JP5472503B2 - 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.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１およびＲ^１２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、Ｒｆはフルオロポリエーテル基であり、ＸおよびＹは、互いに同一または異なる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、ａは１以上１００以下、ｂは０以上１００以下、ｃは０以上２００以下、ｄは０以上２００以下であり、ｂおよびｃの和は少なくとも１であり、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。） According to one aspect of the present invention, there is provided a fluoropolyether group-containing silicone compound represented by the following general formula (I).

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are each independently an alkyl group or an aryl group Rf is a fluoropolyether group, X and Y are the same or different divalent organic groups, Z is a silyl group containing a hydrolyzable moiety, a is 1 or more and 100 or less, b is 0 or more and 100 or less, c is 0 or more and 200 or less, d is 0 or more and 200 or less, the sum of b and c is at least 1, and the order of presence of each repeating unit in parentheses is arbitrary in the formula .)

The fluoropolyether group-containing silicone compound of the present invention comprises a siloxane skeleton, a fluoropolyether group (Rf-) bonded to Si atoms constituting the siloxane skeleton (via a divalent organic group X), and a siloxane skeleton. It has at least one of a silyl group (-Z) including a hydrolyzable site bonded to a Si atom (via a divalent organic group Y) and an alkoxy group directly bonded to a Si atom forming a siloxane skeleton. The fluoropolyether group (Rf-) contributes to water repellency and oil repellency, and thus antifouling properties. Further, the siloxane skeleton contributes to the surface slipperiness. Furthermore, the silyl group (-Z) containing a hydrolyzable site and the alkoxy group (-OR ⁷ ) directly bonded to the Si atom contribute 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.

In the general formula (I), Rf is preferably a perfluoropolyether group, but part of the fluorine atom may be substituted with a hydrogen atom or another halogen atom. Perfluoropolyether groups can further enhance water and oil repellency and thus antifouling properties.
For example, Rf is the following formula:
^{_{R 13 - (OC 4 F 8}} ) k - (OC 3 F 6) l - (OC 2 F 4) m - (OCF 2) n -
Wherein R ¹³ is an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms, preferably a perfluoroalkyl group having 1 to 16 carbon atoms, and k , L, m and n are each independently an integer of 0 or more and 200 or less, the sum of k, l, m and n is at least 1, and the order of presence of each repeating unit in parentheses is represented by the formula It may be a fluoropolyether group represented by:
More specifically, Rf is represented by the following formula:
_{CF 3 CF 2 CF 2 - (} OCF 2 CF 2 CF 2) l '-OCF 2 CF 2 -
(Wherein, l ′ is an integer of 1 or more and 200 or less).

In the above general formula (I), Z represents the following formula:
-SiT _x R ¹⁴ _3-x
(Wherein T is a hydroxyl group or a hydrolyzable group, R ¹⁴ is a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, and x is 1, 2 or 3). It may be.

In the above general formula (I), R ⁷ may be an alkyl group having 1 to 4 carbon atoms.

In the above general formula (I), X represents the following formula:
_{- (CH 2) p -O- (} CH 2) q -
(Wherein p is an integer of 1 to 20 and q is an integer of 2 to 20). In the general formula (I), X represents the following formula:
_{- (CH 2) s -CONH- (} CH 2) t -
(Wherein s is an integer of 0 or more and 10 or less, and t is an integer of 2 or more and 10 or less).

In the above general formula (I), Y represents the following formula:
- _{(CH 2) r} -
(Wherein, r is an integer of 2 or more and 20 or less).

  According to another aspect of the present invention, a surface treatment agent comprising the above-mentioned fluoropolyether group-containing silicone compound is also provided. Such a surface treatment agent can impart water repellency, oil repellency, antifouling property, and surface slipperiness to a substrate, and is not particularly limited, but is suitably used as an antifouling coating agent. obtain.

  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, the term “transparent” may be anything that can be generally recognized as transparent. For example, it means that having a haze value of 5% or less.

