JP5397561B2 - Fluoropolyether group-containing silicone compound - Google Patents

Description

  The present invention relates to silicone compounds containing fluoropolyether groups, in particular perfluoropolyether groups. The present invention also relates to a surface treatment agent using such a fluoropolyether group-containing silicone compound.

  It is known that certain fluorine-containing silane compounds can provide excellent water repellency, oil repellency, antifouling properties and the like when used for surface treatment of a substrate. A layer obtained from a surface treatment agent containing a fluorine-containing silane compound (hereinafter also referred to as a surface treatment layer) is applied as a so-called functional thin film to various substrates such as glass, plastic, fiber, and building materials. .

  As such a fluorine-containing silane compound, a perfluoropolyether group-containing silane compound having a perfluoropolyether group in the molecular main chain and a hydrolyzable group bonded to a Si atom at the molecular terminal or terminal part is known. (See Patent Documents 1 and 2). When this surface treatment agent containing a perfluoropolyether group-containing silane compound is applied to a substrate, the hydrolyzable groups bonded to Si atoms are bonded to each other by reacting with the substrate and between the compounds. A treatment layer can be formed.

Special table 2008-534696 gazette International Publication No. 97/07155 Special table 2009-541498 gazette JP 2011-116947 A JP 2011-178835 A

  Since the layer obtained from the surface treatment agent containing a perfluoropolyether group-containing silane compound can exhibit the above-described functions even in a thin film, it is suitable for optical members such as glasses and touch panels that require optical transparency or transparency. It is preferably used. In particular, in these applications, in addition to anti-fouling properties that prevent water and oil repellency, dirt such as fingerprints from sticking, surface slipperiness that can be easily wiped even if dirt such as fingerprints is attached. Desired.

  Furthermore, in recent years, with the rapid spread of smartphones and tablet terminals, it is desired to provide an excellent tactile sensation (usability) when a user touches and operates a display panel with a finger. Yes. For this reason, it is required to realize surface slipperiness higher than that in the past.

  However, a layer obtained from a conventional surface treatment agent containing a perfluoropolyether group-containing silane compound is no longer sufficient to meet the increasing demand for improved surface slipperiness.

  With regard to the release agent, a fluoroalkyl group-containing silicone compound having a siloxane skeleton in the molecular main chain and a C1-C6 fluoroalkyl group in the molecular side chain is known (see Patent Document 3). about). However, such a fluoroalkyl group-containing silicone compound has releasability but does not provide water repellency, oil repellency, antifouling property and the like to the substrate.

Regarding the surface treatment agent used for providing water repellency, oil repellency, antifouling property, etc., it has a divalent perfluoropolyether group and a siloxane skeleton in the molecular main chain, and has a siloxane skeleton. There are known perfluoropolyether group-containing silicone compounds in which Si atoms are linked via a repeating unit of — (CH ₂ ) —, and a hydrolyzable group is bonded to the linked Si atoms. (See Patent Documents 4 and 5). However, even such a perfluoropolyether group-containing silicone compound is not always satisfactory in terms of surface slipperiness.

  An object of the present invention is to provide a novel fluoropolyether group-containing silicone compound that can form a layer having water repellency, oil repellency, and antifouling properties and high surface slipperiness. Moreover, an object of this invention is to provide the surface treating agent etc. which are obtained using this fluoro polyether group containing silicone compound.

（これら式中、Ｒ^１は置換または非置換のメチル基であり、Ｒｆはフルオロポリエーテル基を含む基であり、Ｘは３価の有機基であり、Ｙは２価の有機基であり、Ｚは加水分解可能な部位を含むシリル基であり、Ｓ^１は一価のオルガノポリシロキサン基であり、Ｓ^２は二価のオルガノポリシロキサン基であり、ｍは１以上５以下である。）
なお、本明細書を通じて、ある一般式中に同じ記号が複数存在している場合、これらは互いに独立して選択され得る。 According to one aspect of the present invention, there is provided a fluoropolyether group-containing silicone compound having a structure represented by any of the following general formulas (Ia), (Ib), (IIa) and (IIb).

(In these formulas, R ¹ is a substituted or unsubstituted methyl group, Rf is a group containing a fluoropolyether group, X is a trivalent organic group, Y is a divalent organic group, Z is a silyl group containing a hydrolyzable site, S ¹ is a monovalent organopolysiloxane group, S ² is a divalent organopolysiloxane group, and m is 1 or more and 5 or less.)
In addition, throughout this specification, when there are a plurality of the same symbols in a general formula, these can be selected independently of each other.

The fluoropolyether group-containing silicone compound of the present invention comprises a fluoropolyether group (in Rf), an organopolysiloxane group (S ¹ or S ² ), and a silyl group (Z) containing a hydrolyzable site. Have. The fluoropolyether group (in Rf) contributes to water repellency and oil repellency as well as antifouling properties. Further, the siloxane skeleton of the organopolysiloxane group (S ¹ or S ² ) contributes to surface slipperiness. Furthermore, the silyl group (Z) containing a hydrolyzable site contributes to friction durability. According to such a fluoropolyether group-containing silicone compound, it becomes possible to form a layer having water repellency, oil repellency, antifouling properties, high surface slipperiness, and friction durability.

（式中、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７およびＲ^８は、それぞれ独立してアルキル基またはアリール基であり、ｎは１以上２００以下である。）
で表されるオルガノポリシロキサン基であってよい。 In the above general formulas (Ia) and (Ib), S ¹ represents the following formula:

(In the formula, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently an alkyl group or an aryl group, and n is 1 or more and 200 or less.)
It may be an organopolysiloxane group represented by:

（式中、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６およびＲ^７は、それぞれ独立してアルキル基またはアリール基であり、ｎは１以上２００以下である。）
で表されるオルガノポリシロキサン基であってよい。 In the above general formulas (IIa) and (IIb), S ² represents the following formula:

(In the formula, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently an alkyl group or an aryl group, and n is 1 or more and 200 or less.)
It may be an organopolysiloxane group represented by:

In the above general formulas (Ia), (Ib), (IIa) and (IIb), Rf is preferably a group containing a perfluoropolyether group, but a part of the fluorine atoms are hydrogen atoms or other halogen atoms. May be substituted. Perfluoropolyether groups can further enhance water and oil repellency and thus antifouling properties.
For example, Rf is the following formula:
_{^{- (R 9) j -R 10}} -R 11 -
[Wherein R ⁹ is a C 1-15 perfluoroalkylene group,
j is 0 or 1,
R ¹⁰ has the following formula:
_{- (OC 4 F 8) v} - (OC 3 F 6) a - (OC 2 F 4) b - (OCF 2) c -
Wherein a, b, c and v are each independently an integer of 0 or more and 200 or less, the sum of a, b, c and v is at least 1, and each repeating unit enclosed in parentheses The order of presence of is arbitrary in the formula.)
A perfluoropolyether group represented by
R ¹¹ has the following formula:
− (Q) _d − (CFZ ′) _e −
(In the formula, Q represents an oxygen atom or a divalent polar group, Z ′ represents a fluorine atom or a lower fluoroalkyl group, and d and e are each independently an integer of 0 to 50, (The sum of e is at least 1, and the order in which each repeating unit in parentheses is present is arbitrary in the formula.)
It is group represented by these. ]
It may be a group represented by

Also, for example, in the above general formulas (Ia), (Ib), (IIa) and (IIb), Rf represents the following formula:
_{-CF 2 CF 2 - (OCF 2} CF 2 CF 2) a '-OCF 2 CF 2 -
(Wherein, a ′ is an integer of 1 to 200)
The perfluoropolyether group represented by these may be sufficient.

In the above general formulas (Ia), (Ib), (IIa) and (IIb), Z represents the following formula:
-SiT _x R ¹² _3-x
(In the formula, T is a hydroxyl group or a hydrolyzable group, R ¹² is a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, and x is 1, 2 or 3.)
The silyl group represented by these may be sufficient.

（これら式中、ｐは１以上１０以下の整数であり、Ｒ^１３は２価の有機基であり、式の左端がＲｆに結合し、式の右端がＳ^１またはＳ^２に結合し、式の下端がＹに結合する。）
で表される基であってよい。 In the above general formulas (Ia), (Ib), (IIa) and (IIb), X is any one of the following formulas:

(In these formulas, p is an integer of 1 to 10, R ¹³ is a divalent organic group, the left end of the formula is bonded to Rf, the right end of the formula is bonded to S ¹ or S ² , The lower end of is bonded to Y.)
It may be a group represented by

In the general formulas (Ia), (Ib), (IIa) and (IIb), Y represents the following formula:
-OCONH- _{(CH 2) r} -
(In the formula, r is an integer of 1 to 10, and the left end of the formula is bonded to X, and the right end of the formula is bonded to Z.)
It may be a group represented by

  According to another aspect of the present invention, a surface treatment agent comprising the above-mentioned fluoropolyether group-containing silicone compound is also provided. The surface treatment agent of the present invention contains at least one of the fluoropolyether group-containing silicone compound represented by the general formula (Ia) and the fluoropolyether group-containing silicone compound represented by the general formula (Ib), Both of them may be included. Further, the surface treating agent of the present invention is at least one of the fluoropolyether group-containing silicone compound represented by the general formula (IIa) and the fluoropolyether group-containing silicone compound having a structure represented by the general formula (IIb). One may be included and both of these may be included. However, the surface treatment composition of the present invention may contain any of the fluoropolyether group-containing silicone compounds having the structure represented by the general formulas (Ia), (Ib), (IIa) and (IIb). What is necessary is just to include these 2 types or more in arbitrary combinations. Such a surface treatment agent of the present invention can impart water repellency, oil repellency, antifouling property, and surface slipperiness to a substrate, and is not particularly limited, but is suitable as an antifouling coating agent. Can be used.

  According to still another aspect of the present invention, an article includes a substrate and a layer (surface treatment layer) formed on the surface of the substrate from the fluoropolyether group-containing silicone compound or the surface treatment agent. Is also provided. The layer in such an article has water repellency, oil repellency, antifouling properties and high surface slipperiness.

  The article obtained by the present invention is not particularly limited, but may be, for example, an optical member. Optical members are highly demanded to improve surface slipperiness, and the present invention can be suitably used. The substrate can be, for example, glass or transparent plastic. In the present invention, “transparent” may be anything that can be generally recognized as transparent, but for example, it means a haze value of 3% or less.

