ｑ１は５～２５０の整数で、ｐ１＋ｑ１は２０～４５０の整数であり、ｐ１とｑ１が付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。）
［１０］
　［１］～［９］のいずれかに記載の含フッ素エーテル組成物を含む表面処理剤。
［１１］
　［１０］に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 fluorinated ether composition, surface treatment agent and article.
[1]
A fluorine-containing ether composition comprising a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end, represented by the following average composition formula (1), and/or a partial (hydrolyzed) condensate thereof:

[In the formula, RF ¹ is CF ₃ O- or CF ₃ CF ₂ O-, the molar ratio of CF ₃ O- to CF ₃ CF ₂ O- (CF ₃ CF ₂ O-/CF ₃ O-) is 0.01 or more and 0.17 or less, RF ² is --CF ₂ O- or --CF ₂ CF ₂ O-, and Rf is a group represented by the following formula (2):

(In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms. d is an integer of 1 to 6. p, q, r, s, t, u, and v are each an integer of 0 to 450, where p+q+r+s+t+u+v=10 to 450, and each of these units may be linear or branched. In addition, each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be randomly bonded.)
wherein U is a single bond or a divalent to pentavalent organic group, Z is independently a single bond, or a carbon atom, a silicon atom, a nitrogen atom, -SiR'= (R' is an alkyl group having 1 to 4 carbon atoms) or a trivalent to nonavalent organic group, Y is independently a divalent hydrocarbon group which may have one or more bonds selected from a fluorine atom, a silicon atom and a siloxane bond, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, a is independently 2 or 3 for each unit bonded to a silicon atom, b is independently an integer of 1 to 8, and c is an integer of 1 to 4.]
[2]
The fluorinated ether composition according to [1], wherein in RF ² in the formula (1), the molar ratio of --CF ₂ O-- to --CF ₂ CF ₂ O-- (--CF ₂ CF ₂ O--/--CF ₂ O--) is 1.05 or more and 1.2 or less.
[3]
The fluorine-containing ether composition according to [1] or [2], wherein, in the formula (1), X is selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxy-substituted alkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen group.
[4]
In the formula (1), U is a single bond, a carbonyl group, an amide group, a group represented by the following formula:

(In the formula, B is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent polyether group, and B' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.)
or a di- to pentavalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more atoms or groups selected from an oxygen atom, a sulfur atom, a hydroxyl group, a polyether group, a diorganosilylene group, a linear divalent organopolysiloxane residue having 2 to 100 silicon atoms, a silalkylene group, a silarylene group, a secondary amino group, a tertiary amino group, an ether group, a carbonyl group, an amide group, and an ester group.
[5]
The fluorine-containing ether composition according to any of [1] to [4], wherein, in formula (1), Z is a single bond, a carbon atom, a silicon atom, a nitrogen atom, a linear, branched or cyclic tri- to octavalent organopolysiloxane residue having 3 to 13 silicon atoms, a trivalent isocyanuric group, or a trivalent triazine ring-containing group.
[6]
The fluorine-containing ether composition according to any one of [1] to [5], wherein in the formula (1), Y is a group selected from the group consisting of alkylene groups having 1 to 10 carbon atoms, alkylene groups having 1 to 10 carbon atoms and containing a fluorine atom, alkylene groups having 1 to 10 carbon atoms and containing an arylene group having 6 to 8 carbon atoms, divalent groups in which alkylene groups having 1 to 10 carbon atoms are bonded to each other via a silalkylene structure or a silarylene structure, and a divalent group in which an alkylene group having 2 to 10 carbon atoms is bonded to a bond of a linear divalent organopolysiloxane residue having 2 to 10 silicon atoms, or a branched or cyclic divalent organopolysiloxane residue having 3 to 10 silicon atoms.
[7]
The fluorine-containing ether composition according to any one of [1] to [6], further comprising 25 mass% or less of a fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups at both ends, represented by the following general formula (3), and/or a partial (hydrolyzed) condensate thereof:

[In the formula, U, Z, Y, R, X, a, b, and c are independently the same as above, and Rf′ is represented by the following formula (4):

(In the formula, W, d, p, q, r, s, t, u, v, and p+q+r+s+t+u+v are the same as above. d' is an integer of 1 to 6. Each of these units may be linear or branched. In addition, each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be bonded randomly.)
is a divalent fluoropolyether group represented by the following formula:
[8]
The fluorine-containing ether composition according to any one of [1] to [7], further comprising 30 mass% or less of a fluoropolyether group-containing polymer represented by the following general formula (5):
A-Rf'-A (5)
In the formula, A is independently a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing hydrocarbon group having a terminal group of CF ₃ —, CF ₂ H—, CF ₃ CF ₂ —, or CF ₃ CFH— and which may contain an oxygen atom. Rf′ is a group represented by the following formula (4):

(In the formula, W, d, p, q, r, s, t, u, v, and p+q+r+s+t+u+v are the same as above. d' is an integer of 1 to 6. Each of these units may be linear or branched. In addition, each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be bonded randomly.)
is a divalent fluoropolyether group represented by the following formula:
[9]
The fluorine-containing ether composition according to any one of [1] to [8], wherein the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end, represented by the formula (1), is at least one selected from those represented by the following formulas:

(In the formula, RF ¹ and RF ² are the same as above, p1 is an integer of 5 to 440, q1 is an integer of 5 to 250, p1+q1 is an integer of 20 to 450, and each repeating unit shown in parentheses with p1 and q1 may be randomly bonded.)
[10]
A surface treatment agent comprising the fluorinated ether composition according to any one of [1] to [9].
[11]
An article surface-treated with the surface treatment agent according to [10].

The fluorine-containing ether composition of the present invention contains a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end, and is represented by the above average composition formula (1) taking into account the molar ratio of the terminal groups, fluorooxymethyl group and fluorooxyethyl group, and/or a partial (hydrolyzed) condensate thereof. An article that has been surface-treated with a surface treatment agent containing the fluorine-containing ether composition has improved properties in terms of water and oil repellency, as well as stain resistance, heat resistance, surface peelability, and eraser abrasion resistance.

In the present invention, the number average molecular weight (Mn) of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group and/or its partial (hydrolyzed) condensate, or the fluorinated ether composition can be calculated from the characteristic peak intensity ratio of ^19F -NMR analysis.

In addition, in the present invention, the "partial (hydrolyzed) condensate" of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group is obtained by partially condensing the hydroxyl groups of the fluoropolyether group-containing polymer having a silanol group, or the hydroxyl groups of the fluoropolyether group-containing polymer having a hydrolyzable silyl group, which have been partially hydrolyzed in advance by a known method.

［式中、ＲＦ¹はＣＦ₃Ｏ－又はＣＦ₃ＣＦ₂Ｏ－であり、ＣＦ₃Ｏ－とＣＦ₃ＣＦ₂Ｏ－のモル比（ＣＦ₃ＣＦ₂Ｏ－／ＣＦ₃Ｏ－）が０．０１以上０．１７以下である。ＲＦ²は－ＣＦ₂Ｏ－又は－ＣＦ₂ＣＦ₂Ｏ－であり、Ｒｆは下記式（２）

（式中、Ｗは１以上の水素原子を含むフルオロアルキレン基である。ｄは１～６の整数であり、ｐ、ｑ、ｒ、ｓ、ｔ、ｕ、ｖはそれぞれ０～４５０の整数で、ｐ＋ｑ＋ｒ＋ｓ＋ｔ＋ｕ＋ｖ＝１０～４５０であり、これら各単位は直鎖状であっても分岐状であってもよい。また、ｐ、ｑ、ｒ、ｓ、ｔ、ｕ、ｖが付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。）
で表される２価のフルオロポリエーテル基であり、Ｕは単結合又は２～５価の有機基であり、Ｚは独立に単結合、又は炭素原子、ケイ素原子、窒素原子、－ＳｉＲ’＝（Ｒ’は炭素数１～４のアルキル基）もしくは３～９価の有機基であり、Ｙは独立にフッ素原子、ケイ素原子及びシロキサン結合から選ばれる１種もしくは２種以上を有していてもよい２価炭化水素基であり、Ｒは独立に炭素数１～４のアルキル基又はフェニル基であり、Ｘは独立に水酸基又は加水分解性基であり、ａはケイ素原子に結合する単位毎に独立して２又は３であり、ｂは独立に１～８の整数であり、ｃは１～４の整数である。］ The fluorine-containing ether composition (fluoropolyether group-containing polymer composition) of the present invention contains a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one terminal, represented by the following average composition formula (1), and/or a partial (hydrolyzed) condensate thereof:

[In the formula, RF ¹ is CF ₃ O- or CF ₃ CF ₂ O-, the molar ratio of CF ₃ O- to CF ₃ CF ₂ O- (CF ₃ CF ₂ O-/CF ₃ O-) is 0.01 or more and 0.17 or less, RF ² is --CF ₂ O- or --CF ₂ CF ₂ O-, and Rf is a group represented by the following formula (2):

(In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms. d is an integer of 1 to 6. p, q, r, s, t, u, and v are each an integer of 0 to 450, where p+q+r+s+t+u+v=10 to 450, and each of these units may be linear or branched. In addition, each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be randomly bonded.)
wherein U is a single bond or a divalent to pentavalent organic group, Z is independently a single bond, or a carbon atom, a silicon atom, a nitrogen atom, -SiR'= (R' is an alkyl group having 1 to 4 carbon atoms) or a trivalent to nonavalent organic group, Y is independently a divalent hydrocarbon group which may have one or more bonds selected from a fluorine atom, a silicon atom and a siloxane bond, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, a is independently 2 or 3 for each unit bonded to a silicon atom, b is independently an integer of 1 to 8, and c is an integer of 1 to 4.]