  According to the present invention, a novel fluoropolyether group-containing silicone compound is provided, which comprises a siloxane skeleton, a fluoropolyether group bonded (indirectly) to Si atoms forming the siloxane skeleton, and a siloxane skeleton. And having at least one of a silyl group containing a hydrolyzable site bonded (directly) to the Si atom formed and an alkoxy group bonded directly to the Si atom forming the siloxane skeleton, thereby providing water repellency, oil repellency, A layer having antifouling property, 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 this invention is represented by the following general formula (I).

In the general formula (I), R ^{1 to} R ¹² 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 ^{1 to} R ¹² include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, hexyl group and dodecyl group; substituted alkyl groups such as chloromethyl group; unsubstituted aryl groups such as phenyl group and naphthyl group Groups; substituted aryl groups such as 4-chlorophenyl and 2-methylphenyl groups are included. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group is more preferable.

However, R ⁷ is preferably a substituted or unsubstituted, linear or branched alkyl group having 1 to 4 carbon atoms. Examples of R ⁷ include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, n-butyl group and isobutyl group; substituted alkyl groups such as chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group is more preferable.
In the compound of the present invention, the alkoxy group (—OR ⁷ ) bonded to Si forming the siloxane skeleton can be bonded by reacting with the base material and between the compounds. Excellent friction durability) (compared to silicone oil and fluorine-containing oil).

  In the general formula (I), Rf is a fluoropolyether group. Rf can have a linear, branched or cyclic structure with respect to the ether bond chain, but is preferably linear. Rf is preferably a perfluoropolyether group, but a part of the fluorine atom may be substituted with a hydrogen atom or another halogen atom.

More specifically, Rf is represented by the following formula:
^{_{R 13 - (OC 4 F 8}} ) k - (OC 3 F 6) l - (OC 2 F 4) m - (OCF 2) n -
It is preferable that it is the perfluoro polyether group represented by these.
In this formula, R ¹³ is an alkyl group having 1 to 16 carbon atoms (for example, linear or branched) which may be substituted with one or more fluorine atoms, preferably one Or it is a C1-C3 linear or branched alkyl group which may be substituted by more fluorine 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, specifically —CF ₃ , —CF ₂ CF ₃ , or —CF ₂ CF ₂ CF ₃ .
k, l, m and n each represent the number of three types of repeating units of perfluoropolyether constituting the main skeleton of the polymer, and are each independently an integer of 0 to 200, preferably 1 to 100. The sum of k, l, m and n is at least 1, preferably 1 or more and 100 or less. In addition, for convenience, the order of existence of each repeating unit with parentheses k, l, m, and n 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) - and - (OCF Any one of (CF ₃ ) CF (CF ₃ )) — may be used, but — (OCF ₂ CF ₂ CF ₂ CF ₂ ) — is preferred. -(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.
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 3 CF 2 CF 2 - (} OCF 2 CF 2 CF 2) l '-OCF 2 CF 2 -
It may be a perfluoropolyether group represented by: In the formula, l ′ is an integer of 1 to 200, preferably an integer of 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.

  In the general formula (I), X is a linking group that bonds between Rf and Si forming the siloxane skeleton. X should just be a bivalent organic group, Preferably it has 1-20 carbon atoms, More preferably, it has 1-12 carbon atoms.

More particularly, X is the following formula:
_{- (CH 2) p -O- (} CH 2) q -
It may be a group represented by In this formula, p is an integer of 1 to 20, preferably 1 to 10, and q is an integer of 2 to 20, preferably 2 to 10. Examples of groups represented by the formula include —CH ₂ —O—CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ —O—CH ₂ CH ₂ CH ₂ —, —CH ₂ —O—CH _2. CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ —O—CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ — and the like are included (however, the left end of the formula is bonded to Rf, (The right end of is bonded to Si.)

X is the following formula:
_{- (CH 2) s -CONH- (} CH 2) t -
The group represented by these may be sufficient. In this formula, s is an integer of 0 or more and 10 or less, preferably 0, and t is an integer of 2 or more and 10 or less. Examples of the group represented by the formula include —CONH—CH ₂ CH ₂ CH ₂ —, —CONH—CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ — and the like (provided that the left end of the formula is (It shall be bonded to Rf, and the right end of the formula shall be bonded to Si).