  According to the present invention, a novel fluoropolyether group-containing silicone compound is provided, which compound has a fluoropolyether group, an organopolysiloxane group, and a silyl group containing a hydrolyzable moiety. Thus, a layer having water repellency, oil repellency and antifouling properties, high surface slipperiness, and friction durability can be formed. Furthermore, according to this invention, the surface treating agent obtained using such a fluoro polyether group containing silicone compound and the articles | goods to which they are applied are also provided.

  Hereinafter, although the fluoropolyether group containing silicone compound of this invention, a surface treating agent, and the articles | goods obtained by applying them are explained in full detail, this invention is not limited to this.

Fluoropolyether group-containing silicone compound The fluoropolyether group-containing silicone compound of the present invention is represented by any one of the following general formulas (Ia), (Ib), (IIa) and (IIb) In the case of general formula (IIb), it has a structure represented by general formula (IIb), and the same applies to the following).

In the general formulas (Ia), (Ib), (IIa) and (IIb), R ¹ is a substituted or unsubstituted methyl group. Examples of the substituent for the methyl group include halogen atoms such as fluorine, iodine and bromine. R ¹ may be a methyl group substituted with a fluorine atom, and is preferably a trifluoromethyl group (CF ₃ —).

  In the general formulas (Ia), (Ib), (IIa) and (IIb), Rf is a group containing a fluoropolyether group. The fluoropolyether group of Rf can take a linear, branched or cyclic structure with respect to the ether bond chain, but is preferably linear. The fluoropolyether group of Rf is preferably a perfluoropolyether group, but a part of the fluorine atoms may be substituted with a hydrogen atom or another halogen atom. Furthermore, it is more preferable that Rf is a perfluoropolyether group as a whole.

More specifically, Rf is represented by the following formula:
_{^{- (R 9) j -R 10}} -R 11 -
It is preferable that it is group represented by these.
In this formula, R ⁹ is a C 1-15 (for example, linear or branched) perfluoroalkyl group, preferably a C 1-2 perfluoroalkyl group (—CF ₂ —, — C ₂ F ₄ -) it is. j may be 0 or 1.
In the above formula, R ¹⁰ represents the following formula:
_{- (OC 4 F 8) v} - (OC 3 F 6) a - (OC 2 F 4) b - (OCF 2) c -
The perfluoropolyether group represented by these. In this formula, a, b, c and v each represent the number of four types of repeating units of perfluoropolyether constituting the main skeleton of the polymer, and are independently from 0 to 200, preferably from 1 to 100 And the sum of a, b, c and v is at least 1, preferably 1 or more and 100 or less. In addition, for convenience, the order of presence of each repeating unit with parentheses a, b, c, or v is described in a specific order in the formula, but the order of bonding of these repeating units is limited to this. It is not optional. Among these repeating units, — (OC ₄ F ₈ ) — represents — (OCF ₂ CF ₂ CF ₂ CF ₂ ) —, — (OCF (CF ₃ ) CF ₂ CF ₂ ) —, — (OCF ₂ CF (CF _{3) CF 2) -, -} (OCF 2 CF 2 CF (CF 3)) -, - (OC (CF 3) 2 CF 2) -, - (OCF 2 C (CF 3) 2) -, - (OCF (CF ₃ ) CF (CF ₃ ))-,-(OCF (C ₂ F ₅ ) CF ₂ )-and-(OCF ₂ CF (C ₂ F ₅ ))-may be used, but preferably _{- (OCF 2 CF 2 CF 2} CF 2) - a. -(OC ₃ F ₆ )-may be any of-(OCF ₂ CF ₂ CF ₂ )-,-(OCF (CF ₃ ) CF ₂ )-and-(OCF ₂ CF (CF ₃ ))-. good, preferably _{- (OCF 2 CF 2 CF 2} ) - a. - _(OC 2 _{F 4)} - is, - _{(OCF 2} CF 2) - and _{- (OCF (CF 3))} - but may be any of, preferably - _{(OCF 2} CF 2) - a.
In the above formula, R ¹¹ represents the following formula:
− (Q) _d − (CFZ ′) _e −
It is group represented by these. In this formula, Q represents an oxygen atom (—O—) or another divalent polar group. When Q is an oxygen atom, Rf is a perfluoropolyether group as a whole. Examples of the divalent polar group include —O—, —COO—, —OCO—, —CONH—, —COS—, —SCO— and the like, preferably —O—, —COO—, —CONH. -. Z ′ represents a fluorine atom or a lower fluoroalkyl group, for example, a fluoroalkyl group having 1 to 3 carbon atoms. In this formula, d and e are each independently 0 or more and 50 or less, preferably an integer of 0 to 20, for example, an integer of 1 to 20, and the sum of d and e is at least 1, preferably 1 to 10. It is. d and e are more preferably integers of 0 to 2, and even more preferably d = 0 or 1, and e = 2. Further, the order of presence of each repeating unit with subscripts d and e attached in parentheses is described in a specific order in the formula for the sake of convenience, but the bonding order of these repeating units is not limited to this, and is arbitrary. It is.
Such a compound having a perfluoropolyether group can exhibit excellent water repellency and oil repellency, and thus antifouling properties (for example, preventing adhesion of dirt such as fingerprints).

Specifically, Rf is the following formula:
_{-CF 2 CF 2 - (OCF 2} CF 2 CF 2) a '-OCF 2 CF 2 -
The perfluoropolyether group represented by these may be sufficient. In the formula, a ′ is an integer of 1 to 200, preferably 1 to 100. In this case, the perfluoropolyether group has a linear structure, and can have higher friction durability than the case of having a branched structure, and also has an advantage that synthesis is easy.

^{S 2} in ^{S 1} and the general formula (IIa) and (IIb) in the general formula (Ia) and (Ib) are both a linear organopolysiloxane group, terminal (linear group And more specifically, S ¹ is one end and S ² is both ends), and is preferably a group that binds to X described later. The linear organopolysiloxane group can have any suitable organic group in the side chain.
A compound having a siloxane skeleton can exhibit excellent surface slipperiness (or lubricity, for example, inconspicuousness such as fingerprints and excellent tactile sensation to fingers).

式中、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７およびＲ^８は、それぞれ独立して、置換または非置換のアルキル基あるいは置換または非置換のアリール基である。かかる置換または非置換のアルキル基は、好ましくは炭素数１〜２０、より好ましくは炭素数１〜１２を有する。置換または非置換のアリール基は、好ましくは炭素数６〜２０、より好ましくは炭素数６〜１２を有する。アルキル基の置換基としては、塩素原子などのハロゲン原子が挙げられる。アリール基の置換基としては、塩素原子などのハロゲン原子や、また、例えばメチル基などの炭素数１〜１０のアルキル基が挙げられる。Ｒ^２〜Ｒ^８の例には、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基およびドデシル基などの非置換アルキル基；クロロメチル基などの置換アルキル基；フェニル基およびナフチル基などの非置換アリール基；４−クロロフェニル基および２−メチルフェニル基などの置換アリール基が含まれる。それらの中でも、アルキル基、特に非置換アルキル基が好ましく、メチル基がより好ましい。
また、式中、ｎは１以上２００以下、好ましくは１以上１００以下である。１つの化合物のみに着目すれば、ｎは整数であるが、本発明の化合物は上記一般式（Ｉａ）で表される複数の化合物の混合物、上記一般式（Ｉｂ）で表される複数の化合物の混合物、上記一般式（ＩＩａ）で表される複数の化合物の混合物、または上記一般式（ＩＩｂ）で表される複数の化合物の混合物であってよく、この場合、ｎは、かかる混合物の平均組成を表す実数であり得る。 More specifically, S ¹ may be an organopolysiloxane group represented by the following formula:

In the formula, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Such a substituted or unsubstituted alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms. The substituted or unsubstituted aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. Examples of the substituent of the alkyl group include a halogen atom such as a chlorine atom. Examples of the substituent for the aryl group include a halogen atom such as a chlorine atom, and an alkyl group having 1 to 10 carbon atoms such as a methyl group. Examples of R ^{2 to} R ⁸ include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group and dodecyl group; substituted alkyl groups such as chloromethyl group; phenyl group and naphthyl group Unsubstituted aryl groups; substituted aryl groups such as 4-chlorophenyl group and 2-methylphenyl group are included. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group is more preferable.
In the formula, n is 1 or more and 200 or less, preferably 1 or more and 100 or less. Focusing on only one compound, n is an integer, but the compound of the present invention is a mixture of a plurality of compounds represented by the above general formula (Ia), a plurality of compounds represented by the above general formula (Ib) A mixture of a plurality of compounds represented by the above general formula (IIa), or a mixture of a plurality of compounds represented by the above general formula (IIb), where n is the average of such mixtures It can be a real number representing the composition.

式中、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６およびＲ^７、ならびにｎについては、上記と同様の説明が当て嵌まる。 S ² may be an organopolysiloxane group represented by the following formula.

In the formula, the same explanation as above applies to R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ , and n.

In the general formulas (Ia), (Ib), (IIa) and (IIb), X is a bond between Rf and S ¹ or S ² (more specifically, Si forming a siloxane skeleton) and Y described later. A linking group. X should just be a trivalent organic group.

で表される基（但し、式の左端がＲｆに結合し、式の右端がＳ^１またはＳ^２に結合し、式の下端がＹに結合するものとする）であってよい。これら式中、ｐは１以上１０以下、好ましくは１以上５以下の整数であり、Ｒ^１３は２価の有機基である。Ｒ^１３は、特に限定されないが、例えば−（ＣＨ_２）_ｑ’−Ｏ−（ＣＨ_２）_ｑ−であってよく、ｑは１以上２０以下、好ましくは１以上１０以下の整数であり、ｑ’は１以上１０以下、好ましくは１以上５以下の整数、代表的には１である。 More particularly, X is one of the following formulas:

A group represented by (wherein, the left end of the formula is bonded to Rf, the right end of the formula is bound to S ¹ or S ^2, the lower end of the expression is assumed to bind to Y) may be. In these formulas, p is an integer of 1 to 10, preferably 1 to 5, and R ¹³ is a divalent organic group. R ¹³ is not particularly limited, and may be, for example, — (CH ₂ ) _{q ′} —O— (CH ₂ ) _q —, where q is an integer of 1 to 20, preferably 1 to 10. 'Is an integer from 1 to 10, preferably from 1 to 5, typically 1.