In the above formula (1), RF ¹ is CF ₃ O- or CF ₃ CF ₂ O-, and the molar ratio of CF ₃ O- to CF ₃ CF ₂ O- (CF ₃ CF ₂ O-/CF ₃ O-) is 0.01 or more and 0.17 or less, more preferably 0.04 or more and 0.16 or less. If the molar ratio is less than 0.01, the resulting cured coating cannot maintain high heat resistance. If it exceeds 0.17, the antifouling performance and eraser abrasion durability of the resulting cured coating are reduced. If the molar ratio is in the range of 0.01 or more and 0.17 or less, the resulting cured coating can simultaneously exhibit all the required characteristics of antifouling, heat resistance, surface peelability, and eraser abrasion durability. The molar ratio can be calculated from the characteristic peak intensity ratio of ¹⁹ F-NMR analysis.

In the above formula (1), ^RF2 is _-CF2O- or _-CF2CF2O- , and the molar ratio of _-CF2O- to _-CF2CF2O- ( _-CF2CF2O -/- _{CF2O- )} is preferably 1.05 or more and _1.2 or less, more preferably 1.1 or more and less than 1.2. If the molar ratio is less than 1.05, the heat resistance _of the obtained cured coating may decrease, and if it exceeds 1.2, the release properties of the surface of the obtained cured coating may decrease. The molar ratio can be calculated from the characteristic peak intensity ratio of ^19F -NMR analysis.

（式中、Ｗは１以上の水素原子を含むフルオロアルキレン基である。ｄは１～６の整数であり、ｐ、ｑ、ｒ、ｓ、ｔ、ｕ、ｖはそれぞれ０～４５０の整数で、ｐ＋ｑ＋ｒ＋ｓ＋ｔ＋ｕ＋ｖ＝１０～４５０であり、これら各単位は直鎖状であっても分岐状であってもよい。また、ｐ、ｑ、ｒ、ｓ、ｔ、ｕ、ｖが付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。） In the above formula (1), Rf is a divalent fluoropolyether group represented by the following formula (2).

(In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms. d is an integer of 1 to 6. p, q, r, s, t, u, and v are each an integer of 0 to 450, where p+q+r+s+t+u+v=10 to 450, and each of these units may be linear or branched. In addition, each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be randomly bonded.)

In the above formula (2), W is a fluoroalkylene group containing one or more hydrogen atoms, and examples thereof include perfluoroalkylene groups such as _CF2 , _C2F4 , _{C3F6 , C4F8 , C5F10 , and C6F12 , in} which one or two fluorine atoms are replaced by hydrogen atoms.

In the above formula (2), d is an integer of 1 to 6, preferably an integer of 1 to 3, and more preferably 1 or 2.
In addition, p, q, r, s, t, u, and v are each an integer of 0 to 450, preferably p is an integer of 5 to 440, q is an integer of 5 to 250, r is an integer of 0 to 180, s is an integer of 0 to 100, t is an integer of 0 to 100, u is an integer of 0 to 100, and v is an integer of 0 to 100, and p+q+r+s+t+u+v is 10 to 450, preferably 20 to 200, and p+q is 20 to 450, particularly preferably 20 to 200. If p+q+r+s+t+u+v is smaller than the upper limit, the adhesion and curability are good, and if it is larger than the lower limit, the characteristics of the fluoropolyether group can be fully exhibited, which is preferable. Each unit may be linear or branched. In addition, each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be randomly bonded.

（式中、ｐ’、ｑ’、ｒ’はそれぞれ１以上の整数であり、その上限は上記ｐ、ｑ、ｒの上限と同じであり、これらｐ’、ｑ’、ｒ’の合計は２０～４５０である。また、ｐ’、ｑ’、ｒ’が付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。） Specific examples of Rf include the following.

(In the formula, p', q', and r' are each an integer of 1 or more, the upper limit of which is the same as the upper limit of p, q, and r above, and the sum of p', q', and r' is 20 to 450. In addition, each repeating unit shown in parentheses with p', q', and r' may be bonded randomly.)

In the above formula (1), the number average molecular weight of the fluoropolyether group represented by RF ¹ -RF ² -Rf- is preferably 1,000 to 50,000, more preferably 2,000 to 20,000. If the number average molecular weight is less than 1,000, the amount of fluorine is insufficient, and the antifouling properties of the resulting cured coating may decrease, while if it exceeds 50,000, the surface properties of the resulting cured coating may become unstable. In the present invention, the number average molecular weight (Mn) can be calculated by gel permeation chromatography (GPC) analysis using a fluorine-based solvent as a developing solvent, ¹⁹ F-NMR, or other means.

（式中、Ｂは水素原子、炭素数１～２０の１価炭化水素基又は１価のポリエーテル基であり、Ｂ’は水素原子又は炭素数１～２０の１価炭化水素基である。）
又は酸素原子、硫黄原子、水酸基、ポリエーテル基、ジメチルシリレン基等のジオルガノシリレン基、ケイ素原子数２～１００個、好ましくは２～５０個の直鎖状の２価のオルガノポリシロキサン残基、シルアルキレン基、シルアリーレン基、２級アミノ基、３級アミノ基、エーテル基、カルボニル基、アミド基、及びエステル基から選ばれる１種又は２種以上の原子又は基を含んでいてもよい炭素数１～２０の２～５価、好ましくは２～４価の炭化水素基である。 In the above formula (1), U is a single bond or a divalent to pentavalent organic group, and is preferably a single bond, a carbonyl group, an amide group, or a group represented by the following formula:

(In the formula, B is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent polyether group, and B' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.)
or a di- to pentavalent, preferably di- to tetravalent, hydrocarbon group having 1 to 20 carbon atoms which may contain one or more atoms or groups selected from oxygen atoms, sulfur atoms, hydroxyl groups, polyether groups, diorganosilylene groups such as dimethylsilylene groups, linear divalent organopolysiloxane residues having 2 to 100, preferably 2 to 50, silicon atoms, silalkylene groups, silarylene groups, secondary amino groups, tertiary amino groups, ether groups, carbonyl groups, amide groups, and ester groups.

In the above formula, examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms for B and B' include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl groups; branched alkyl groups such as isopropyl, isobutyl, tert-butyl, neopentyl, and thexyl groups; cyclic alkyl groups such as cyclopentyl and cyclohexyl groups; alkenyl groups such as vinyl, allyl, and propenyl groups; aryl groups such as phenyl and tolyl groups; and aralkyl groups such as benzyl and phenethyl groups.
As the monovalent polyether group for B, those represented by the formula --(C _e1 H _2e1 O) _e --CH ₃ (e1 is an integer of 1 to 6, and e is an integer of 1 to 30) are preferred.

（式中、Ｒ¹はメチル基、エチル基、プロピル基、ブチル基等の炭素数１～４のアルキル基、又はフェニル基等の炭素数６～１０のアリール基であり、Ｒ¹は同一でも異なっていてもよい。ｇは１～９９の整数、好ましくは１～４９の整数である。） Examples of the linear divalent organopolysiloxane residue having 2 to 100, preferably 2 to 50, silicon atoms which may be contained in the divalent to pentavalent hydrocarbon group include those shown below.

(In the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or an aryl group having 6 to 10 carbon atoms, such as a phenyl group, and R ¹ may be the same or different. g is an integer of 1 to 99, preferably an integer of 1 to 49.)

（式中、Ｒ¹は上記と同じであり、Ｒ²はメチレン基、エチレン基、プロピレン基、ブチレン基等の炭素数１～４のアルキレン基、又はフェニレン基等の炭素数６～１０のアリーレン基である。） Examples of the silalkylene group and silarylene group include those shown below.

(In the formula, R ¹ is the same as above, and R ² is an alkylene group having 1 to 4 carbon atoms, such as a methylene group, an ethylene group, a propylene group, or a butylene group, or an arylene group having 6 to 10 carbon atoms, such as a phenylene group.)

（式中、ｆは独立に１～４の整数であり、ｌ１、ｌ２は１～４の整数であり、ｎは１～１００の整数であり、ｅは１～３０の整数である。） Examples of U include the following groups in addition to a single bond: It is preferable that the left bond is bonded to Rf and the other bond is bonded to Z.

(In the formula, f is independently an integer of 1 to 4, l1 and l2 are integers of 1 to 4, n is an integer of 1 to 100, and e is an integer of 1 to 30.)

In the above formula (1), Z is independently a single bond, or a carbon atom, a silicon atom, a nitrogen atom, -SiR' = (R' is an alkyl group having 1 to 4 carbon atoms such as a methyl group or an ethyl group), or a trivalent to nonavalent, preferably trivalent to heptavalent, organic group, preferably a single bond, a carbon atom, a silicon atom, a nitrogen atom, a linear, branched or cyclic trivalent to octavalent organopolysiloxane residue having 3 to 13 silicon atoms, particularly 3 to 5 silicon atoms, a trivalent isocyanuric group or a trivalent triazine ring-containing group.