  However, X is not limited to these, and any appropriate divalent organic group can be applied as long as it bonds between Rf and Si forming the siloxane skeleton.

In the above general formula (I), Z is a silyl group containing a hydrolyzable moiety. More specifically, Z is the following formula:
-SiT _x R ¹⁴ _3-x
The silyl group represented by these may be sufficient. In this formula, T and R ¹⁴ 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 4 carbon atoms, preferably -OA (alkoxy group). Examples of A include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; substituted alkyl groups such as 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 ¹⁴ is 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 4 carbon atoms.
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 formula (I), Y is a linking group that bonds between Si and Z forming a siloxane skeleton. Y should just be a divalent organic group, Preferably it has 1-20 carbon atoms, More preferably, it has 1-12 carbon atoms. Y may be the same as X or different.

More particularly, Y represents the following formula:
- _{(CH 2) r} -
It may be a group represented by In this formula, r is an integer of 2 or more and 20 or less, preferably an integer of 2 or more and 10 or less.

  However, Y is not limited to these, and any appropriate divalent organic group can be applied as long as it bonds between Si and Z forming the siloxane skeleton.

In the general formula (I), a is 1 or more and 100 or less, preferably 1 or more and 10 or less, b is 0 or more and 100 or less, preferably 0 or more and 20 or less, c is 0 or more and 200 or less, preferably 0 or more and 20 or less, d is 0 or more and 200 or less, preferably 0 or more and 50 or less, and the sum of b and c is at least 1, preferably 1 or more and 20 or less. Focusing on only one compound, a, b, c and d are integers, but the compound of the present invention may be a mixture of a plurality of compounds represented by the above general formula (I). a, b, c, d may be real numbers representing the average composition of such a mixture. In addition, for convenience, the order of existence of each repeating unit with parentheses a, b, c, and d is described in a specific order in the formula, but the binding order of these repeating units is limited to this. It is not optional.
Such 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).

  The fluoropolyether group-containing silicone compound represented by the general formula (I) of the present invention has been described above. Such a compound preferably has an average molecular weight of 1000 to 30000, 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^１〜Ｒ^６、Ｒ^８〜Ｒ^１２、ａ、ｂ、ｃ、ｄは上記の通りであり、典型的には、Ｒ^４、Ｒ^５、Ｒ^６は同じであり得る。）で表される化合物を、以下の一般式（ＩＩｂ）または（ＩＩｃ）：
Ｒｆ−（ＣＨ_２）_ｐ−Ｏ−（ＣＨ_２）_ｑ−２−ＣＨ＝ＣＨ_２ ・・・（ＩＩｂ）
Ｒｆ−（ＣＨ_２）_ｓ−ＣＯＮＨ−（ＣＨ_２）_ｔ−２−ＣＨ＝ＣＨ_２ ・・・（ＩＩｃ）
（これら式中、Ｒｆ、ｐ、ｑ、ｓ、ｔは上記の通りである。）で表される化合物、および、ｂがゼロでない場合には以下の一般式（ＩＩｄ）：
ＣＨ_２＝ＣＨ−（ＣＨ_２）_ｒ−２−Ｚ ・・・（ＩＩｄ）
（式中、Ｚ、ｒは上記の通りである。）で表される化合物とヒドロシリル化反応に付し、および、ｃがゼロでない場合にはＲ^７ＯＨ（式中、Ｒ^７は上記の通りである。）と脱水素カップリング反応に付すことにより得ることができる。
この例により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について、一般式（Ｉ）中、Ｘは以下の式：
−（ＣＨ_２）_ｐ−Ｏ−（ＣＨ_２）_ｑ−
（式中、ｐおよびｑは上記の通りであり、式の左端がＲｆに結合し、式の右端がＳｉに結合するものとする。）または以下の式：
−（ＣＨ_２）_ｓ−ＣＯＮＨ−（ＣＨ_２）_ｔ−
（式中、ｓおよびｔは上記の通りであり、式の左端がＲｆに結合し、式の右端がＳｉ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：
−（ＣＨ_２）_ｒ−
（式中、ｒは上記の通りである。）で表される基となる。 For example, the fluoropolyether group-containing silicone compound represented by the general formula (I) is represented by the following general formula (IIa):