However, X is not limited to the above example, and any suitable divalent organic compound can be used as long as it bonds between Rf and S ¹ or S ² (more specifically, Si forming a siloxane skeleton) and Y described later. Groups can be applied.

In the general formulas (Ia), (Ib), (IIa) and (IIb), Z is a silyl group containing a hydrolyzable moiety. More specifically, Z is the following formula:
-SiT _x R ¹² _3-x
The silyl group represented by these may be sufficient. In this formula, T and R ¹² are groups bonded to Si, and x is 1, 2 or 3.

T represents a hydroxyl group or a hydrolyzable group. Examples of hydrolyzable groups include —OA, —OCOA, —O—N═C (A) ₂ , —N (A) ₂ , —NHA, halogen (in these formulas, A is substituted or unsubstituted) Represents an alkyl group having 1 to 3 carbon atoms, preferably -OA (alkoxy group). Examples of A include an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, and an isopropyl group; and a substituted alkyl group such as a chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group is more preferable. The hydroxyl group is not particularly limited, but may be a group produced by hydrolysis of a hydrolyzable group.

R ¹² represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms (eg, linear or branched), preferably an alkyl group having 1 to 22 carbon atoms, more preferably a linear chain having 1 to 3 carbon atoms. Or a branched alkyl group (CH ₃ —, C ₂ H ₅ —, C ₃ H ₇ —).
In the compound of the present invention, the hydrolyzable group (-T) bonded to Si can be bonded by reacting with the substrate and between the compounds, and the compound having such a group is, for example, a silicone described later. Excellent friction durability (relative to oil and fluorine-containing oil).

  In the general formulas (Ia), (Ib), (IIa), and (IIb), Y is a linking group that bonds between X and Z. Y may be a divalent organic group.

More particularly, Y represents the following formula:
-OCONH- _{(CH 2) r} -
(Wherein, the left end of the formula is bonded to X and the right end of the formula is bonded to Z). In this formula, r is an integer of 1 to 10, preferably 1 to 5.

  However, Y is not limited to the above example, and any appropriate divalent organic group can be applied as long as it binds between X and Z.

  In the general formula (IIb), m is 1 or more and 5 or less, preferably 1 or more and 3 or less. Focusing on only one compound, m is an integer, but the compound of the present invention may be a mixture of a plurality of compounds having the structure represented by the general formula (IIb), in which case m is It can be a real number representing the average composition of such a mixture.

  The fluoropolyether group-containing silicone compound represented by the general formulas (Ia), (Ib), (IIa) and (IIb) of the present invention has been described above. The fluoropolyether group-containing silicone compound represented by the general formula (Ia) preferably has an average molecular weight of 1000 to 30000, for example. Moreover, it is preferable that the fluoro polyether group containing silicone compound represented by general formula (Ib) has an average molecular weight of 2000-15000, for example. The fluoropolyether group-containing silicone compound represented by the general formula (IIa) preferably has an average molecular weight of 1000 to 30000, for example. Moreover, it is preferable that the fluoro polyether group containing silicone compound represented by general formula (IIb) has an average molecular weight of 2000-15000, for example. Thereby, the high solubility with respect to a solvent is acquired, and there exists an advantage that a synthesis | combination is easy. In the present invention, “average molecular weight” refers to a number average molecular weight.

  Such a fluoropolyether group-containing silicone compound of the present invention can be produced by any appropriate method.

（式中、Ｒ^１３およびＳ^１は上記の通りである。）
で表される化合物を、フルオロポリエーテル系原料として以下の一般式（ｉｉ）または（ｉｉｉ）：
Ｒ^１−Ｒｆ−（ＣＨ_２）_ｐ−ＯＨ ・・・（ｉｉ）
Ｒ^１−Ｒｆ−（ＣＨ_２）_ｐ−ＮＨ_２ ・・・（ｉｉｉ）
（式中、Ｒ^１、Ｒｆ、ｐは上記の通りである。）
で表される化合物とエポキシ開環反応に付し、およびシリル基含有原料として以下の一般式（ｉｖ）：
ＯＣＮ−（ＣＨ_２）_ｒ−Ｚ ・・・（ｉｖ）
（式中、Ｚ、ｒは上記の通りである。）
で表される化合物とウレタン結合形成反応に付すことによって得ることができる。 For example, the fluoropolyether group-containing silicone compound represented by the above general formula (Ia) is a silicone-based raw material represented by the following general formula (i):

(Wherein R ¹³ and S ¹ are as described above.)
As a fluoropolyether-based material, the following general formula (ii) or (iii):
R ¹ —Rf— (CH ₂ ) _p —OH (ii)
R ¹ —Rf— (CH ₂ ) _p —NH ₂ (iii)
(Wherein R ¹ , Rf, and p are as described above.)
And the following general formula (iv) as a silyl group-containing raw material:
_{OCN- (CH 2) r -Z ···} (iv)
(In the formula, Z and r are as described above.)
It can obtain by attaching | subjecting to a urethane bond formation reaction with the compound represented by these.

（式中、Ｒ^１３およびＳ^１は上記の通りである。）で表される化合物を、フルオロポリエーテル系原料として以下の一般式（ｉｉ’）または（ｉｉｉ’）：
ＨＯ−（ＣＨ_２）_ｐ−Ｒｆ−（ＣＨ_２）_ｐ−ＯＨ ・・・（ｉｉ’）
Ｈ_２Ｎ−（ＣＨ_２）_ｐ−Ｒｆ−（ＣＨ_２）_ｐ−ＮＨ_２ ・・・（ｉｉｉ’）
（式中、Ｒｆ、ｐは上記の通りである。）
で表される化合物とエポキシ開環反応に付し、およびシリル基含有原料として以下の一般式（ｉｖ）：
ＯＣＮ−（ＣＨ_２）_ｒ−Ｚ ・・・（ｉｖ）
（式中、Ｚ、ｓは上記の通りである。）で表される化合物とウレタン結合形成反応に付すことによって得ることができる。 Further, for example, the fluoropolyether group-containing silicone compound represented by the general formula (Ib) is represented by the following general formula (i):

(Wherein R ¹³ and S ¹ are as described above), the following general formula (ii ′) or (iii ′) as a fluoropolyether-based raw material:
_{HO- (CH 2) p -Rf- (} CH 2) p -OH ··· (ii ')
_{H 2 N- (CH 2) p} -Rf- (CH 2) p -NH 2 ··· (iii ')
(In the formula, Rf and p are as described above.)
And the following general formula (iv) as a silyl group-containing raw material:
_{OCN- (CH 2) r -Z ···} (iv)
(Wherein Z and s are as described above) and can be obtained by subjecting the compound to a urethane bond forming reaction.

（式中、Ｒ^１３およびＳ^１は上記の通りである。）で表される化合物を、フルオロポリエーテル系原料として以下の一般式（ｉｉ）または（ｉｉｉ）：
Ｒ^１−Ｒｆ−（ＣＨ_２）_ｐ−ＯＨ ・・・（ｉｉ）
Ｒ^１−Ｒｆ−（ＣＨ_２）_ｐ−ＮＨ_２ ・・・（ｉｉｉ）
（式中、Ｒ^１、Ｒｆ、ｐは上記の通りである。）
で表される化合物とエポキシ開環反応に付し、およびシリル基含有原料として以下の一般式（ｉｖ）：
ＯＣＮ−（ＣＨ_２）_ｒ−Ｚ ・・・（ｉｖ）
（式中、Ｚ、ｒは上記の通りである。）
で表される化合物とウレタン結合形成反応に付すことによって得ることができる。 Further, for example, the fluoropolyether group-containing silicone compound represented by the general formula (IIa) is a silicone-based raw material represented by the following general formula (i ′):

(Wherein R ¹³ and S ¹ are as described above), the following general formula (ii) or (iii):
R ¹ —Rf— (CH ₂ ) _p —OH (ii)
R ¹ —Rf— (CH ₂ ) _p —NH ₂ (iii)
(Wherein R ¹ , Rf, and p are as described above.)
And the following general formula (iv) as a silyl group-containing raw material:
_{OCN- (CH 2) r -Z ···} (iv)
(In the formula, Z and r are as described above.)
It can obtain by attaching | subjecting to a urethane bond formation reaction with the compound represented by these.

（式中、Ｒ^１３およびＳ^１は上記の通りである。）
で表される化合物を、フルオロポリエーテル系原料として以下の一般式（ｉｉ’）または（ｉｉｉ’）：
ＨＯ−（ＣＨ_２）_ｐ−Ｒｆ−（ＣＨ_２）_ｐ−ＯＨ ・・・（ｉｉ’）
Ｈ_２Ｎ−（ＣＨ_２）_ｐ−Ｒｆ−（ＣＨ_２）_ｐ−ＮＨ_２ ・・・（ｉｉｉ’）
（式中、Ｒｆ、ｐは上記の通りである。）
で表される化合物とエポキシ開環反応に付し、およびシリル基含有原料として以下の一般式（ｉｖ）：
ＯＣＮ−（ＣＨ_２）_ｒ−Ｚ ・・・（ｉｖ）
（式中、Ｚ、ｓは上記の通りである。）
で表される化合物とウレタン結合形成反応に付すことによって得ることができる。
この例において得られるフルオロポリエーテル基含有シリコーン化合物は、具体的には、使用するフルオロポリエーテル系原料にもよるが、以下の式のいずれかで表される化合物となる。

Further, for example, a fluoropolyether group-containing silicone compound having a structure represented by the above general formula (IIb) is used as a silicone-based raw material in the following general formula (i ′):

(Wherein R ¹³ and S ¹ are as described above.)
As a fluoropolyether-based material, the following general formula (ii ′) or (iii ′):
_{HO- (CH 2) p -Rf- (} CH 2) p -OH ··· (ii ')
_{H 2 N- (CH 2) p} -Rf- (CH 2) p -NH 2 ··· (iii ')
(In the formula, Rf and p are as described above.)
And the following general formula (iv) as a silyl group-containing raw material:
_{OCN- (CH 2) r -Z ···} (iv)
(In the formula, Z and s are as described above.)
It can obtain by attaching | subjecting to a urethane bond formation reaction with the compound represented by these.
Specifically, the fluoropolyether group-containing silicone compound obtained in this example is a compound represented by any of the following formulas, although it depends on the fluoropolyether-based raw material used.