［式中、Ｒ¹、Ｒ²は上記と同じであり、Ｒ¹、Ｒ²はそれぞれ同一でも異なっていてもよい。Ｒ³は独立にＲ¹又は下記一般式（６）

（式中、Ｒ¹は上記と同じであり、Ｒ¹は同一でも異なっていてもよい。ｍ８は１～６の整数、好ましくは１であり、左側の結合手がＳｉと結合する。）
で表される基であり、Ｒ³の少なくとも１つは式（６）である。Ｒ⁴は独立に単結合又は下記一般式（７）

（式中、Ｒ²、Ｒ³は上記と同じであり、Ｒ²、Ｒ³はそれぞれ同一でも異なっていてもよい。ｍ９は０～６の整数、好ましくは０～３の整数、より好ましくは０又は１であり、ｍ１０は０～６の整数、好ましくは０～２の整数、より好ましくは０又は１であり、ｍ９＋ｍ１０≠０である。括弧内に示される各繰り返し単位はランダムに結合されていてよい。左側の結合手がＳｉと結合する。）
で表される基である。ｍ１は１～９の整数、好ましくは１～４の整数であり、ｍ２は０～９の整数、好ましくは０～３の整数であり、ｍ３は２～６の整数、好ましくは３～５の整数、ｍ４は０～８の整数、好ましくは０又は１で、ｍ３＋ｍ４は３～１０の整数、好ましくは３～５の整数であり、ｍ５は２又は３であり、ｍ６は３～９の整数、好ましくは３～７の整数であり、ｍ７は０～９の整数、好ましくは０～３の整数であり、括弧内に示される各繰り返し単位はランダムに結合されていてよい。但し、それぞれのオルガノポリシロキサン残基のケイ素原子数は３～１３個である。］ Examples of the linear, branched or cyclic tri- to octavalent organopolysiloxane residue having 3 to 13 silicon atoms, particularly 3 to 5 silicon atoms, include those represented by the following general formula:

[In the formula, R ¹ and R ² are the same as above, and R ¹ and R ² may be the same or different. R ³ independently represents R ¹ or a group represented by the following general formula (6):

(In the formula, R ¹ is the same as above, and R ¹ may be the same or different. m8 is an integer of 1 to 6, preferably 1, and the left bond is bonded to Si.)
At least one of ^R3 is represented by formula (6). ^R4 is independently a single bond or a group represented by the following general formula (7):

(In the formula, R ² and R ³ are the same as above, and R ² and R ³ may be the same or different. m9 is an integer of 0 to 6, preferably an integer of 0 to 3, more preferably 0 or 1. m10 is an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and m9+m10≠0. Each repeating unit shown in parentheses may be bonded randomly. The bond on the left side is bonded to Si.)
m1 is an integer of 1 to 9, preferably an integer of 1 to 4, m2 is an integer of 0 to 9, preferably an integer of 0 to 3, m3 is an integer of 2 to 6, preferably an integer of 3 to 5, m4 is an integer of 0 to 8, preferably 0 or 1, m3+m4 is an integer of 3 to 10, preferably an integer of 3 to 5, m5 is 2 or 3, m6 is an integer of 3 to 9, preferably an integer of 3 to 7, and m7 is an integer of 0 to 9, preferably an integer of 0 to 3, and each repeating unit shown in parentheses may be bonded randomly. However, the number of silicon atoms in each organopolysiloxane residue is 3 to 13.]

Examples of Z include the following groups in addition to a single bond: It is preferable that the left bond is bonded to U, and the other bond is bonded to Y.

In the above formula (1), b is independently an integer from 1 to 8, preferably an integer from 1 to 6, and more preferably an integer from 1 to 3, and c is an integer from 1 to 4, preferably an integer from 1 to 3, and more preferably 1 or 2.

In the above formula (1), Y is a divalent hydrocarbon group which may have one or more independently selected from fluorine atoms, silicon atoms, and siloxane bonds. Examples of the divalent hydrocarbon group which may have one or more selected from fluorine atoms, silicon atoms, and siloxane bonds include alkylene groups having 1 to 10 carbon atoms, such as methylene groups, ethylene groups, propylene groups, butylene groups, hexylene groups, and octylene groups, alkylene groups having 1 to 10 carbon atoms and containing fluorine atoms, It is a group selected from the group consisting of alkylene groups having 1 to 10 carbon atoms including an arylene group having 6 to 8 carbon atoms (alkylene-arylene groups having 7 to 18 carbon atoms), divalent groups in which alkylene groups having 1 to 10 carbon atoms are bonded to each other via a silalkylene structure or a silarylene structure, and divalent groups in which an alkylene group having 2 to 10 carbon atoms is bonded to a bond of a linear divalent organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic divalent organopolysiloxane residue having 3 to 10 silicon atoms. Among these, alkylene groups having 1 to 10 carbon atoms, preferably 2 to 5 carbon atoms, and more preferably 2 or 3 carbon atoms are preferred.

（式中、Ｒ¹は上記と同じであり、Ｒ¹は同一でも異なっていてもよい。ｇ１は１～９の整数、好ましくは１～３の整数であり、ｇ２は１～８の整数、好ましくは１～３の整数である。） Here, examples of the silalkylene group and silarylene group include those similar to those shown for U.
Examples of the divalent organopolysiloxane residue which is linear having 2 to 10 silicon atoms or branched or cyclic having 3 to 10 silicon atoms include those shown below.

(In the formula, R ¹ is the same as above, and R ¹ may be the same or different. g1 is an integer of 1 to 9, preferably an integer of 1 to 3, and g2 is an integer of 1 to 8, preferably an integer of 1 to 3.)

Specific examples of Y include the following: In the following structure, it is preferable that the left bond is bonded to Z and the right bond is bonded to Si.

In the above formula (1), X is a hydroxyl group or a hydrolyzable group which may be different from each other. Examples of such X include alkoxy groups having 1 to 10 carbon atoms, such as hydroxyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, and tert-butoxy group; alkoxy-substituted alkoxy groups having 2 to 10 carbon atoms, such as methoxymethoxy group, methoxyethoxy group, ethoxymethoxy group, and ethoxyethoxy group; acyloxy groups having 2 to 10 carbon atoms, such as acetoxy group and propionoxy group; alkenyloxy groups having 2 to 10 carbon atoms, such as vinyloxy group, allyloxy group, propenoxy group, and isopropenoxy group; and halogen groups, such as chlorine group, bromo group, and iodo group. Among these, methoxy group, ethoxy group, isopropenoxy group, and chlorine group are preferable.

In the above formula (1), R is independently an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group, of which the methyl group and the ethyl group are preferred.

In the above formula (1), a is independently 2 or 3 for each unit bonded to a silicon atom, with 3 being preferred from the standpoint of reactivity and adhesion to the substrate.

The fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end, represented by the above average composition formula (1), may have the following structure. By changing the combination of Rf, U, Z, Y, R, X, and a in the above formula (1), several types of fluoropolyether group-containing polymers having a silanol group or a hydrolyzable silyl group at one end can be obtained. In the following formula, RF ¹ and RF ² are the same as above, p1 is an integer of 5 to 440, q1 is an integer of 5 to 250, p1 + q1 is an integer of 20 to 450, and each repeating unit shown in parentheses with p1 and q1 may be randomly bonded.

Examples of methods for preparing the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end, represented by the above average composition formula (1), include those described in Japanese Patent No. 6451279, Japanese Patent No. 6119656, Japanese Patent No. 6828744, Japanese Patent No. 6524955, and Japanese Patent No. 6521091, and further include the following methods.
[Preparation method 1]
A fluoropolyether group-containing polymer having an olefin moiety (alkenyl group) is dissolved in a solvent, for example, a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and an organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group (halogenated silyl group, alkoxysilyl group, etc.) is mixed, and aged for 1 to 72 hours, preferably 10 to 36 hours, more preferably about 12 hours in the presence of a hydrosilylation reaction catalyst, for example, a toluene solution of a chloroplatinic acid/vinylsiloxane complex, at a temperature of 40 to 120° C., preferably 60 to 100° C., more preferably about 80° C. Note that, when an organosilicon compound having a halogen atom as the hydrolyzable silyl group is used in the organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group, the substituent (halogen atom) on the silyl group may then be converted to another hydrolyzable group, for example, an alkoxy group such as a methoxy group.

［式中、ＲＦ¹、ＲＦ²、Ｒｆ、Ｕ、Ｚ、ｂ、ｃは上記と同じであり、Ｕ’はエーテル基を含んでいてもよい炭素数１～１８の２～５価、好ましくは２又は３価の炭化水素基である。） Here, in the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end represented by the above average composition formula (1), the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group) can be exemplified by the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group) represented by the following average composition formula (8) or (9).

[In the formula, RF ¹ , RF ² , Rf, U, Z, b, and c are the same as above, and U′ is a divalent to pentavalent, preferably divalent or trivalent, hydrocarbon group having 1 to 18 carbon atoms which may contain an ether group.]

（式中、ｌ１は１～４の整数であり、ｌ２’は０～２の整数であり、ｆ’は独立に０～２の整数である。） In the above average composition formula (9), U' is a divalent to pentavalent, preferably divalent or trivalent, hydrocarbon group having 1 to 18 carbon atoms which may contain an ether group. Specific examples include those shown below.

(In the formula, l1 is an integer of 1 to 4, l2' is an integer of 0 to 2, and f' is independently an integer of 0 to 2.)

（式中、ＲＦ¹、ＲＦ²、ｐ１、ｑ１、ｐ１＋ｑ１は上記と同じであり、ｐ１とｑ１が付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。） Examples of the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group) represented by the above average composition formula (8) include the following.

(In the formula, RF ¹ , RF ² , p1, q1, and p1+q1 are the same as above, and the repeating units shown in parentheses with p1 and q1 may be bonded randomly.)