(Wherein R ^{1 to} R ⁶ , R ^{8 to} R ¹² , a, b, c, and d are as described above, and typically R ⁴ , R ⁵ , and R ⁶ may be the same.) A compound represented by the following general formula (IIb) or (IIc):
_{Rf- (CH 2) p -O- (} CH 2) q-2 -CH = CH 2 ··· (IIb)
_{Rf- (CH 2) s -CONH- (} CH 2) t-2 -CH = CH 2 ··· (IIc)
(Wherein Rf, p, q, s, and t are as described above), and when b is not zero, the following general formula (IId):
_{CH 2 = CH- (CH 2)} r-2 -Z ··· (IId)
(Wherein Z and r are as described above) and hydrosilylation reaction with a compound represented by the formula: and when c is not zero, R ⁷ OH (wherein R ⁷ is as described above) And a dehydrogenation coupling reaction.
Regarding the fluoropolyether group-containing silicone compound obtained by this example, in general formula (I), X represents the following formula:
_{- (CH 2) p -O- (} CH 2) q -
(Wherein p and q are as described above, the left end of the formula is bonded to Rf and the right end of the formula is bonded to Si) or the following formula:
_{- (CH 2) s -CONH- (} CH 2) t -
(Wherein s and t are as described above, the left end of the formula is bonded to Rf and the right end of the formula is bonded to Si), and Y is the following formula:
- _{(CH 2) r} -
(Wherein, r is as described above).

  Any of these hydrosilylation reactions and dehydrogenation coupling reactions may proceed without a solvent or in a solvent. Examples of such solvents include perfluoroaliphatic hydrocarbons, aromatic hydrocarbons having fluorine-containing substituents (for example, bis (trifluoromethyl) benzene), hydrofluoroethers, etc., and these may be used alone or as 2 More than one species can be used in combination.

  The hydrosilylation reaction can be carried out in the presence of a catalyst such as platinum, for example at 0 to 130 ° C., conveniently under normal pressure. When carrying out the hydrosilylation reaction with the compound of the general formula (IIb) or (IIc) and the hydrosilylation reaction with the compound of the general formula (IId), these compounds of the general formula (IIb) or (IIc) and ( It is possible to carry out these hydrosilylation reactions together by previously mixing the compound of IId) in a solvent and adding the compound of the above general formula (IIa) in the presence of a catalyst. It is preferable because it can be controlled.

The dehydrogenation coupling reaction can be carried out in the presence of a catalyst such as platinum, for example at 0 to 130 ° C., conveniently under normal pressure. When carrying out the dehydrogenation coupling reaction, it is possible to control the heat of reaction by carrying out the dehydrogenation coupling reaction by adding R ⁷ OH to the reaction mixture after carrying out the hydrosilylation reaction. preferable.

  Although the fluoropolyether group-containing silicone compound of the present invention has been described with reference to production examples, the fluoropolyether group-containing silicone compound of the present invention is not limited to those produced by such examples.

  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.

  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, the silicone oil is, for example, 0 to 80 parts by mass, preferably 0 to 40 parts by mass with respect to 100 parts by mass of the fluoropolyether group-containing silicone compound represented by the general formula (I). Can 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, for example, 0 to 80 parts by mass, preferably 0 to 40 parts by mass with respect to 100 parts by mass of the fluoropolyether group-containing silicone compound represented by the general formula (I). May be included in parts.