（式中、ｐおよびＲ^１３は上記の通りであり、式の左端がＲｆに結合し、式の右端がＳ^１に結合し、式の下端がＹに結合するものとする。）
で表される基となり、Ｙは以下の式：
−ＯＣＯＮＨ−（ＣＨ_２）_ｒ−
（式中、ｒは上記の通りであり、式の左端がＸに結合し、式の右端がＺに結合するものとする）
で表される基となる。 For the fluoropolyether group-containing silicone compound obtained by any of these examples, X is one of the following formulas depending on the fluoropolyether-based raw material used:

(Wherein, p and R ¹³ are as described above, the left end of the formula is bonded to Rf, the right end of the formula is bound to S ^1, the lower end of the expression is assumed to bind to Y.)
Y is a group represented by the following formula:
-OCONH- _{(CH 2) r} -
(In the formula, r is as described above, and the left end of the formula is bonded to X and the right end of the formula is bonded to Z)
It becomes the group represented by.

Further, for example, as a fluoropolyether-based raw material, a raw material in which a compound represented by the general formula (ii) and a compound represented by the general formula (ii ′) are mixed, or represented by the general formula (iii) A raw material in which the compound and the compound represented by the general formula (iii ′) are mixed (in these raw materials, a fluorine-containing oil represented by the general formula R ¹ —Rf—F described later may further be mixed). ) May be used. Moreover, for example, a raw material in which a compound represented by the general formula (i) and a compound represented by the general formula (i ′) are mixed may be used as the silicone-based raw material. In such a case, in the obtained reaction mixture, the fluoropolyether group-containing silicone compound represented by the general formulas (Ia), (Ib), (IIa) and (IIb) is appropriately mixed depending on the raw materials used. Will be.

  The epoxy ring-opening reaction and the urethane bond forming reaction may be allowed to proceed without a solvent or in a solvent. Examples of such solvents include perfluoroaliphatic hydrocarbons, aromatic hydrocarbons having fluorine-containing substituents (eg, bis (trifluoromethyl) benzene), hydrofluoroethers, and the like alone or Two or more kinds may be used in combination.

  The epoxy ring-opening reaction can be carried out in the presence of a catalyst such as an acid, for example, at 0 to 150 ° C., conveniently under normal pressure. The urethane bond forming reaction can be carried out in the presence of a catalyst such as organotin, organotitanium and amine compound, for example, at 20 to 150 ° C., conveniently under normal pressure. When carrying out the epoxy ring-opening reaction and the urethane bond forming reaction, it is preferable to react under a nitrogen stream from the viewpoint of suppressing the condensation reaction.

  Although the four fluoropolyether group-containing silicone compounds of the present invention have been described with reference to production examples, the fluoropolyether group-containing silicone compound of the present invention is limited to those produced by these examples. It is not a thing.

  Although the compound of this invention is useful in a surface treating agent as mentioned below, it is not limited to this, For example, it can be used also as a lubrication agent and a compatibilizing agent.

-Surface treatment agent The surface treatment agent (or surface treatment composition) of this invention should just contain the fluoro polyether group containing silicone compound of this invention mentioned above. Specifically, at least one of the fluoropolyether group-containing silicone compound represented by the general formula (Ia) and the fluoropolyether group-containing silicone compound represented by the general formula (Ib) is included, and both of these are included. May be included. When these are used in combination, the compound represented by the general formula (Ia) and the compound represented by the general formula (Ib) may exist in a mass ratio of 1: 1 to 9: 1, for example. It is not limited to. In addition, at least one of the fluoropolyether group-containing silicone compound represented by the general formula (IIa) and the fluoropolyether group-containing silicone compound represented by the general formula (IIb) is included, and both of these are included. Also good. When these are used in combination, the compound represented by the general formula (IIa) and the compound represented by the general formula (IIb) can exist in a mass ratio of 1: 1 to 9: 1, for example. It is not limited to. However, the surface treatment composition of the present invention only needs to contain any of the fluoropolyether group-containing silicone compounds represented by the general formulas (Ia), (Ib), (IIa) and (IIb), Two or more of these may be included in any combination.

  The surface treatment agent only needs to contain a fluoropolyether group-containing silicone compound as a main component or an active ingredient. Here, the “main component” means a component having a content in the surface treatment agent exceeding 50%, and the “active ingredient” is formed on the substrate to be surface-treated to form a surface treatment layer, It means a component that can express some function (water repellency, oil repellency, antifouling property, surface slipperiness, friction durability, etc.).

  The surface treatment agent of the present invention contains the above-mentioned fluoropolyether group-containing silicone compound, has water repellency, oil repellency, antifouling properties, has high surface slipperiness, and has friction durability. Since the surface treatment layer can be formed, it is suitably used as an antifouling coating agent.

  Furthermore, the surface treating agent of the present invention can be understood as a silicone oil (for example, non-fluorine type) silicone compound (hereinafter referred to as “silicone oil” for the purpose of distinguishing from the fluoropolyether group-containing silicone compound of the present invention). May be included. Silicone oil contributes to further improving the surface slipperiness of the surface treatment layer.

  In the surface treatment agent of the present invention, for a total of 100 parts by mass of the fluoropolyether group-containing silicone compounds represented by the general formulas (Ia), (Ib), (IIa) and (IIb), the silicone oil is, for example, 0 to 80 parts by mass, preferably 0 to 40 parts by mass may be included.

  As such a silicone oil, for example, a linear or cyclic silicone oil having a siloxane bond of 2000 or less can be used. The linear silicone oil may be so-called straight silicone oil and modified silicone oil. Examples of the straight silicone oil include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil. Examples of the modified silicone oil include those obtained by modifying straight silicone oil with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol and the like. Examples of the cyclic silicone oil include cyclic dimethylsiloxane oil.

  Further, the surface treatment agent of the present invention may contain a fluoropolyether compound that can be understood as a fluorine-containing oil, preferably a perfluoropolyether compound (hereinafter, distinguished from the fluoropolyether group-containing silicone compound of the present invention). For this purpose, it is called “fluorinated oil”). The fluorine-containing oil contributes to further improving the surface slipperiness of the surface treatment layer.

  In the surface treatment agent of the present invention, the fluorine-containing oil is based on 100 parts by mass of the fluoropolyether group-containing silicone compounds represented by the general formulas (Ia), (Ib), (IIa) and (IIb), For example, it may be contained at 0 to 80 parts by mass, preferably 0 to 40 parts by mass.

Examples of such fluorine-containing oils include compounds represented by the following general formula (IV) (perfluoropolyether compounds).
^{_{R 21 - (OC 4 F 8}} ) v '' - (OC 3 F 6) a '' - (OC 2 F 4) b '' - (OCF 2) c '' -R 22 ··· (IV)
In the formula, R ²¹ represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms, and may preferably be substituted with one or more fluorine atoms. It is a C1-C3 alkyl group. Preferably, the alkyl group optionally substituted by one or more fluorine atoms is a fluoroalkyl group in which the terminal carbon atom is CF ₂ H— and all other carbon atoms are fully substituted by fluorine. Or a perfluoroalkyl group, more preferably a perfluoroalkyl group.
R ²² represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms, preferably substituted with one or more fluorine atoms. And an alkyl group having 1 to 3 carbon atoms. Preferably, the alkyl group optionally substituted by one or more fluorine atoms is a fluoroalkyl group in which the terminal carbon atom is CF ₂ H— and all other carbon atoms are fully substituted by fluorine. Or a perfluoroalkyl group, more preferably a perfluoroalkyl group.
a ″, b ″, c ″ and v ″ each represent the number of four types of repeating units of perfluoropolyether constituting the main skeleton of the polymer, each independently an integer of 0 to 300, It is an integer of 1 to 300, and the sum of a ″, b ″, c ″ and v ″ is at least 1, preferably 1 to 100. The order of presence of each repeating unit with the subscripts a ″, b ″, c ″ or v ″ and enclosed in parentheses is arbitrary in the formula. Among these repeating units, — (OC ₄ F ₈ ) — represents — (OCF ₂ CF ₂ CF ₂ CF ₂ ) —, — (OCF (CF ₃ ) CF ₂ CF ₂ ) —, — (OCF ₂ CF (CF _{3) CF 2) -, -} (OCF 2 CF 2 CF (CF 3)) -, - (OC (CF 3) 2 CF 2) -, - (OCF 2 C (CF 3) 2) -, - (OCF (CF ₃ ) CF (CF ₃ ))-,-(OCF (C ₂ F ₅ ) CF ₂ )-and-(OCF ₂ CF (C ₂ F ₅ ))-may be used, preferably- _{(OCF 2 CF 2 CF 2 CF} 2) - a. -(OC ₃ F ₆ )-may be any of-(OCF ₂ CF ₂ CF ₂ )-,-(OCF (CF ₃ ) CF ₂ )-and-(OCF ₂ CF (CF ₃ ))-. well, preferably _{- (OCF 2 CF 2 CF 2} ) - a. - _(OC 2 _{F 4)} - is, - _{(OCF 2} CF 2) - and _{- (OCF (CF 3))} - but may be any of, preferably - _{(OCF 2} CF 2) - a.

As an example of the perfluoropolyether compound represented by the above general formula (IV), it may be a compound represented by any of the following general formulas (IVa) and (IVb) (one kind or a mixture of two or more kinds). ).
^{_{R 21 - (OCF 2 CF 2}} CF 2) a '''-R 22 ··· (IVa)
^{_{R 21 - (OCF 2 CF 2}} CF 2 CF 2) v '''- (OCF 2 CF 2 CF 2) a''' - (OCF 2 CF 2) b '''- (OCF 2) c''' -R ²² (IVb)
In these formulas, R ²¹ and R ²² are as described above; in formula (IVa), a ′ ″ is an integer of 1 to 100; in formula (IVb), v ′ ″ and a ″. 'Is independently an integer of 1 to 30 and b''' and c '''are each independently an integer of 1 to 300. The order of presence of each repeating unit in parentheses with subscripts a ′ ″, b ′ ″, c ′ ″ or v ′ ″ is arbitrary in the formula. )

  The compound represented by the general formula (IVa) and the compound represented by the general formula (IVb) may be used alone or in combination. It is preferable to use the compound represented by the general formula (IVb) rather than the compound represented by the general formula (IVa) because higher surface slip properties can be obtained. When these are used in combination, it is preferable to use the compound represented by the general formula (IVa) and the compound represented by the general formula (IVb) at a mass ratio of 1: 1 to 1:30. According to such a mass ratio, a surface treating agent having an excellent balance between surface slipperiness and friction durability can be obtained.