（式中、ＲＦ¹、ＲＦ²、ｐ１、ｑ１、ｐ１＋ｑ１は上記と同じであり、ｐ１とｑ１が付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。） Examples of the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group) represented by the above average composition formula (9) include the following.

(In the formula, RF ¹ , RF ² , p1, q1, and p1+q1 are the same as above, and the repeating units shown in parentheses with p1 and q1 may be bonded randomly.)

（式中、Ｚ、Ｙ、Ｒ、Ｘ、ａ、ｂ、ｃは上記と同じである。Ｙ¹は水素原子、又はフッ素原子、ケイ素原子及びシロキサン結合から選ばれる１種もしくは２種以上を有していてもよい１価炭化水素基である。） In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end, represented by the above average composition formula (1), examples of the organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group include compounds represented by the following general formula (10) or (11).

(In the formula, Z, Y, R, X, a, b, and c are the same as above. ^Y1 is a hydrogen atom, or a monovalent hydrocarbon group which may have one or more bonds selected from a fluorine atom, a silicon atom, and a siloxane bond.)

In the above formula (10), Y ¹ is a hydrogen atom, or a monovalent hydrocarbon group which may have one or more bonds selected from silicon atoms and siloxane bonds, and is preferably a hydrogen atom, a monovalent group in which a hydrogen atom and an alkylene group having 1 to 10 carbon atoms are bonded via a silalkylene structure or a silarylene structure, or a monovalent group in which a hydrogen atom and an alkylene group having 2 to 10 carbon atoms are bonded to a bond of a linear divalent organopolysiloxane residue having 2 to 10 silicon atoms, or a branched or cyclic divalent organopolysiloxane residue having 3 to 10 silicon atoms.

Specific examples of Y ¹ include the following groups.

Examples of the compound represented by the above general formula (10) include the following.

Examples of the compound represented by the general formula (11) include the following.

In the preparation of a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end, represented by the above average composition formula (1), the amount of the organosilicon compound used when reacting a fluoropolyether group-containing polymer having an olefin moiety (alkenyl group) with an organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group is such that the amount of SiH group in the organosilicon compound is 1 to 4 equivalents, more preferably 1 to 2.5 equivalents, and even more preferably about 1.2 equivalents per equivalent of the olefin moiety (alkenyl group) in the fluoropolyether group-containing polymer.

When a fluoropolyether group-containing polymer having an olefin moiety (alkenyl group) represented by the above average composition formula (8) is used as the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group), a compound represented by the above general formula (10) is used as the organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group, and when a fluoropolyether group-containing polymer having an olefin moiety (alkenyl group) represented by the above average composition formula (9) is used as the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group), a compound represented by the above general formula (11) is used as the organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group.

In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end represented by the above average composition formula (1), the solvent may be, for example, a fluorine-based solvent. Examples of the fluorine-based solvent include hydrofluoroether (HFE) solvents such as 1,3-bis(trifluoromethyl)benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, and 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane (manufactured by 3M, product name: Novec series), and perfluoro-based solvents composed of fully fluorinated compounds (manufactured by 3M, product name: Fluorinert series).
The amount of the solvent used is 10 to 300 parts by mass, preferably 30 to 150 parts by mass, and more preferably about 50 parts by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group).

In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end represented by the above average composition formula (1), examples of the hydrosilylation reaction catalyst include the following: platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylene alcohols, etc., platinum group metal catalysts such as tetrakis(triphenylphosphine)palladium and chlorotris(triphenylphosphine)rhodium, etc. Preferred are platinum compounds such as vinylsiloxane coordination compounds.
The amount of the hydrosilylation catalyst used is preferably 0.01 to 100 ppm, more preferably 0.1 to 50 ppm, calculated as transition metal (by mass) based on the mass of the fluoropolyether group-containing polymer having an olefin moiety (alkenyl group).

In the case where an organosilicon compound having a halogen atom as the hydrolyzable silyl group is used in an organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group in the molecule, the substituent (halogen atom) on the silyl group may then be converted to another hydrolyzable group, for example, an alkoxy group such as a methoxy group. Examples of reagents that can be used when converting the substituent (halogen atom) on the silyl group to another hydrolyzable group include alcohols having 1 to 10 carbon atoms, such as methanol, ethanol, propanol, isopropanol, and butanol.
The amount of the compound used is 10 to 200 parts by mass, more preferably 40 to 100 parts by mass, and even more preferably 65 parts by mass, based on 100 parts by mass of an addition reaction product of a fluoropolyether group-containing polymer having an olefin moiety (alkenyl group) and an organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group (such as a halogenated silyl group or an alkoxysilyl group) in the molecule.

を使用し、ＳｉＨ基とシラノール基又は加水分解性シリル基とを有する有機ケイ素化合物として、トリメトキシシランを使用した場合には、下記式で表される化合物が得られる。

For example, a fluoropolyether group-containing polymer having an olefin moiety (alkenyl group) is a compound represented by the following formula:

and when trimethoxysilane is used as the organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group, a compound represented by the following formula is obtained.

Other methods for preparing the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end, represented by the above average composition formula (1), include the following methods.
[Preparation method 2]
A fluoropolyether group-containing polymer having a SiH group is dissolved in a solvent, for example, a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, and mixed with an organosilicon compound having, for example, an olefin moiety (alkenyl group) and a silanol group or a hydrolyzable silyl group (halogenated silyl group, alkoxysilyl group, etc.), and aged for 1 to 72 hours, preferably 10 to 36 hours, more preferably about 12 hours, in the presence of a hydrosilylation reaction catalyst, for example, a toluene solution of a chloroplatinic acid/vinylsiloxane complex, at a temperature of 40 to 120° C., preferably 60 to 100° C., more preferably about 80° C. Note that when an organosilicon compound having a halogen atom as the hydrolyzable silyl group is used in the organosilicon compound having a SiH group and a silanol group or a hydrolyzable silyl group, the substituent (halogen atom) on the silyl group may then be converted to another hydrolyzable group, for example, an alkoxy group such as a methoxy group.

（式中、ＲＦ¹、ＲＦ²、Ｒｆ、Ｕ、Ｚ、ｂ、ｃは上記と同じである。） An example of the fluoropolyether group-containing polymer having a SiH group is a compound represented by the following average composition formula (12).

(In the formula, RF ¹ , RF ² , Rf, U, Z, b, and c are the same as above.)

（式中、ＲＦ¹、ＲＦ²、ｐ１、ｑ１、ｐ１＋ｑ１は上記と同じであり、ｐ１とｑ１が付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。） Examples of the compound represented by the above average composition formula (12) include the following.

(In the formula, RF ¹ , RF ² , p1, q1, and p1+q1 are the same as above, and the repeating units shown in parentheses with p1 and q1 may be bonded randomly.)

（式中、Ｒ、Ｘ、ａは上記と同じである。Ｙ²は末端にアルケニル基を有し、フッ素原子、ケイ素原子及びシロキサン結合から選ばれる１種もしくは２種以上を有していてもよい１価炭化水素基である。） An example of an organosilicon compound having an olefin moiety (alkenyl group) and a silanol group or a hydrolyzable silyl group is a compound represented by the following general formula (13).

(In the formula, R, X, and a are the same as above. ^Y2 is a monovalent hydrocarbon group having an alkenyl group at the terminal and which may have one or more bonds selected from a fluorine atom, a silicon atom, and a siloxane bond.)

In the above formula (13), ^Y2 is a monovalent hydrocarbon group which has an alkenyl group at its terminal and which may have one or more bonds selected from a fluorine atom, a silicon atom and a siloxane bond, and examples of such a monovalent hydrocarbon group include those represented by the following formula:

Examples of the compound represented by the above general formula (13) include the following.

In the preparation [Preparation Method 2] of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end represented by the above average composition formula (1), the amount of the organosilicon compound used when reacting the fluoropolyether group-containing polymer having a SiH group with an organosilicon compound having an olefin moiety (alkenyl group) and a silanol group or a hydrolyzable silyl group can be such that the amount of the olefin moiety (alkenyl group) in the organosilicon compound is 1 to 4 equivalents, more preferably 1 to 2.5 equivalents, and even more preferably about 1.2 equivalents, per equivalent of the SiH group in the fluoropolyether group-containing polymer.

In the preparation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end represented by the above average composition formula (1) [Preparation method 2], the solvent may be, for example, a fluorine-based solvent. Examples of the fluorine-based solvent include the same ones as those exemplified in Preparation method 1.
The amount of the solvent used may be 10 to 300 parts by mass, preferably 30 to 150 parts by mass, and more preferably about 50 parts by mass, per 100 parts by mass of the fluoropolyether group-containing polymer having SiH groups.

In the preparation [Preparation Method 2] of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end, represented by the above average composition formula (1), examples of the hydrosilylation reaction catalyst include those similar to those exemplified in Preparation Method 1. Preferred are platinum-based compounds such as vinylsiloxane coordination compounds.
The amount of the hydrosilylation catalyst used is preferably 0.01 to 100 ppm, more preferably 0.1 to 50 ppm, calculated as transition metal (by mass) based on the mass of the fluoropolyether group-containing polymer having SiH groups.

In the case of using an organosilicon compound having an olefin moiety (alkenyl group) and a silanol group or a hydrolyzable silyl group, in which an organosilicon compound having a halogen atom as the hydrolyzable silyl group is used, the substituent (halogen atom) on the silyl group may then be converted to another hydrolyzable group, for example, an alkoxy group such as a methoxy group, and examples of reagents that can be used to convert the substituent (halogen atom) on the silyl group to another hydrolyzable group include those similar to those exemplified in Preparation Method 1. The amount used may also be the same as in Preparation Method 1.