Examples of such fluorine-containing oils include compounds represented by the following general formula (IV) (perfluoropolyether compounds).
^{_{R 21 - (OC 4 F 8}} ) k '' - (OC 3 F 6) l '' - (OC 2 F 4) m '' - (OCF 2) n '' -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.
k ″, l ″, m ″ and n ″ each represent the number of three types of repeating units of perfluoropolyether constituting the main skeleton of the polymer, each independently an integer of 0 to 300 And the sum of k ″, l ″, m ″ and n ″ is at least 1, preferably 1-100. The order of existence of each repeating unit with subscripts k ″, l ″, m ″, n ″ 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) l '''-R 22 ··· (IVa)
^{_{R 21 - (OCF 2 CF 2}} CF 2 CF 2) k '''- (OCF 2 CF 2 CF 2) l''' - (OCF 2 CF 2) m '''- (OCF 2) n''' -R ²² (IVb)
In these formulas, R ²¹ and R ²² are as described above; in formula (IVa), l ′ ″ is an integer of 1 to 100; in formula (IVb), k ′ ″ and l ″ 'Is independently an integer of 1 to 30 and m''' and n '''are each independently an integer of 1 to 300. In these formulas, the order of presence of each repeating unit in parentheses with the suffix k ″ ′, l ′ ″, m ′ ″ or n ′ ″ 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 fluorine-containing oil may be a compound represented by the general formula Rf-F (wherein Rf is as described above, preferably a perfluoropolyether group). The compound represented by Rf-F is preferable in that high affinity is obtained with each compound represented by the general formula (I).

  The fluorine-containing oil preferably has an average molecular weight of 1000 to 30000. Thereby, high surface slipperiness can be obtained. More specifically, the level of the average molecular weight can be selected according to the structure of the second compound used so that the desired surface slipperiness can be obtained. Typically, in the case of the compound represented by the general formula (IVa), it preferably has an average molecular weight of 2000 to 6000, and in the case of the compound represented by the general formula (IVb), 8000 to 30000 It is preferable to have an average molecular weight of In the range of these average molecular weights, 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-containing silane compound is, for example, 0 to 80 parts by mass, preferably 100 parts by mass of the fluoropolyether group-containing silicone compound represented by the general formula (I). May be included at 0 to 40 parts by weight.

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。
ｋ、ｌ、ｍおよびｎ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３種の繰り返し単位数をそれぞれ表わし、互いに独立して０以上２００以下の整数であって、ｋ、ｌ、ｍおよびｎの和は少なくとも１、好ましくは１〜１００である。添字ｋ、ｌ、ｍ、ｎ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。
ｅ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、ｅ、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, preferably may be substituted with one or more fluorine atoms. A good 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.
k, l, m and n each represent the number of three types of repeating units of perfluoropolyether constituting the main skeleton of the polymer, and are each independently an integer of 0 or more and 200 or less, and k, l, m And the sum of n is at least 1, preferably 1-100. The order of presence of each repeating unit with subscripts k, l, m, and n 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.
e 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 , e, 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。
ｋ、ｌ、ｍおよびｎ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３種の繰り返し単位数をそれぞれ表わし、互いに独立して０以上２００以下の整数であって、ｋ、ｌ、ｍおよびｎの和は少なくとも１、好ましくは１〜１００である。添字ｋ、ｌ、ｍ、ｎ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。
ｅ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、ｅ、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.
k, l, m and n each represent the number of three types of repeating units of perfluoropolyether constituting the main skeleton of the polymer, and are each independently an integer of 0 or more and 200 or less, and k, l, m And the sum of n is at least 1, preferably 1-100. The order of presence of each repeating unit with subscripts k, l, m, and n 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.
e 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 an 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 , e, h, i, and x, but they may be the same or different.

In the general formula (Va), (Vb), (VIa), (VIb), - (OC 4 F 8) k - (OC 3 F 6) l - (OC 2 F 4) m - (OCF 2) n - _{is, - (OCF 2 CF 2 CF} 2) l '- can be a. In the formula, l ′ is an integer of 1 to 200, preferably an integer of 1 to 100. Further, typically, Z ′ is a fluorine atom and e 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 compound that is non-reactive with respect to the substrate with respect to 100 parts by mass of the fluoropolyether group-containing silicone compound represented by the general formula (I) is, for example, 0 -80 mass parts, Preferably it may be contained at 0-40 mass parts, and a perfluoropolyether group containing silane compound may be contained at 0-80 mass parts, for example, Preferably it is 0-40 mass parts.