From another viewpoint, the fluorinated oil is represented by the general formula R ¹ -Rf-F (wherein R ¹ and Rf are as described above, and R ¹ is preferably a trifluoromethyl group). It may be a compound. The compound represented by R ¹ -Rf-F is preferable in that high affinity is obtained with each compound represented by the above general formulas (Ia), (Ib), (IIa) and (IIb).

  The fluorine-containing oil preferably has an average molecular weight of 1000 to 30000, more preferably 3000 to 30000. Thereby, high surface slipperiness can be obtained.

  The surface treatment agent of the present invention may contain a perfluoropolyether group-containing silane compound. The perfluoropolyether group-containing silane compound contributes to the water repellency, oil repellency, antifouling property, surface slipperiness and friction durability of the surface treatment layer, and can contribute to improvement of friction durability.

  In the surface treatment agent of the present invention, the perfluoropolyether group is based on 100 parts by mass of the fluoropolyether group-containing silicone compounds represented by the general formulas (Ia), (Ib), (IIa) and (IIb). A containing silane compound may be contained, for example in 0-80 mass parts, Preferably it is 0-40 mass parts.

これら式中、Ｒ^３１は、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１〜１６のアルキル基を表し、好ましくは、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１〜３のアルキル基である。好ましくは、上記１個またはそれ以上のフッ素原子により置換されていてもよいアルキル基は、末端炭素原子がＣＦ_２Ｈ−であり他のすべての炭素原子がフッ素により全置換されているフルオロアルキル基、またはパーフルオロアルキル基であり、より好ましくはパーフルオロアルキル基である。
ａ、ｂ、ｃおよびｖは、ポリマーの主骨格を構成するパーフルオロポリエーテルの４種の繰り返し単位数をそれぞれ表し、互いに独立して０以上２００以下の整数、
例えば１以上２００以下の整数であって、ａ、ｂ、ｃおよびｖの和は少なくとも１、好ましくは１〜１００である。添字ａ、ｂ、ｃまたはｖを付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。これら繰り返し単位のうち、−（ＯＣ_４Ｆ_８）−は、−（ＯＣＦ_２ＣＦ_２ＣＦ_２ＣＦ_２）−、−（ＯＣＦ（ＣＦ_３）ＣＦ_２ＣＦ_２）−、−（ＯＣＦ_２ＣＦ（ＣＦ_３）ＣＦ_２）−、−（ＯＣＦ_２ＣＦ_２ＣＦ（ＣＦ_３））−、−（ＯＣ（ＣＦ_３）_２ＣＦ_２）−、−（ＯＣＦ_２Ｃ（ＣＦ_３）_２）−、−（ＯＣＦ（ＣＦ_３）ＣＦ（ＣＦ_３））−、−（ＯＣＦ（Ｃ_２Ｆ_５）ＣＦ_２）−および−（ＯＣＦ_２ＣＦ（Ｃ_２Ｆ_５））−のいずれであってもよく、好ましくは−（ＯＣＦ_２ＣＦ_２ＣＦ_２ＣＦ_２）−である。−（ＯＣ_３Ｆ_６）−は、−（ＯＣＦ_２ＣＦ_２ＣＦ_２）−、−（ＯＣＦ（ＣＦ_３）ＣＦ_２）−および−（ＯＣＦ_２ＣＦ（ＣＦ_３））−のいずれであってもよく、好ましくは−（ＯＣＦ_２ＣＦ_２ＣＦ_２）−である。−（ＯＣ_２Ｆ_４）−は、−（ＯＣＦ_２ＣＦ_２）−および−（ＯＣＦ（ＣＦ_３））−のいずれであってもよいが、好ましくは−（ＯＣＦ_２ＣＦ_２）−である。
ｋは０または１である。
ｆは１以上１０以下の整数である。
ｇは０以上２以下の整数である。
Ｘ’は水素原子またはハロゲン原子を表す。ハロゲン原子は、好ましくはヨウ素原子、塩素原子、フッ素原子である。
Ｙ’は水素原子または低級アルキル基を表す。低級アルキル基は、好ましくは炭素数１〜２０のアルキル基である。
Ｚ’はフッ素原子または低級フルオロアルキル基を表す。低級フルオロアルキル基は、例えば炭素数１〜３のフルオロアルキル基、好ましくは炭素数１〜３のパーフルオロアルキル基、より好ましくはトリフルオロメチル基、ペンタフルオロエチル基、更に好ましくはトリフルオロメチル基である。
ＴおよびＲ^３２はＳｉに結合した基である。
Ｔは水酸基または加水分解可能な基を表す。加水分解可能な基の例としては、−ＯＡ、−ＯＣＯＡ、−Ｏ−Ｎ＝Ｃ（Ａ）_２、−Ｎ（Ａ）_２、−ＮＨＡ、ハロゲン（これら式中、Ａは、置換または非置換の炭素数１〜３のアルキル基を示す）などが挙げられる。水酸基は、特に限定されないが、加水分解可能な基が加水分解して生じたものであってよい。
Ｒ^３２は水素原子または炭素数１〜２２のアルキル基を表し、好ましくは炭素数１〜２２のアルキル基、より好ましくは炭素数１〜３のアルキル基である。
ｘは１、２または３である。
なお、式中、Ｘ’、Ｙ’、Ｚ’、Ｔ、Ｒ^３２、ｋ、ｆ、ｇ、ｘは複数存在するが、互いに同じであっても、異なっていてもよい。 Examples of such a perfluoropolyether group-containing silane compound include compounds represented by any one of the following general formulas (Va) and (Vb) (may be one kind or a mixture of two or more kinds).

In these formulas, R ³¹ represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms, and preferably substituted with one or more fluorine atoms. Or an alkyl group having 1 to 3 carbon atoms. Preferably, the alkyl group optionally substituted by one or more fluorine atoms is a fluoroalkyl group in which the terminal carbon atom is CF ₂ H— and all other carbon atoms are fully substituted by fluorine. Or a perfluoroalkyl group, more preferably a perfluoroalkyl group.
a, b, c and v each represent the number of four types of repeating units of perfluoropolyether constituting the main skeleton of the polymer, each independently an integer of 0 to 200,
For example, it is an integer of 1 or more and 200 or less, and the sum of a, b, c and v is at least 1, preferably 1 to 100. The order of presence of each repeating unit with subscripts a, b, c or v and enclosed in parentheses is arbitrary in the formula. Among these repeating units, — (OC ₄ F ₈ ) — represents — (OCF ₂ CF ₂ CF ₂ CF ₂ ) —, — (OCF (CF ₃ ) CF ₂ CF ₂ ) —, — (OCF ₂ CF (CF _{3) CF 2) -, -} (OCF 2 CF 2 CF (CF 3)) -, - (OC (CF 3) 2 CF 2) -, - (OCF 2 C (CF 3) 2) -, - (OCF (CF ₃ ) CF (CF ₃ ))-,-(OCF (C ₂ F ₅ ) CF ₂ )-and-(OCF ₂ CF (C ₂ F ₅ ))-may be used, preferably- _{(OCF 2 CF 2 CF 2 CF} 2) - a. -(OC ₃ F ₆ )-may be any of-(OCF ₂ CF ₂ CF ₂ )-,-(OCF (CF ₃ ) CF ₂ )-and-(OCF ₂ CF (CF ₃ ))-. well, preferably _{- (OCF 2 CF 2 CF 2} ) - a. - _(OC 2 _{F 4)} - is, - _{(OCF 2} CF 2) - and _{- (OCF (CF 3))} - but may be any of, preferably - _{(OCF 2} CF 2) - a.
k is 0 or 1.
f is an integer of 1 or more and 10 or less.
g is an integer of 0 or more and 2 or less.
X ′ represents a hydrogen atom or a halogen atom. The halogen atom is preferably an iodine atom, a chlorine atom, or a fluorine atom.
Y ′ represents a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms.
Z ′ represents a fluorine atom or a lower fluoroalkyl group. The lower fluoroalkyl group is, for example, a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, a pentafluoroethyl group, still more preferably a trifluoromethyl group. It is.
T and R ³² are groups bonded to Si.
T represents a hydroxyl group or a hydrolyzable group. Examples of hydrolyzable groups include —OA, —OCOA, —O—N═C (A) ₂ , —N (A) ₂ , —NHA, halogen (in these formulas, A is substituted or unsubstituted) And an alkyl group having 1 to 3 carbon atoms). The hydroxyl group is not particularly limited, but may be a group produced by hydrolysis of a hydrolyzable group.
R ³² represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 22 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.
x is 1, 2 or 3.
In the formula, there are a plurality of X ′, Y ′, Z ′, T, R ³² , k, f, g, and x, but they may be the same or different.