を使用し、オレフィン部位（アルケニル基）とシラノール基又は加水分解性シリル基とを有する有機ケイ素化合物として、ＫＢＭ－１０８３（７－オクテニルトリメトキシシラン、信越化学工業株式会社製）を使用した場合には、下記式で表される化合物が得られる。

For example, the fluoropolyether group-containing polymer having a SiH group may be a compound represented by the following formula:

and KBM-1083 (7-octenyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) is used as the organosilicon compound having an olefin moiety (alkenyl group) and a silanol group or a hydrolyzable silyl group, a compound represented by the following formula is obtained.

を使用し、１，１，３，３－テトラメチルジシロキサンを使用して共加水分解した場合には、下記式で表される化合物が得られる。

In addition, the following method can also be mentioned. For example, a compound represented by the following formula

is used and cohydrolyzed with 1,1,3,3-tetramethyldisiloxane to give a compound of the formula:

When the compound represented by the above formula is used as the fluoropolyether group-containing polymer having a SiH group, and KBM-1083 (7-octenyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) is used as the organosilicon compound having an olefin moiety (alkenyl group) and a silanol group or a hydrolyzable silyl group, the compound represented by the following formula is obtained.

The number average molecular weight of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end and/or its partial (hydrolyzed) condensate represented by the above average composition formula (1) is preferably 1,000 to 53,000, more preferably 2,000 to 23,000, even more preferably 2,500 to 13,000, and particularly preferably 3,000 to 8,300. If the number average molecular weight is less than 1,000, the antifouling properties of the resulting cured coating may decrease, and if it exceeds 53,000, the surface properties of the resulting cured coating may become unstable. The above number average molecular weight can be achieved by rectification or molecular distillation of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end and/or its partial (hydrolyzed) condensate represented by the above average composition formula (1).

In the fluorine-containing ether composition (fluoropolyether group-containing polymer composition) of the present invention, the amount of the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end and/or its partial (hydrolyzed) condensate, represented by the above-mentioned average composition formula (1), in the fluorine-containing ether composition (particularly the total amount of the fluoropolyether group-containing polymer), is preferably 70 to 100 mass %, more preferably 80 to 100 mass %. If it is less than 70 mass %, the heat resistance decreases, and it may not be possible to obtain a cured coating that has both stain resistance, heat resistance, surface peelability, and eraser abrasion resistance.

［式中、Ｕ、Ｚ、Ｙ、Ｒ、Ｘ、ａ、ｂ、ｃは独立に上記と同じであり、Ｒｆ’は下記式（４）

（式中、Ｗ、ｄ、ｐ、ｑ、ｒ、ｓ、ｔ、ｕ、ｖ、ｐ＋ｑ＋ｒ＋ｓ＋ｔ＋ｕ＋ｖは上記と同じである。ｄ’は１～６の整数である。これら各単位は直鎖状であっても分岐状であってもよい。また、ｐ、ｑ、ｒ、ｓ、ｔ、ｕ、ｖが付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。）
で表される２価のフルオロポリエーテル基である。）］ The fluorine-containing ether composition of the present invention may further contain, if necessary, a fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups at both ends, represented by the following general formula (3), and/or a partial (hydrolyzed) condensate thereof (polymer containing functional fluoropolyether groups at both ends), which has the effect of further improving heat resistance.

[In the formula, U, Z, Y, R, X, a, b, and c are independently the same as above, and Rf′ is represented by the following formula (4):

(In the formula, W, d, p, q, r, s, t, u, v, and p+q+r+s+t+u+v are the same as above. d' is an integer of 1 to 6. Each of these units may be linear or branched. In addition, each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be bonded randomly.)
is a divalent fluoropolyether group represented by the following formula:

In the above formula (3), Rf' is a divalent fluoropolyether group represented by the above formula (4), and W, d, p, q, r, s, t, u, v, and p+q+r+s+t+u+v in formula (4) can be exemplified as those exemplified for Rf in the above formula (1).

In the above formula (4), d' is an integer from 1 to 6, preferably an integer from 1 to 3, and more preferably 1 or 2.

（式中、ｐ’、ｑ’、ｒ’はそれぞれ１以上の整数であり、その上限は上記ｐ、ｑ、ｒの上限と同じであり、これらｐ’、ｑ’、ｒ’の合計は２０～４５０である。ｒ２’、ｒ３’はそれぞれ１以上の整数であり、ｒ２’とｒ３’の合計は３５～１８０である。また、ｐ’、ｑ’、ｒ’が付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。） Specific examples of Rf' include the following.

(In the formula, p', q', and r' are each integers of 1 or more, the upper limit of which is the same as the upper limit of p, q, and r above, and the sum of p', q', and r' is 20 to 450. r2' and r3' are each integers of 1 or more, and the sum of r2' and r3' is 35 to 180. In addition, each repeating unit shown in parentheses with p', q', and r' may be bonded randomly.)

In the above formula (4), the number average molecular weight of the fluoropolyether group represented by Rf' is preferably 1,000 to 50,000, and more preferably 2,000 to 20,000. If the number average molecular weight is less than 1,000, the amount of fluorine is insufficient, and the stain-resistant properties of the resulting cured coating may decrease, while if it exceeds 50,000, the surface properties of the resulting cured coating may become unstable.

In addition, in the fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups at both ends represented by the general formula (3), U, Z, Y, R, X, a, b, c, and W, d, p, q, r, s, t, u, v, and p+q+r+s+t+u+v in Rf in the fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups at one end represented by the above-mentioned average composition formula (1) may be the same or different.

（式中、ｐ２は５～４４０の整数、ｑ２は５～２５０の整数で、ｐ２＋ｑ２は２０～４５０の整数であり、ｐ２とｑ２が付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。） Examples of the fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups at both ends (functional fluoropolyether group-containing polymer at both ends) represented by the general formula (3) include the following.

(In the formula, p2 is an integer of 5 to 440, q2 is an integer of 5 to 250, and p2+q2 is an integer of 20 to 450, and each repeating unit shown in parentheses with p2 and q2 may be randomly bonded.)

The number average molecular weight of the fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups at both ends and/or its partial (hydrolyzed) condensate represented by the above general formula (3) is preferably 1,000 to 56,000, more preferably 2,000 to 26,000, even more preferably 2,600 to 16,000, and particularly preferably 3,100 to 14,000. If the number average molecular weight is less than 1,000, the antifouling properties of the resulting cured coating may decrease, and if it exceeds 56,000, the surface properties of the resulting cured coating may become unstable. The above number average molecular weight can be achieved by rectification or molecular distillation of the fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups at both ends and/or its partial (hydrolyzed) condensate represented by the above general formula (3).

In the fluorine-containing ether composition (fluoropolyether group-containing polymer composition) of the present invention, the amount of the fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups at both ends and/or its partial (hydrolyzed) condensate (both-end functional fluoropolyether group-containing polymer) represented by the general formula (3) is preferably 0 to 25 mass %, particularly 0 to 15 mass %, in the fluorine-containing ether composition (particularly the total amount of the fluoropolyether group-containing polymer). If it exceeds 25 mass %, the surface peelability decreases, and it may not be possible to obtain a cured coating that has both antifouling properties, heat resistance, surface peelability, and eraser abrasion resistance. When it is added, it is preferably 5 mass % or more, particularly 8 mass % or more in the fluorine-containing ether composition (particularly the total amount of the fluoropolyether group-containing polymer).

The fluorine-containing ether composition of the present invention may further contain a fluoropolyether group-containing polymer (non-functional fluoropolyether polymer) represented by the following general formula (5) if necessary, which can further improve the surface peelability.
A-Rf'-A (5)
₍ In the formula, Rf' is the same as defined above. A independently represents a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing hydrocarbon group which terminates in _CF3- , _CF2H- , _CF3CF2- , or _CF3CFH- and which may contain an oxygen atom.)

In the above formula (5), Rf' is the same as Rf' in the above formula (3), and examples of Rf' include those similar to those exemplified as Rf' (the divalent fluoropolyether group represented by formula (4)). Rf' may be the same as or different from Rf' in formula (3).

In the above formula (5), A is independently a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing hydrocarbon group whose terminal is _CF3- , _CF2H- , _{CF3CF2- , or CF3CFH-} and which may contain an oxygen atom _, and specific examples include a fluorine atom, a hydrogen atom, _CF3- , _CF2H- , _CF2CF3- , _CF3CFH- , _CF3O- , _CF3CF2O- , etc.

（式中、ｐ３、ｑ３、ｒ３はそれぞれ独立に０～４５０の整数であり、かつ、ｐ３、ｑ３、ｒ３の合計は２０～４５０であり、ｒ４、ｒ５はそれぞれ２０～４５０の整数である。ｐ３、ｑ３、ｒ３が付された括弧内に示される各繰り返し単位はランダムに結合されていてよい。） Examples of the fluoropolyether group-containing polymer (non-functional fluoropolyether polymer) represented by the general formula (5) include the following.

(In the formula, p3, q3, and r3 are each independently an integer of 0 to 450, the sum of p3, q3, and r3 is 20 to 450, and r4 and r5 are each an integer of 20 to 450. Each repeating unit shown in parentheses with p3, q3, and r3 may be bonded randomly.)