-Article Next, an article obtained using such a surface treating agent will be described. The article of the present invention comprises a base material and a layer formed on the surface of the base material from the above-mentioned fluoropolyether group-containing silicone compound or surface treatment agent (hereinafter simply referred to as a surface treatment agent). Surface treatment layer). 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 perfluoroalkyl ethers (such as a perfluoroalkyl group and alkyl Etc. can be linear or branched)). These solvents can be used alone or as a mixture of two or more. Among these, perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) and / or hydrofluoro ether is preferable, and 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 compound represented by the above general formula (I), all of T contained in Z are hydroxyl groups (and when present, the general formulas (Va), (Vb), (VIa) and (VIb In the case where T ′ is all hydroxyl groups in the compound represented by any of the above), water 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, hydrolyzable groups bonded to Si of the fluoropolyether group-containing silicone compound (and perfluoropolyether group-containing silane compound, if present) in the surface treatment agent It is considered that water acts on the 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, between the fluoropolyether group-containing silicone compound (and perfluoropolyether group-containing silane compound, if present), a group bonded to Si after hydrolysis (the above general formula (I)) In the compound represented by the formula (1), when all of T contained in Z is a hydroxyl group, it is the hydroxyl group. 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 are mixed between the compounds bonded in this way.) As a result, the fluoropolyether group-containing silicone compound (and when present) Is a bond between the perfluoropolyether group-containing silane compound) and a bond is formed between the compound and the substrate (and, if present, silicone oil and / or fluorine-containing oil) Is retained or trapped by affinity for fluoropolyether group-containing silicone compounds (and perfluoropolyether group-containing silane compounds).

  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 disc, DVD disc, CD-R, or MO; optical fiber or the like.

  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 4, fluoropolyether group-containing silicone compounds were synthesized in the following Synthesis Examples 1 to 4, respectively, and a surface treating agent was prepared using each compound obtained from these, and a surface treatment layer Formed.

Synthesis example 1
An average composition of CF ₃ CF ₂ CF ₂ O- (CF ₂ CF ₂ CF ₂ O) ₂₀ -CF ₂ CF ₂ CH ₂ OCH ₂ CH was added to a 200 mL four-necked flask equipped with a reflux condenser, thermometer and stirrer. = Xylene solution containing 4 mg of Pt (catalyst) as a complex of 40 g of perfluoropolyether-modified allyl ether represented by CH ₂ , 40 g of m-xylene hexafluoride (solvent) and 1,2-divinyltetramethylsiloxane 0.1 mL was added and stirred at 5 ° C. Thereafter, 19 g of siloxane represented by an average composition Me ₃ SiO— (Me ₂ SiO) ₁₃ — (MeHSiO) ₁₃ —SiMe ₃ (the symbol Me represents a methyl group, the same shall apply hereinafter) was added dropwise. Subsequently, 10 g of ethanol was added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 2 hours. Thereafter, the temperature was raised to 60 ° C. by heating and the mixture was stirred for 2 hours. Subsequently, the solvent and the like were distilled off under reduced pressure to obtain Compound 1 represented by the following formula.

Synthesis example 2
An average composition of CF ₃ CF ₂ CF ₂ O- (CF ₂ CF ₂ CF ₂ O) ₂₀ -CF ₂ CF ₂ CH ₂ OCH ₂ CH was added to a 200 mL four-necked flask equipped with a reflux condenser, thermometer and stirrer. As a complex of 40 g of perfluoropolyether-modified allyl ether represented by = CH ₂ , 1.6 g of allyltrimethoxysilane, 40 g of m-xylene hexafluoride (solvent), and 1,2-divinyltetramethylsiloxane, Pt A xylene solution (0.1 mL) containing 4 mg of (catalyst) was added and stirred at 5 ° C. Thereafter, 19 g of siloxane represented by an average composition Me ₃ SiO— (Me ₂ SiO) ₁₃ — (MeHSiO) ₁₃ —SiMe ₃ was dropped. Subsequently, 10 g of methanol was added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 2 hours. Thereafter, the temperature was raised to 60 ° C. by heating and the mixture was stirred for 2 hours. Subsequently, the solvent and the like were distilled off under reduced pressure to obtain Compound 2 represented by the following formula.