これら式中、Ｒ^３１は、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１〜１６のアルキル基を表し、好ましくは、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１〜３のアルキル基である。好ましくは、上記１個またはそれ以上のフッ素原子により置換されていてもよいアルキル基は、末端炭素原子がＣＦ_２Ｈ−であり他のすべての炭素原子がフッ素により全置換されているフルオロアルキル基、またはパーフルオロアルキル基であり、より好ましくはパーフルオロアルキル基である。
ａ、ｂ、ｃおよびｖは、ポリマーの主骨格を構成するパーフルオロポリエーテルの４種の繰り返し単位数をそれぞれ表し、互いに独立して０以上２００以下の整数、例えば１以上２００以下の整数であって、ａ、ｂ、ｃおよびｖの和は少なくとも１、好ましくは１〜１００である。添字ａ、ｂ、ｃまたはｖを付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。これら繰り返し単位のうち、−（ＯＣ_４Ｆ_８）−は、−（ＯＣＦ_２ＣＦ_２ＣＦ_２ＣＦ_２）−、−（ＯＣＦ（ＣＦ_３）ＣＦ_２ＣＦ_２）−、−（ＯＣＦ_２ＣＦ（ＣＦ_３）ＣＦ_２）−、−（ＯＣＦ_２ＣＦ_２ＣＦ（ＣＦ_３））−、−（ＯＣ（ＣＦ_３）_２ＣＦ_２）−、−（ＯＣＦ_２Ｃ（ＣＦ_３）_２）−、−（ＯＣＦ（ＣＦ_３）ＣＦ（ＣＦ_３））−、−（ＯＣＦ（Ｃ_２Ｆ_５）ＣＦ_２）−および−（ＯＣＦ_２ＣＦ（Ｃ_２Ｆ_５））−のいずれであってもよいが、好ましくは−（ＯＣＦ_２ＣＦ_２ＣＦ_２ＣＦ_２）−である。−（ＯＣ_３Ｆ_６）−は、−（ＯＣＦ_２ＣＦ_２ＣＦ_２）−、−（ＯＣＦ（ＣＦ_３）ＣＦ_２）−および−（ＯＣＦ_２ＣＦ（ＣＦ_３））−のいずれであってもよく、好ましくは−（ＯＣＦ_２ＣＦ_２ＣＦ_２）−である。−（ＯＣ_２Ｆ_４）−は、−（ＯＣＦ_２ＣＦ_２）−および−（ＯＣＦ（ＣＦ_３））−のいずれであってもよいが、好ましくは−（ＯＣＦ_２ＣＦ_２）−である。
ｋは０または１である。
ｈは１または２である。
ｉは２以上２０以下の整数である。
Ｚ’はフッ素原子または低級フルオロアルキル基を表す。低級フルオロアルキル基は、例えば炭素数１〜３のフルオロアルキル基、好ましくは炭素数１〜３のパーフルオロアルキル基、より好ましくはトリフルオロメチル基、ペンタフルオロエチル基、更に好ましくはトリフルオロメチル基である。
ＴおよびＲ^３２はＳｉに結合した基である。
Ｔは水酸基または加水分解可能な基を表す。加水分解可能な基の例としては、−ＯＡ、−ＯＣＯＡ、−Ｏ−Ｎ＝Ｃ（Ａ）_２、−Ｎ（Ａ）_２、−ＮＨＡ、ハロゲン（これら式中、Ａは、置換または非置換の炭素数１〜３のアルキル基を示す）などが挙げられる。水酸基は、特に限定されないが、加水分解可能な基が加水分解して生じたものであってよい。
Ｒ^３２は水素原子または炭素数１〜２２のアルキル基を表し、好ましくは炭素数１〜２２のアルキル基、より好ましくは炭素数１〜３の直鎖状または分枝状のアルキル基である。
ｘは１、０または３である。
なお、式中、Ｚ’、Ｔ、Ｒ^３２、ｋ、ｈ、ｉ、ｘは複数存在するが、互いに同じであっても、異なっていてもよい。 Another example of the perfluoropolyether group-containing silane compound is a compound represented by any one of the following general formulas (VIa) and (VIb) (which may be one or a mixture of two or more). It is done.

In these formulas, R ³¹ represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms, and preferably substituted with one or more fluorine atoms. Or an alkyl group having 1 to 3 carbon atoms. Preferably, the alkyl group optionally substituted by one or more fluorine atoms is a fluoroalkyl group in which the terminal carbon atom is CF ₂ H— and all other carbon atoms are fully substituted by fluorine. Or a perfluoroalkyl group, more preferably a perfluoroalkyl group.
a, b, c and v each represent the number of four types of repeating units of perfluoropolyether constituting the main skeleton of the polymer, and are each independently an integer of 0 to 200, for example, an integer of 1 to 200 And the sum of a, b, c and v is at least 1, preferably 1-100. The order of presence of each repeating unit with subscripts a, b, c or v and enclosed in parentheses is arbitrary in the formula. Among these repeating units, — (OC ₄ F ₈ ) — represents — (OCF ₂ CF ₂ CF ₂ CF ₂ ) —, — (OCF (CF ₃ ) CF ₂ CF ₂ ) —, — (OCF ₂ CF (CF _{3) CF 2) -, -} (OCF 2 CF 2 CF (CF 3)) -, - (OC (CF 3) 2 CF 2) -, - (OCF 2 C (CF 3) 2) -, - (OCF (CF ₃ ) CF (CF ₃ ))-,-(OCF (C ₂ F ₅ ) CF ₂ )-and-(OCF ₂ CF (C ₂ F ₅ ))-may be used, but preferably _{- (OCF 2 CF 2 CF 2} CF 2) - a. -(OC ₃ F ₆ )-may be any of-(OCF ₂ CF ₂ CF ₂ )-,-(OCF (CF ₃ ) CF ₂ )-and-(OCF ₂ CF (CF ₃ ))-. well, preferably _{- (OCF 2 CF 2 CF 2} ) - a. - _(OC 2 _{F 4)} - is, - _{(OCF 2} CF 2) - and _{- (OCF (CF 3))} - but may be any of, preferably - _{(OCF 2} CF 2) - a.
k is 0 or 1.
h is 1 or 2.
i is an integer of 2 or more and 20 or less.
Z ′ represents a fluorine atom or a lower fluoroalkyl group. The lower fluoroalkyl group is, for example, a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, a pentafluoroethyl group, still more preferably a trifluoromethyl group. It is.
T and R ³² are groups bonded to Si.
T represents a hydroxyl group or a hydrolyzable group. Examples of hydrolyzable groups include —OA, —OCOA, —O—N═C (A) ₂ , —N (A) ₂ , —NHA, halogen (in these formulas, A is substituted or unsubstituted) And an alkyl group having 1 to 3 carbon atoms). The hydroxyl group is not particularly limited, but may be a group produced by hydrolysis of a hydrolyzable group.
R ³² represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 22 carbon atoms, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms.
x is 1, 0 or 3.
In the formula, there are a plurality of Z ′, T, R ³² , k, h, i, and x, but they may be the same or different.

In the general formula (Va), (Vb), (VIa), (VIb), - (OC 4 F 8) v - (OC 3 F 6) a - (OC 2 F 4) b - (OCF 2) c -Is:
− (OCF ₂ CF ₂ CF ₂ ) _{a ′} −
(Wherein, a ′ is an integer of 1 to 200, preferably an integer of 1 to 100)
Or _{- (OCF 2 CF 2 CF 2} CF 2) v '- (OCF 2 CF 2 CF 2) a' - (OCF 2 CF 2) b '- (OCF 2) c' -
(Wherein v ′ and a ′ are integers of 1 or more and 30 or less, b ′ and c ′ are integers of 1 or more and 300 or less, and suffixes a ′, b ′, c ′ or v ′ are attached. The order of presence of each repeating unit in parentheses is arbitrary in the formula.)
It may be. Further, typically, Z ′ is a fluorine atom and k is 1.

  Although the molecular weight of a perfluoro polyether group containing silane compound is not specifically limited, For example, you may have an average molecular weight of 1000-12000. Among these ranges, an average molecular weight of 2,000 to 10,000 is preferable from the viewpoint of water repellency, oil repellency, surface slipperiness (for example, fingerprint wiping property) and friction durability.

  The surface treating agent of the present invention may contain both a non-reactive compound (for example, silicone oil and / or fluorine-containing oil) and a perfluoropolyether group-containing silane compound. In this case, in the surface treatment agent of the present invention, the substrate is based on 100 parts by mass of the fluoropolyether group-containing silicone compounds represented by the general formulas (Ia), (Ib), (IIa) and (IIb). The non-reactive compound can be included, for example, in an amount of 0 to 80 parts by mass, preferably 0 to 40 parts by mass, and the perfluoropolyether group-containing silane compound is, for example, 0 to 80 parts by mass, preferably 0. It can be included at ~ 40 parts by weight.

-Article Next, an article obtained using such a surface treating agent will be described. The article of the present invention comprises a substrate and a fluoropolyether group-containing silicone compound or surface represented by the above-mentioned general formula (Ia), (Ib), (IIa) and / or (IIb) on the surface of the substrate And a layer (surface treatment layer) formed from a treatment agent (hereinafter simply referred to as a surface treatment composition). This article can be manufactured, for example, as follows.

  First, a base material is prepared. The substrate that can be used in the present invention is, for example, glass, resin (natural or synthetic resin, for example, a general plastic material, plate, film, or other forms), metal (aluminum, copper May be a single metal such as iron or a composite of an alloy), ceramics, semiconductor (silicon, germanium, etc.), fiber (woven fabric, non-woven fabric, etc.), fur, leather, wood, ceramics, stone, etc. It can be made of any material.

For example, when the article to be manufactured is an optical member, the material constituting the surface of the substrate may be an optical member material such as glass or transparent plastic. Moreover, when the article to be manufactured is an optical member, some layer (or film) such as a hard coat layer or an antireflection layer may be formed on the surface (outermost layer) of the substrate. As the antireflection layer, either a single-layer antireflection layer or a multilayer antireflection layer may be used. Examples of inorganic materials that can be used for the antireflection layer include SiO ₂ , SiO, ZrO ₂ , TiO ₂ , TiO, Ti ₂ O ₃ , Ti ₂ O ₅ , Al ₂ O ₃ , Ta ₂ O ₅ , CeO ₂ , MgO. , Y ₂ O ₃ , SnO ₂ , MgF ₂ , WO _{3 and the} like. These inorganic substances may be used alone or in combination of two or more thereof (for example, as a mixture). When a multilayer antireflection layer is used, it is preferable to use SiO ₂ and / or SiO for the outermost layer. When the article to be manufactured is an optical glass component for a touch panel, a thin film using a transparent electrode such as indium tin oxide (ITO) or indium zinc oxide is provided on a part of the surface of the substrate (glass). It may be. In addition, the base material is an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating film layer, a polarizing film, a phase difference film, according to the specific specifications and the like. And a liquid crystal display module or the like.

  The shape of the substrate is not particularly limited. In addition, the surface region of the base material on which the surface treatment layer is to be formed may be at least part of the surface of the base material, and can be appropriately determined according to the use and specific specifications of the article to be manufactured.