The number average molecular weight of the fluoropolyether group-containing polymer represented by the above general formula (5) is preferably 1,000 to 50,000, more preferably 2,000 to 20,000, even more preferably 2,500 to 10,000, and particularly preferably 3,000 to 8,000. If the number average molecular weight is less than 1,000, the fluoropolyether group-containing polymer represented by the above formula (5) in the obtained cured coating may volatilize in a heating environment, and if it exceeds 50,000, the surface properties of the obtained cured coating may become unstable. The above number average molecular weight can be obtained by rectifying or molecular distilling the fluoropolyether group-containing polymer represented by the above general formula (5).

In the fluorine-containing ether composition (fluoropolyether group-containing polymer composition) of the present invention, the amount of the fluoropolyether group-containing polymer (nonfunctional fluoropolyether group-containing polymer) represented by general formula (5) is desirably 0 to 30 mass %, and especially 0 to 20 mass %, in the fluorine-containing ether composition (particularly the total amount of fluoropolyether group-containing polymers). If it exceeds 30 mass %, the eraser abrasion resistance decreases, and it may not be possible to obtain a cured coating that has both stain resistance, heat resistance, surface peelability, and eraser abrasion resistance. If it is added, it is preferably 0.1 mass % or more, and especially 1 mass % or more in the fluorine-containing ether composition (particularly the total amount of fluoropolyether group-containing polymers).

The fluorine-containing ether composition of the present invention can be prepared by uniformly mixing predetermined amounts of a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end and/or a partial (hydrolyzed) condensate thereof, which is represented by the above-mentioned average composition formula (1), and, if necessary, a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at both ends and/or a partial (hydrolyzed) condensate thereof, which is represented by the general formula (3), or a fluoropolyether group-containing polymer represented by the general formula (5), in accordance with a conventional method.

The fluorine-containing ether composition of the present invention preferably has a number average molecular weight of 1,000 to 56,000, more preferably 2,000 to 26,000, even more preferably 2,500 to 16,000, and particularly preferably 3,000 to 8,600. If the number average molecular weight is less than 1,000, the stain resistance and heat resistance of the resulting cured coating may decrease, and if it exceeds 56,000, the surface properties of the resulting cured coating may become unstable. The above number average molecular weight can be achieved by rectifying or molecular distilling the fluorine-containing ether composition.

The present invention further provides a surface treatment agent comprising the above fluorinated ether composition.
If necessary, the surface treatment agent may contain a hydrolysis condensation catalyst, for example, an organotin compound (dibutyltin dimethoxide, dibutyltin dilaurate, etc.), an organotitanium compound (tetra n-butyl titanate, etc.), an organic acid (acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid, etc.), or an inorganic acid (hydrochloric acid, sulfuric acid, etc.). Among these, acetic acid, tetra n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid, etc. are particularly preferable.
The amount of the hydrolysis and condensation catalyst added is a catalytic amount, and is usually 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass, per 100 parts by mass of the fluorine-containing ether composition (particularly the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group in the composition and/or its partial (hydrolysis) condensate).

The surface treatment agent may contain a suitable solvent. Examples of such solvents include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, tridecafluorooctane, hexafluoropropene trimer, etc.), fluorine-modified aromatic hydrocarbon solvents (1,3-bis(trifluoromethyl)benzene, etc.), fluorine-modified ether solvents (methyl perfluorobutyl ether, methyl perfluorohexyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), methyl perfluoroheptenyl ether, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, 1,1,2,2-tetrafluoroethyl methyl ether, hexafluoroisopropyl methyl ether, etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum benzine, toluene, xylene, etc.), and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, fluorine-modified solvents are preferable in terms of solubility, wettability, etc., and 1,3-bis(trifluoromethyl)benzene, perfluoro(2-butyltetrahydrofuran), perfluorotributylamine, ethyl perfluorobutyl ether, methyl perfluorohexyl ether, tridecafluorooctane, and 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether are particularly preferable.

Two or more of the above solvents may be mixed, and it is preferable to dissolve the fluorinated ether composition uniformly. The optimal concentration of the fluorinated ether composition to be dissolved in the solvent varies depending on the processing method, and may be any amount that is easy to weigh. In the case of direct coating, however, it is preferable that the concentration is 0.01 to 10 parts by mass, and particularly 0.05 to 5 parts by mass, per 100 parts by mass of the solvent and the fluorinated ether composition in total, and in the case of vapor deposition processing, it is preferable that the concentration is 1 to 100 parts by mass, and particularly 3 to 30 parts by mass, per 100 parts by mass of the solvent and the fluorinated ether composition in total.

The surface treatment agent of the present invention can be applied to a substrate by known methods such as brushing, dipping, spraying, and vapor deposition. The heating method during vapor deposition may be either resistance heating or electron beam heating, and is not particularly limited. The curing temperature varies depending on the curing method. For example, in the case of direct coating (brushing, dipping, spraying, etc.), it is preferable to apply the agent at 25 to 200°C, especially 25 to 150°C, for 30 minutes to 36 hours, especially 1 to 18 hours. Furthermore, when applying the agent by vapor deposition, it is preferable to apply the agent at a temperature in the range of 20 to 200°C for 1 to 24 hours. It may also be cured under humidification. For example, in the case of spray coating, the agent is diluted in a fluorine-based solvent to which moisture has been added beforehand, and then hydrolyzed, i.e., Si-OH is generated, and then spray coating is performed, which results in rapid curing after coating.

The thickness of the cured coating is selected appropriately depending on the type of substrate, but is usually 0.1 to 100 nm, and particularly 1 to 20 nm. The thickness can be measured by, for example, spectral reflectance measurement, X-ray reflectance measurement, spectroscopic ellipsometry measurement, X-ray fluorescence measurement, etc.

The substrate to be treated with the surface treatment agent of the present invention is not particularly limited, and may be made of various materials such as paper, cloth, metal and its oxide, glass, plastic, ceramic, quartz, etc. The surface treatment agent of the present invention can impart water and oil repellency to the substrate. In particular, it can be suitably used as a surface treatment agent for _SiO2- treated glass or film.

　Articles that can be treated with the surface treatment agent of the present invention include car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game devices, eyeglass lenses, camera lenses, lens filters, sunglasses, medical equipment such as gastroscopes, copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflective films and other optical articles. The surface treatment agent of the present invention can prevent the adhesion of fingerprints and sebum to the above-mentioned articles and can also impart scratch resistance, making it particularly useful as a water- and oil-repellent layer for lenses, touch panel displays, anti-reflective films and the like.

The surface treatment agent of the present invention is also useful as an anti-fouling coating for sanitary products such as bathtubs and washbasins, as an anti-fouling coating for window glass or tempered glass for automobiles, trains, aircraft, etc., headlamp covers, etc., as a water- and oil-repellent coating for exterior wall building materials, as a coating to prevent oil stains for kitchen building materials, as an anti-fouling and anti-posting/anti-graffiti coating for telephone booths, as a coating to prevent fingerprints from adhering to artworks, etc., as a fingerprint-preventing coating for compact discs, DVDs, etc., as a release agent or paint additive for molds, as a resin modifier, as a flowability modifier or dispersibility modifier for inorganic fillers, and as a lubricity improver for tapes, films, etc.

In particular, the surface treatment agent of the present invention can impart a cured coating that is excellent in water and oil repellency, as well as stain resistance, heat resistance, surface peelability, and eraser abrasion resistance.

The present invention will be described in more detail below with reference to synthesis examples, working examples, and comparative examples, but the present invention is not limited to the following working examples. In addition, in the following formula, the repeating units shown in parentheses with p1 and q1, p2 and q2, and p3 and q3 are randomly bonded. Furthermore, the film thickness is a value measured by a spectroscopic ellipsometry measurement method using a spectroscopic ellipsometer.

The number average molecular weights (Mn) of the fluoropolyether group-containing polymer and the fluorinated ether composition are values calculated from the characteristic peak intensity ratios of the terminal structure and main chain structure of the fluoropolyether group-containing polymer based on ¹ H-NMR analysis and ¹⁹ F-NMR analysis. The ^RF1 molar ratio (CF ₃ CF ₂ O-/CF ₃ O-), RF2 ^molar ratio (-CF ₂ CF ₂ O-/-CF ₂ O-), p1, q1, p2, q2, p3, and q3 were calculated from the characteristic peak intensity ratios of ¹⁹ F-NMR analysis.

Raw material polymers A to G having the compositions shown in Table 1 below and represented by the following average composition formula (I) were prepared.

[Synthesis Example 1]
With reference to Japanese Patent No. 6451279, polymers containing a functional fluoropolyether group at one end and represented by the average composition formula (II) below and having the composition shown in Table 2 below (A-II, B-II, C-II, and G-II in Table 2) were synthesized using raw material polymers A, B, C, and G represented by the average composition formula (I) below and having the composition shown in Table 1 as starting materials.

[Synthesis Example 2]
With reference to Japanese Patent No. 6,119,656 and Japanese Patent No. 6,828,744, polymers containing a functional fluoropolyether group at one end (C-III and F-III in Table 2) having the composition shown in Table 2 and represented by the average composition formula (III) below were synthesized using raw material polymers C and F having the composition shown in Table 1 and represented by the average composition formula (I) below as starting materials.

[Synthesis Example 3]
With reference to Japanese Patent No. 6,119,656 and Japanese Patent No. 6,524,955, a polymer containing a functional fluoropolyether group at one end (B-IV in Table 2) having the composition shown in Table 2 and represented by the following average composition formula (IV) was synthesized using raw material polymer B having the composition shown in Table 1 and represented by the average composition formula (I).