  As such a base material, at least a surface portion thereof may be made of a material originally having a hydroxyl group. Examples of such materials include glass, and metals (particularly base metals) on which a natural oxide film or a thermal oxide film is formed on the surface, ceramics, and semiconductors. Alternatively, if it does not suffice if it has hydroxyl groups, such as resin, or if it does not have hydroxyl groups originally, it can be introduced to the surface of the substrate by applying some pretreatment to the substrate. Or increase it. Examples of such pretreatment include plasma treatment (for example, corona discharge) and ion beam irradiation. The plasma treatment can be preferably used for introducing or increasing hydroxyl groups on the surface of the base material and for cleaning the base material surface (removing foreign matter or the like). As another example of such pretreatment, an interfacial adsorbent having a carbon-carbon unsaturated bond group is previously formed on the surface of the substrate by the LB method (Langmuir-Blodgett method) or the chemical adsorption method. And then cleaving the unsaturated bond in an atmosphere containing oxygen, nitrogen or the like.

  Alternatively, as such a base material, at least a surface portion thereof may be made of a material containing a silicone compound having one or more other reactive groups, for example, Si-H groups, or an alkoxysilane.

  Next, a film of the surface treatment agent is formed on the surface of the base material, and the film is post-treated as necessary, thereby forming a surface treatment layer from the surface treatment agent.

  The film formation of the surface treatment agent can be performed by applying the surface treatment agent to the surface of the substrate so as to cover the surface. The coating method is not particularly limited. For example, wet coating methods and dry coating methods can be used.

  Examples of wet coating methods include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating and similar methods.

  Examples of dry coating methods include vacuum deposition, sputtering, CVD and similar methods. Specific examples of the vacuum deposition method include resistance heating, electron beam, high frequency heating, ion beam, and similar methods. Specific examples of the CVD method include plasma-CVD, optical CVD, thermal CVD, and similar methods.

  Furthermore, coating by the atmospheric pressure plasma method is also possible.

When using the wet coating method, the surface treatment agent can be diluted with a solvent and then applied to the substrate surface. From the viewpoint of the stability of the surface treating agent and the volatility of the solvent, the following solvents are preferably used: perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (for example, perfluorohexane, perfluoromethylcyclohexane and perfluoro). -1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (eg bis (trifluoromethyl) benzene); polyfluoroaliphatic hydrocarbons; hydrofluoroethers (HFE) (eg perfluoropropylmethyl ether (C ₃ F ₇ OCH ₃ ), perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ), perfluorobutyl ethyl ether (C ₄ F ₉ OC ₂ H ₅ ), perfluorohexyl methyl ether (C ₂ F ₅ CF (OCH) _{3) C 3 F 7)} alkyl perfluoro a such Etc. Kill ether (perfluoroalkyl group and the alkyl group may be linear or branched)). These solvents can be used alone or as a mixture of two or more. Among these, hydrofluoroether is preferable, and perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) and / or perfluorobutyl ethyl ether (C ₄ F ₉ OC ₂ H ₅ ) is particularly preferable.

  The film formation is preferably carried out so that the surface treatment agent is present in the film together with a catalyst for hydrolysis and dehydration condensation. For simplicity, in the case of the wet coating method, after diluting the surface treatment agent with a solvent, the catalyst may be added to the diluted solution of the surface treatment agent immediately before application to the substrate surface. In the case of the dry coating method, the surface treatment agent added with a catalyst is vacuum-deposited as it is, or a vacuum is formed using a pellet-like material obtained by impregnating a surface treatment agent added with a catalyst into a porous metal such as iron or copper. A vapor deposition process may be performed.

  Any suitable acid or base can be used for the catalyst. As the acid catalyst, for example, acetic acid, formic acid, trifluoroacetic acid and the like can be used. Moreover, as a base catalyst, ammonia, organic amines, etc. can be used, for example.

  Next, the film is post-treated as necessary. Although this post-processing is not specifically limited, For example, a water supply and drying heating may be implemented sequentially, and it may be implemented as follows in detail. In the compounds represented by any one of the general formulas (Ia), (Ib), (IIa) and (IIb), when all T contained in Z is a hydroxyl group, moisture supply is not necessarily required. .

  After the surface treatment agent is formed on the substrate surface as described above, moisture is supplied to this film (hereinafter also referred to as a precursor film). The method for supplying moisture is not particularly limited, and for example, methods such as dew condensation due to a temperature difference between the precursor film (and the substrate) and the surrounding atmosphere, or spraying of steam (steam) may be used.

  When moisture is supplied to the precursor film, a fluoropolyether group-containing silicone compound represented by the general formula (Ia), (Ib), (IIa) and / or (IIb) in the surface treatment agent (and present) In this case, it is considered that water acts on the hydrolyzable group bonded to Si of the perfluoropolyether group-containing silane compound), and the compound can be hydrolyzed quickly.

  The water supply can be performed, for example, in an atmosphere of 0 to 500 ° C., preferably 100 ° C. or higher and 300 ° C. or lower. By supplying moisture in such a temperature range, hydrolysis can be advanced. Although the pressure at this time is not specifically limited, it can be simply a normal pressure.

  Next, the precursor film is heated on the surface of the base material in a dry atmosphere exceeding 60 ° C. The drying heating method is not particularly limited, and the temperature of the precursor film together with the base material is over 60 ° C., preferably over 100 ° C., for example, 500 ° C. or less, preferably 300 ° C. or less, and What is necessary is just to arrange | position in the atmosphere of saturated water vapor pressure. Although the pressure at this time is not specifically limited, it can be simply a normal pressure.

  Under such an atmosphere, a fluoropolyether group-containing silicone compound represented by any one of the general formulas (Ia), (Ib), (IIa) and / or (IIb) (and perfluoro if present) Among the polyether group-containing silane compounds), a group bonded to Si after hydrolysis (in the compounds represented by any one of the above general formulas (Ia), (Ib), (IIa) and (IIb)), When all of the contained T is a hydroxyl group, it is the hydroxyl group (the same applies to the following), and they are rapidly dehydrated and condensed. Moreover, between such a compound and a base material, it reacts rapidly between the group couple | bonded with Si after the hydrolysis of the said compound, and the reactive group which exists in the base-material surface, and it exists in the base-material surface. When the reactive group is a hydroxyl group, dehydration condensation is performed. (Note that silicone oil and / or fluorine-containing oil is mixed between the compounds bonded in this way.) As a result, the general formulas (Ia), (Ib), (IIa) And / or a bond between the fluoropolyether group-containing silicone compound represented by (IIb) (and the perfluoropolyether group-containing silane compound, if present), and the compound and the substrate (And, if present, the silicone oil and / or fluorine-containing oil is represented by any of the general formulas (Ia), (Ib), (IIa) and / or (IIb)) Retained or captured by affinity for fluoropolyether group-containing silicone compounds (and perfluoropolyether group-containing silane compounds) That).

  The above water supply and drying heating may be carried out continuously by using superheated steam.

  Superheated steam is a gas obtained by heating saturated steam to a temperature higher than the boiling point, and exceeds 100 ° C. under normal pressure, generally 500 ° C. or lower, for example, 300 ° C. or lower, and has a boiling point. It is a gas that has become an unsaturated water vapor pressure by heating to a temperature exceeding. When the substrate on which the precursor film is formed is exposed to superheated water vapor, first, dew condensation occurs on the surface of the precursor film due to the temperature difference between the superheated water vapor and the relatively low temperature precursor film. Moisture is supplied to the membrane. Eventually, as the temperature difference between the superheated steam and the precursor film becomes smaller, the moisture on the surface of the precursor film is vaporized in a dry atmosphere by the superheated steam, and the moisture content on the surface of the precursor film gradually decreases. While the amount of moisture on the surface of the precursor film is reduced, that is, while the precursor film is in a dry atmosphere, the precursor film on the surface of the substrate comes into contact with the superheated steam, thereby the temperature of the superheated steam ( It will be heated to a temperature exceeding 100 ° C. under normal pressure. Therefore, if superheated steam is used, moisture supply and drying heating can be carried out continuously only by exposing the substrate on which the precursor film is formed to superheated steam.

  Post-processing can be performed as described above. It should be noted that such post-treatment can be performed to further improve friction durability, but is not essential for producing the articles of the present invention. For example, after applying the surface treatment agent to the substrate surface, it may be left still.

  As described above, the surface treatment layer derived from the film of the surface treatment agent is formed on the surface of the base material, and the article of the present invention is manufactured. The surface treatment layer thus obtained has water repellency, oil repellency, antifouling properties (for example, preventing adhesion of dirt such as fingerprints), surface slipperiness (or lubricity, for example, wiping of dirt such as fingerprints, finger Excellent tactile sensation), friction durability, and the like, and can be suitably used as a functional thin film.

  The article having the surface treatment layer obtained thereby is not particularly limited, but may be an optical member. Examples of optical members include: lenses such as eyeglasses; front protective plates, antireflection plates, polarizing plates, and antiglare plates for displays such as PDP and LCD; for devices such as mobile phones and portable information terminals. Touch panel sheet; Disc surface of an optical disc such as a Blu-ray (registered trademark) disc, DVD disc, CD-R, MO;

  The thickness of the surface treatment layer is not particularly limited. In the case of an optical member, the thickness of the surface treatment layer is preferably in the range of 1 to 30 nm, preferably 1 to 15 nm, from the viewpoint of optical performance, surface slipperiness, friction durability, and antifouling properties.

  Hereinabove, the articles obtained using the surface treatment agent of the present invention have been described in detail. In addition, the use of the surface treating agent of the present invention, the usage method, the manufacturing method of the article, and the like are not limited to those exemplified above.

  The surface treatment agent of the present invention and articles obtained using the same will be described more specifically through the following examples, but the present invention is not limited to these examples.

(Example)
As Examples 1 to 3, a mixture of fluoropolyether group-containing silicone compounds was synthesized in the following Synthesis Examples 1 to 3, and a surface treatment agent was prepared using each mixture obtained from these, A treatment layer was formed.

Synthesis example 1
In a 50 mL four-necked flask equipped with a reflux condenser, a thermometer, a stirrer, a dropping funnel, and a nitrogen gas inlet tube, the following compound (A) (average composition n = 56) as a silicone-based raw material under a nitrogen stream 3 g and a mixture of the following compounds (B) and (C) as fluoropolyether-based raw materials (average composition n ′ = 22, mass ratio 6: 1) to 2.5 g, 1,3-bis (trifluoromethyl) 6 g of benzene was added and dissolved.
After cooling the flask with an ice-water bath, 0.02 g of boron trifluoride-ethyl ether complex was added dropwise and stirred for 15 minutes. Then, it heated up to 70 degreeC and stirred for 10 hours. After cooling to room temperature, 10 g of methanol was added to separate the lower phase (fluorus phase). The solvent was distilled off from the fractionated lower phase to obtain a reaction mixture.
Thereafter, 0.5 g of a 1,3-bis (trifluoromethyl) benzene solution of dibutyltin dilaurate (dibutyltin dilaurate concentration 1 mass%) and 6 g of 1,3-bis (trifluoromethyl) benzene were added to 5 g of the obtained reaction mixture. Then, 0.13 g of the following compound (D) was added as a silyl group-containing raw material, and then heated to 80 ° C. and stirred for 10 hours.

As a result, a mixture of the following compounds (X) and (Y) (average composition n ′ = 22) was obtained. In the mixture, compounds (X) and (Y) were present in a mass ratio of 6: 1.

Synthesis example 2
The compound (B) was synthesized by the same procedure as in Synthesis Example 1 except that 1.4 g of a mixture of compounds (B) and (C) (average composition n ′ = 11, mass ratio 6: 1) was used as the fluoropolyether raw material. A mixture of X) and (Y) (average composition n ′ = 11) was obtained. In the mixture, compounds (X) and (Y) were present in a mass ratio of 6: 1.

Synthesis example 3
The compound (B) was synthesized by the same procedure as in Synthesis Example 1 except that 3.6 g of a mixture of compounds (B) and (C) (average composition n ′ = 31, mass ratio 6: 1) was used as the fluoropolyether-based raw material. A mixture of X) and (Y) (average composition n ′ = 31) was obtained. In the mixture, compounds (X) and (Y) were present in a mass ratio of 6: 1.

-Preparation of surface treatment agent 1,3-bis (trifluoromethyl) was prepared so that the mixture 1 to 3 (mixture of perfluoropolyether group-containing silicone compound) obtained in Synthesis Examples 1 to 3 had a concentration of 20 wt%. ) Surface treatment agents 1 to 3 were prepared by dissolving in benzene.

-Formation of surface treatment layer Each surface treatment agent prepared above was vacuum-deposited on "gorilla" glass (Corning). The processing conditions for the vacuum deposition were set to a pressure of 3.0 × 10 ⁻³ Pa, and 1 mg of each surface treatment agent was deposited per one “gorilla” glass (manufactured by Corning). Thereafter, “Gorilla” glass with a deposited film (manufactured by Corning) was allowed to stand for 24 hours in an atmosphere at a temperature of 20 ° C. and a humidity of 65%. Thereby, a vapor deposition film hardened and a surface treatment layer was formed.

(Comparative example)
In place of the mixtures 1 to 3, the following reference compounds 1 to 2 were used in Comparative Examples 1 to 2, and the following composition 1 was used in Comparative Example 3 in the same manner as in the above Example. A treatment agent was prepared and a surface treatment layer was formed.
Control compound 1
_{Me 3 SiO- (Me 2 SiO)} 13 - (MeHSiO) 13 -SiMe 3
(The symbol Me represents a methyl group.)
Control compound 2
CF ₃ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₂₀ CF ₂ CF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
・ Composition 1
A composition comprising Control Compound 1 and Control Compound 2 mixed at a mass ratio of 1: 1.

(Evaluation)
The surface of the surface treatment layer on the “gorilla” glass (manufactured by Corning) obtained in the above examples and comparative examples was wiped with a waste impregnated with ethanol, and the surface treatment layer was subjected to water / oil repellency and dynamic friction coefficient. (Surface slipperiness), oil-based ink wiping property, and feeling with a finger were evaluated / measured as follows. These results are shown in Table 1.

[Water and oil repellency]
Using a contact angle meter (“DropMaster” manufactured by Kyowa Interface Science Co., Ltd.), the contact angle with respect to water (1 μL) of the surface treatment layer on the “gorilla” glass (manufactured by Corning) and normal hexadecane ( 1 μL) was measured.

[Dynamic friction coefficient (surface slipperiness)]
A dynamic friction coefficient (-) was measured in accordance with ASTM D1894 using a steel ball as a friction element using a surface property measuring machine ("Tribogear TYPE: 14FW", manufactured by Shinto Kagaku Co., Ltd.).

[Oil-based ink wiping off]
Oil-based ink is applied to the surface of the surface treatment layer using an oil-based marking pen (Zebra Co., Ltd., “Hi-Mackey” (registered trademark)), and this is made of pulp waste (Nippon Paper Crecia Co., Ltd., “Kimwipe” (registered) Trademark)) was performed (the operation of pressing the waste cloth against the treated surface by hand and sliding it in one direction), and the wipeability (easiness of wiping) of the oil-based ink was visually evaluated according to the following index.
A: The ink can be completely wiped off easily by one wiping operation. B: A little ink remains in one wiping operation. C: About half of the ink remains in one wiping operation. D: Ink in one wiping operation. Can not wipe off at all

[Finger feeling]
Twenty expert panelists for sensory evaluation touched the treated surface with their fingers, evaluated the feeling of use according to the following criteria, and determined the average.
4: Very good 3: Good 2: Normal 1: Bad

  As can be seen from Table 1, in Examples 1 to 3 using the fluoropolyether group-containing silicone compound of the present invention, the kinetic friction is as small as in Comparative Example 1 using the control compound 1 (polyorganosilicone compound). A coefficient (high surface slipperiness) and excellent use feeling with a finger are obtained, and water and oil repellency (high) is high enough to be comparable to Comparative Example 2 using Control Compound 2 (perfluoropolyether group-containing silane compound). Contact angle) and excellent oil-based ink wiping properties were obtained. In Examples 1 and 2 using the fluoropolyether group-containing silicone compound of the present invention, the water and oil repellency was higher than that in Comparative Example 3 using the composition 1 in which the control compounds 1 and 2 were simply mixed (contact angle). Was large), the coefficient of dynamic friction was small (high surface slipperiness), and the oil-based ink wiping property and the feeling of use with a finger were excellent.

  INDUSTRIAL APPLICABILITY The present invention can be suitably used for forming a surface treatment layer on a variety of substrates, particularly on the surface of optical members that require transparency.

Claims (13)

Any of the following general formulas (Ia), (Ib), (IIa) and (IIb):

[In these formulas, R ¹ represents a substituted or unsubstituted methyl group, Rf represents a group containing a fluoropolyether group, and X represents the following formula:

(In the formula, p is an integer of 1 to 10, R ¹³ is — (CH ₂ ) _{q ′} —O— (CH ₂ ) _q — (wherein q is an integer of 1 to 20; 'is 1 to 10 which is an integer), the left end of the formula is bonded to Rf, the right end of the formula is bound to S ¹ or S ^2, the lower end of the formula is bound to Y.)
Y is a group represented by the following formula:
-OCONH- _{(CH 2) r} -
(In the formula, r is an integer of 1 to 10, and the left end of the formula is bonded to X, and the right end of the formula is bonded to Z.)
In a group represented by, Z is a silyl group containing a hydrolyzable site, S ¹ is the organopolysiloxane group monovalent, S ² is a divalent organopolysiloxane group, m 1 or more and 5 or less. ]
A fluoropolyether group-containing silicone compound having a structure represented by: In the general formulas (Ia) and (Ib), S ¹ represents the following formula:

(In the formula, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently an alkyl group or an aryl group, and n is 1 or more and 200 or less.)
The fluoropolyether group-containing silicone compound according to claim 1, which is an organopolysiloxane group represented by the formula: In the general formulas (IIa) and (IIb), S ² represents the following formula:

(In the formula, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently an alkyl group or an aryl group, and n is 1 or more and 200 or less.)
The fluoropolyether group-containing silicone compound according to claim 1, which is an organopolysiloxane group represented by the formula: In the general formulas (Ia), (Ib), (IIa) and (IIb), Rf represents the following formula:
_{^{- (R 9) j -R 10}} -R 11 -
[Wherein R ⁹ is a C 1-15 perfluoroalkylene group,
j is 0 or 1,
R ¹⁰ has the following formula:
_{- (OC 4 F 8) v} - (OC 3 F 6) a - (OC 2 F 4) b - (OCF 2) c -
Wherein a, b, c and v are each independently an integer of 0 or more and 200 or less, the sum of a, b, c and v is at least 1, and each repeating unit enclosed in parentheses The order of presence of is arbitrary in the formula.)
A perfluoropolyether group represented by
R ¹¹ has the following formula:
− (Q) _d − (CFZ ′) _e −
(In the formula, Q represents an oxygen atom or a divalent polar group, Z ′ represents a fluorine atom or a lower fluoroalkyl group, and d and e are each independently an integer of 0 to 50, (The sum of e is at least 1, and the order in which each repeating unit in parentheses is present is arbitrary in the formula.)
It is group represented by these. ]
The fluoropolyether group containing silicone compound in any one of Claims 1-3 which is group represented by these. In the general formulas (Ia), (Ib), (IIa) and (IIb), Rf represents the following formula:
_{-CF 2 CF 2 - (OCF 2} CF 2 CF 2) a '-OCF 2 CF 2 -
(Wherein, a ′ is an integer of 1 to 200)
The fluoropolyether group-containing silicone compound according to claim 4, wherein the perfluoropolyether group is represented by the formula: In the general formulas (Ia), (Ib), (IIa) and (IIb), Z represents the following formula:
-SiT _x R ¹² _3-x
(In the formula, T is a hydroxyl group or a hydrolyzable group, R ¹² is a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, and x is 1, 2 or 3.)
The fluoropolyether group-containing silicone compound according to any one of claims 1 to 5, which is a silyl group represented by: Fluoropolyether group containing containing a silicone compound, a surface treatment agent according to any one of claims 1-6. The surface treating agent according to claim 7 , comprising a fluoropolyether group-containing silicone compound represented by the general formula (Ia) and a fluoropolyether group-containing silicone compound represented by the general formula (Ib). The surface treating agent according to claim 7 , comprising a fluoropolyether group-containing silicone compound represented by the general formula (IIa) and a fluoropolyether group-containing silicone compound represented by the general formula (IIb). The surface treating agent according to any one of claims 7 to 9 , which is used as an antifouling coating agent. A substrate and a layer formed on the surface of the substrate from the fluoropolyether group-containing silicone compound according to any one of claims 1 to 6 or the surface treatment agent according to any one of claims 7 to 10. Articles containing. The article of claim 11 , wherein the article is an optical member. The article according to claim 11 or 12 , wherein the substrate is glass or transparent plastic.