[Synthesis Example 4]
With reference to Japanese Patent No. 6,119,656 and Japanese Patent No. 6,524,955, polymers containing a functional fluoropolyether group at one end and represented by the average composition formula (V) shown below and having the composition shown in Table 2 below (E-V and F-V in Table 2) were synthesized using raw material polymers E and F represented by the average composition formula (I) and having the composition shown in Table 1 as starting materials, and a compound represented by the following formula (a) as an organosilicon compound having a SiH group and a hydrolyzable terminal group in the molecule.

[Synthesis Example 5]
30 g of raw material polymer A represented by average composition formula (I) having the composition shown in Table 1, 30 g of 1,3-trifluoromethylbenzene, and 6.0 g of 2,2-diallyl-4-penten-1-amine were stirred at 50° C. for 5 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 25 g of a liquid product. The obtained product was confirmed to be a compound represented by average composition formula (VI-a) below by ¹ H-NMR. The RF1 ^molar ratio and RF2 ^molar ratio in formula (VI-a) were the same as the RF1 ^molar ratio and RF2 ^molar ratio in raw material polymer A.

25 g of the compound represented by the average composition formula (VI-a), 10 g of 1,3-trifluoromethylbenzene, 2.0 g of trimethoxysilane, and 0.015 g of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 4.5×10 ⁻⁸ moles of Pt alone) were mixed and aged at 80° C. for 3 hours. Thereafter, the solvent and unreacted matter were distilled off under reduced pressure to obtain 25 g of a liquid product. The obtained product was confirmed by ¹ H-NMR to be a polymer containing a functional fluoropolyether group at one end represented by the following average composition formula (VI). The RF ¹ molar ratio and RF ² molar ratio in formula (VI) were the same as the RF ¹ molar ratio and RF ² molar ratio in the raw material polymer A. The number average molecular weight was 5,071.

[Synthesis Example 6]
A mixture of 100 g of raw material polymer D represented by average composition formula (I) having the composition shown in Table 1, 130 ml of 3-butenyl magnesium bromide, 200 g of Asahiklin AC6000, and 100 g of PF5060 was stirred at 50° C. for 6 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 93 g of a liquid product. The obtained product was confirmed to be a compound represented by the following average composition formula (VII-a) by ¹ H-NMR. The RF1 ^molar ratio and RF2 ^molar ratio in formula (VII-a) were the same as the RF1 ^molar ratio and RF2 ^molar ratio in raw material polymer D.

80 g of the compound represented by the average composition formula (VII-a), 8.8 g of allyl bromide, and 0.14 g of tetrabutylammonium iodide were mixed, and 14.4 g of a 30% by mass aqueous sodium hydroxide solution was added, followed by heating at 50° C. for 24 hours. Thereafter, the solvent and unreacted materials were distilled off under reduced pressure to obtain 75 g of a liquid product. The obtained product was confirmed to be a compound represented by the following average composition formula (VII-b) by ¹ H-NMR. The RF1 ^molar ratio and RF2 ^molar ratio in formula (VII-b) were the same as the RF1 ^molar ratio and RF2 ^molar ratio in raw material polymer D.

70 g of the compound represented by the average composition formula (VII-b), 100 g of 1,3-bis(trifluoromethyl)benzene, 37 g of 2,4,6,8-tetramethylcyclotetrasiloxane, and 8.0×10 ⁻² g of a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid/vinylsiloxane complex) (containing 2.4×10 ⁻⁷ mol as Pt alone) were mixed and stirred at 80° C. for 24 hours. Thereafter, the solvent and unreacted matter were distilled off under reduced pressure to obtain 65 g of a liquid product. The obtained product was confirmed to be a compound represented by the average composition formula (VII-c) below by ¹ H-NMR. The RF ¹ molar ratio and RF ² molar ratio in formula (VII-c) were the same as the RF ¹ molar ratio and RF ² molar ratio in raw material polymer D.

50 g of the compound represented by the average composition formula (VII-c), 100 g of 1,3-bis(trifluoromethyl)benzene, 17.5 g of 7-octenyltrimethoxysilane, and 8.0×10 ⁻² g of a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid/vinylsiloxane complex) (containing 2.4×10 ⁻⁷ mol as Pt alone) were mixed and stirred at 80° C. for 24 hours. Thereafter, the solvent and unreacted matter were distilled off under reduced pressure to obtain 30 g of a liquid product. The obtained product was confirmed by ¹ H-NMR to be a polymer containing a functional fluoropolyether group at one end represented by the following average composition formula (VII). The RF ¹ molar ratio and RF ² molar ratio in formula (VII) were the same as the RF ¹ molar ratio and RF ² molar ratio in raw material polymer D. The number average molecular weight was 6,490.

[Synthesis Example 7]
100 g of a compound represented by the following general formula (H'), 50 g of 1,3-bis(trifluoromethyl)benzene, 7.0 g of trimethoxysilane, and 8.0 x 10 ^-2 g of a toluene solution of platinum-1,3-divinyl-tetramethyldisiloxane complex (chloroplatinic acid/vinylsiloxane complex) (containing 2.4 x 10 ^-7 mol as Pt alone) were mixed and stirred at 80°C for 24 hours. Thereafter, the solvent and unreacted matter were distilled off under reduced pressure to obtain 90 g of a liquid product. The obtained product was confirmed by ¹ H-NMR to be polymer H containing functional fluoropolyether groups at both ends represented by the following general formula (H). The number average molecular weight was 4,720.

[Synthesis Example 8]
With reference to Japanese Patent No. 6451279, a compound represented by the following general formula (J') was used as a starting material to synthesize a polymer J having functional fluoropolyether groups at both ends represented by the following general formula (J). The number average molecular weight was 4,510.

[Synthesis Example 9]
With reference to Japanese Patent No. 6524955, a compound represented by the following general formula (K') was used as a starting material, and a compound represented by the following formula (a) was used as an organosilicon compound having a SiH group and a hydrolyzable terminal group in the molecule to synthesize a polymer K containing functional fluoropolyether groups at both ends represented by the following general formula (K). The number average molecular weight was 4,630.

As a non-functional fluoropolyether polymer, a non-functional fluoropolyether group-containing polymer L (number average molecular weight 4,300) represented by the following general formula (L) was prepared.

The list of the one-terminal functional fluoropolyether group-containing polymers obtained in Synthesis Example 1-6 of the one-terminal functional fluoropolyether group-containing polymer is shown in Table 2. For example, the one-terminal functional fluoropolyether group-containing polymer A-II is a one-terminal functional fluoropolyether group-containing polymer having a structure represented by the above average composition formula (II) obtained by using the raw material polymer A represented by the average composition formula (I) having the composition in Table 1 as the starting material.

The following solvents were used for dilution:
Novec 7200 (3M, ethyl perfluorobutyl ether),
Novec 7300 (3M, methyl perfluorohexyl ether),
Asahiklin AC-6000 (manufactured by AGC Corporation, tridecafluorooctane),
Opteon SF10 (manufactured by Mitsui Chemours Fluoroproducts Co., Ltd., methyl perfluoroheptenyl ether),
Hexafluoropropene trimer (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.),
Hexafluoroisopropyl methyl ether (Tokyo Chemical Industry Co., Ltd.)

[Examples 1 to 19, Comparative Examples 1 to 4]
The polymer obtained in the above Synthesis Example was diluted with a solvent so that the fluorine-containing ether composition, which is a mixture of a polymer containing a functional fluoropolyether group at one end, a polymer containing functional fluoropolyether groups at both ends, and a polymer containing a non-functional fluoropolyether group, had a composition shown in Table 3, was 20 mass% to prepare a surface treatment agent.

Preparation of Surface Treatment Agent and Formation of Cured Coating Cured coatings were produced using the surface treatment agents prepared in Examples 1 to 19 and Comparative Examples 1 to 4. Each surface treatment agent was vacuum-deposited (treatment conditions: pressure: _3.0 ×10 ⁻² Pa, heating temperature: 700° C.) onto glass (Gorilla V, manufactured by Corning Incorporated) whose outermost surface had been coated with SiO 2 to a thickness of 10 nm, and cured for 12 hours in an atmosphere of 25° C. and relative humidity of 50% to form a cured coating with a thickness of 10 nm.

Evaluation of water and oil repellency [measurement of initial water contact angle]
The glass having the cured coating formed thereon was subjected to measurement of the contact angle (water repellency) of the cured coating with respect to water using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25° C., relative humidity: 40%). The results (initial water contact angle) are shown in Table 4.

Evaluation of stain resistance [Evaluation of marker ink wiping ability]
A 1 cm x 1 cm square was drawn on the glass having the cured coating formed thereon using a Pentel Pen 50 (manufactured by Pentel Co., Ltd.), the ink was then dried, and the square was wiped off with tissue paper (manufactured by Kami Shoji Co., Ltd.) The number of times the ink was rubbed until it was wiped off was evaluated.
(Evaluation Criteria)
A: 4 or less rubbing times. B: 5 or more rubbing times. The results of evaluation based on the above evaluation criteria are shown in Table 4.

Evaluation of heat resistance [Measurement of water contact angle after heating]
The glass having the cured coating formed thereon was heated at 250° C. for 24 hours, washed with a neutral detergent Mama Lemon (manufactured by Lion Corporation), and the contact angle with water was measured under the conditions described in [Measurement of initial water contact angle] above (droplet: 2 μl, temperature: 25° C., relative humidity: 40%). The test environmental conditions were 25° C. and relative humidity 40%.
(Evaluation Criteria)
A: The difference in contact angle between [initial water contact angle measurement] and [water contact angle after heating] is less than 6°. B: The difference in contact angle between [initial water contact angle measurement] and [water contact angle after heating] is 6° or more and less than 10°. C: The difference in contact angle between [initial water contact angle measurement] and [water contact angle after heating] is 10° or more. The results of evaluation based on the above evaluation criteria are shown in Table 4.

Evaluation of peelability: A polyester adhesive tape No. 31B (manufactured by Nitto Denko Corporation) was attached to the glass on which the cured coating film was formed as described above, and the glass was left standing for 3 days in a state of being pressed with a load of 1 kgf. The peel strength was then evaluated using an autograph AGS-X10N (manufactured by Shimadzu Corporation). The test environment conditions were a temperature of 25°C, a relative humidity of 50%, a crosshead speed of 300 mm/min, and a test piece width of 19 mm.
(Evaluation Criteria)
A: peeling force less than 0.08 N B: peeling force 0.08 N or more and less than 0.11 N C: peeling force 0.11 N or more The results of evaluation according to the above evaluation criteria are shown in Table 4.

Evaluation of Eraser Abrasion Resistance The glass on which the cured coating was formed was rubbed 3,000 times under the following conditions using a reciprocating abrasion tester (Tribogear, manufactured by Shinto Scientific Co., Ltd.), and the contact angle of the cured coating with water was measured in the same manner as above to evaluate the abrasion resistance. The test environment conditions were 25°C and 40% relative humidity.
(Wear conditions)
Eraser: rubber eraser (manufactured by Minoan)
Travel distance (one way): 40 mm
Traveling speed: 2,400mm/min
Load: 1 kgf/ ⁶ mm2 Φ
(Evaluation Criteria)
A: The difference in contact angle between [measurement of initial water contact angle] and [water contact angle after abrasion] is less than 6°. B: The difference in contact angle between [measurement of initial water contact angle] and [water contact angle after abrasion] is 6° or more and less than 11°. C: The difference in contact angle between [measurement of initial water contact angle] and [water contact angle after abrasion] is 11° or more. The results of evaluation based on the above evaluation criteria are shown in Table 4.

[Examples 20 to 25, Comparative Examples 5 and 6]
The polymer obtained in the above synthesis example was diluted with a solvent so that the fluorine-containing ether composition, which is a mixture of a polymer containing a functional fluoropolyether group at one end, a polymer containing functional fluoropolyether groups at both ends, and a polymer containing a non-functional fluoropolyether group, had a composition shown in Table 5, was 0.1 mass% to prepare a surface treatment agent.

Preparation of surface treatment agent and formation of cured coating film Cured coating films were prepared using the surface treatment agents prepared in Examples 20 to 25 and Comparative Examples 5 and 6. The surface of chemically strengthened glass (Gorilla V, manufactured by Corning Incorporated) that had been plasma-treated and cleaned was spray-coated using a spray coating device (NST-51, manufactured by T&K Corporation). Then, the coating was cured for 12 hours under an atmosphere of 25°C and 50% relative humidity to form a cured coating film with a thickness of 10 nm, and a test specimen was obtained.

The evaluation methods for Examples 20 to 25 and Comparative Examples 5 and 6 were the same as those for Examples 1 to 19 and Comparative Examples 1 to 4. The results (initial contact angle, number of rubs required until the ink was wiped off, water contact angle after heating, and peel value) are shown in Table 6.

From the above results, in Comparative Examples 1 to 3 and 5, the decrease in the water contact angle after heating is kept below 6° compared to the initial water contact angle (i.e., the water contact angle is kept above 100°), but the number of times of rubbing until the ink is wiped off increases, and the water contact angle after eraser wear is greatly reduced. In Comparative Examples 4 and 6, the ink can be wiped off immediately, and the decrease in the water contact angle after eraser wear is kept below 6° (i.e., the water contact angle is kept above 100°), but the heat resistance is weak and the peel value is high. On the other hand, in Examples 1 to 25, by adjusting the molar ratio of CF ₃ CF ₂ O- and CF ₃ O-, which are the terminal groups of the one-terminal functional fluoropolyether group-containing polymer, to within the range of 0.01 to 0.17, good results were obtained in four properties, namely water and oil repellency, antifouling property, heat resistance, surface peelability and eraser wear resistance.

Claims (11)

A fluorine-containing ether composition comprising a fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end, represented by the following average composition formula (1), and/or a partial (hydrolyzed) condensate thereof:

[In the formula, RF ¹ is CF ₃ O- or CF ₃ CF ₂ O-, the molar ratio of CF ₃ O- to CF ₃ CF ₂ O- (CF ₃ CF ₂ O-/CF ₃ O-) is 0.01 or more and 0.17 or less, RF ² is --CF ₂ O- or --CF ₂ CF ₂ O-, and Rf is a group represented by the following formula (2):

(In the formula, W is a fluoroalkylene group containing one or more hydrogen atoms. d is an integer of 1 to 6. p, q, r, s, t, u, and v are each an integer of 0 to 450, where p+q+r+s+t+u+v=10 to 450, and each of these units may be linear or branched. In addition, each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be randomly bonded.)
wherein U is a single bond or a divalent to pentavalent organic group, Z is independently a single bond, or a carbon atom, a silicon atom, a nitrogen atom, -SiR'= (R' is an alkyl group having 1 to 4 carbon atoms) or a trivalent to nonavalent organic group, Y is independently a divalent hydrocarbon group which may have one or more bonds selected from a fluorine atom, a silicon atom and a siloxane bond, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, a is independently 2 or 3 for each unit bonded to a silicon atom, b is independently an integer of 1 to 8, and c is an integer of 1 to 4.] 2. The fluorine-containing ether composition according to claim 1, wherein in RF ² in said formula (1), the molar ratio of --CF ₂ O-- to --CF ₂ CF ₂ O-- (--CF ₂ CF ₂ O--/--CF ₂ O--) is from 1.05 to 1.2. The fluorine-containing ether composition according to claim 1, wherein in formula (1), X is selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxy-substituted alkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen group. In the formula (1), U is a single bond, a carbonyl group, an amide group, a group represented by the following formula:

(In the formula, B is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent polyether group, and B' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.)
or a di- to pentavalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more atoms or groups selected from an oxygen atom, a sulfur atom, a hydroxyl group, a polyether group, a diorganosilylene group, a linear divalent organopolysiloxane residue having 2 to 100 silicon atoms, a silalkylene group, a silarylene group, a secondary amino group, a tertiary amino group, an ether group, a carbonyl group, an amide group, and an ester group. The fluorine-containing ether composition according to claim 1, wherein in formula (1), Z is a single bond, a carbon atom, a silicon atom, a nitrogen atom, a linear, branched or cyclic trivalent to octavalent organopolysiloxane residue having 3 to 13 silicon atoms, a trivalent isocyanuric group, or a trivalent triazine ring-containing group. The fluorine-containing ether composition according to claim 1, wherein in formula (1), Y is a group selected from the group consisting of alkylene groups having 1 to 10 carbon atoms, alkylene groups having 1 to 10 carbon atoms containing a fluorine atom, alkylene groups having 1 to 10 carbon atoms containing an arylene group having 6 to 8 carbon atoms, divalent groups in which alkylene groups having 1 to 10 carbon atoms are mutually bonded via a silalkylene structure or a silarylene structure, and divalent groups in which an alkylene group having 2 to 10 carbon atoms is bonded to a bond of a linear divalent organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic divalent organopolysiloxane residue having 3 to 10 silicon atoms. The fluorine-containing ether composition according to claim 1, further comprising 25 mass% or less of a fluoropolyether group-containing polymer having silanol groups or hydrolyzable silyl groups at both ends, represented by the following general formula (3), and/or a partial (hydrolyzed) condensate thereof:

[In the formula, U, Z, Y, R, X, a, b, and c are independently the same as above, and Rf′ is represented by the following formula (4):

(In the formula, W, d, p, q, r, s, t, u, v, and p+q+r+s+t+u+v are the same as above. d' is an integer of 1 to 6. Each of these units may be linear or branched. In addition, each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be bonded randomly.)
is a divalent fluoropolyether group represented by the following formula: 2. The fluorine-containing ether composition according to claim 1, further comprising 30% by mass or less of a fluoropolyether group-containing polymer represented by the following general formula (5):
A-Rf'-A (5)
In the formula, A is independently a fluorine atom, a hydrogen atom, or a monovalent fluorine-containing hydrocarbon group having a terminal group of CF ₃ —, CF ₂ H—, CF ₃ CF ₂ —, or CF ₃ CFH— and which may contain an oxygen atom. Rf′ is a group represented by the following formula (4):

(In the formula, W, d, p, q, r, s, t, u, v, and p+q+r+s+t+u+v are the same as above. d' is an integer of 1 to 6. Each of these units may be linear or branched. In addition, each repeating unit shown in parentheses with p, q, r, s, t, u, and v may be bonded randomly.)
is a divalent fluoropolyether group represented by the following formula: The fluorine-containing ether composition according to claim 1, wherein the fluoropolyether group-containing polymer having a silanol group or a hydrolyzable silyl group at one end represented by the formula (1) is at least one selected from those represented by the following formulas:

(In the formula, RF ¹ and RF ² are the same as above, p1 is an integer of 5 to 440, q1 is an integer of 5 to 250, p1+q1 is an integer of 20 to 450, and each repeating unit shown in parentheses with p1 and q1 may be randomly bonded.) A surface treatment agent comprising the fluorine-containing ether composition according to any one of claims 1 to 9. An article that has been surface-treated with the surface treatment agent according to claim 10.