Synthesis example 3
An average composition of CF ₃ CF ₂ CF ₂ O- (CF ₂ CF ₂ CF ₂ O) ₂₀ -CF ₂ CF ₂ CH ₂ OCH ₂ CH was added to a 200 mL four-necked flask equipped with a reflux condenser, thermometer and stirrer. = Xylene solution containing 4 mg of Pt (catalyst) as a complex of 40 g of perfluoropolyether-modified allyl ether represented by CH ₂ , 40 g of m-xylene hexafluoride (solvent) and 1,2-divinyltetramethylsiloxane 0.1 mL was added and stirred at 5 ° C. Thereafter, 8.4 g of siloxane represented by an average composition Me ₃ SiO— (Me ₂ SiO) ₅ — (MeHSiO) ₅ —SiMe ₃ was dropped. Subsequently, 10 g of methanol was added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 2 hours. Thereafter, the temperature was raised to 60 ° C. by heating, and the mixture was stirred for 2 hours. Subsequently, the solvent and the like were distilled off under reduced pressure to obtain Compound 3 represented by the following formula.

Synthesis example 4
An average composition of CF ₃ CF ₂ CF ₂ O- (CF ₂ CF ₂ CF ₂ O) ₂₀ -CF ₂ CF ₂ CH ₂ OCH ₂ CH was added to a 200 mL four-necked flask equipped with a reflux condenser, thermometer and stirrer. As a complex of 40 g of perfluoropolyether-modified allyl ether represented by = CH ₂ , 7.0 g of allyltrimethoxysilane, 40 g of m-xylene hexafluoride (solvent), and 1,2-divinyltetramethylsiloxane A xylene solution (0.1 mL) containing 4 mg of Pt (catalyst) was added and stirred at 5 ° C. Thereafter, 8.4 g of siloxane represented by an average composition Me ₃ SiO— (Me ₂ SiO) ₅ — (MeHSiO) ₅ —SiMe ₃ was dropped. Then, it heated up to room temperature and stirred for 2 hours. Thereafter, the temperature was raised to 60 ° C. by heating and the mixture was stirred for 2 hours. Subsequently, the solvent and the like were distilled off under reduced pressure to obtain Compound 4 represented by the following formula.

-Preparation of surface treatment agent (surface treatment composition) The compounds 1 to 4 (perfluoropolyether group-containing silicone compound) obtained in Synthesis Examples 1 to 4 were mixed with 1,3-trimethyl ether so that the concentration became 20 wt%. Surface treatment agents 1 to 4 were prepared by dissolving in fluoromethylbenzene.

-Formation of surface treatment layer Each surface treatment agent prepared above was vacuum-deposited on a slide glass. The processing conditions for vacuum deposition were a pressure of 3.0 × 10 ⁻³ Pa, and 1 mg of each surface treatment agent was deposited per slide glass. Thereafter, the slide glass with a deposited film was allowed to stand for 24 hours in an atmosphere having 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 compounds 1 to 4, 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
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)
After wiping the surface of the surface treatment layer on the slide glass obtained in the above examples and comparative examples with a waste impregnated with ethanol, the surface treatment layer was subjected to water / oil repellency, dynamic friction coefficient (surface slipperiness), oiliness The ink wiping property and the feeling of use 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 to water (1 μL) and the contact angle to normal hexadecane (1 μL) of the surface treatment layer on the slide glass prepared above were measured. did.

[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 understood from Table 1, in Examples 1 to 4 using the fluoropolyether group-containing silicone compound of the present invention, the kinetic friction is as small as that of 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 to 4 using the fluoropolyether group-containing silicone compound of the present invention, the water and oil repellency is higher than that of Comparative Example 3 using the composition 1 in which the control compounds 1 and 2 are 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)

Fluoropolyether group-containing silicone compound represented by the following general formula (I)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are each independently an alkyl group or an aryl group; R ⁷ is an alkyl group having 1 to 4 carbon atoms, Rf is a fluoropolyether group, X and Y are divalent organic groups that are the same or different from each other, and Z includes a hydrolyzable moiety. a silyl group, a is 1 or more and 100 or less, b is 0 or more and 100 or less, c is 1 to 200, d is 0 to 200, the order of the repeating units enclosed in parentheses is the formula Is optional.) In the general formula (I), Rf is the following formula:
_{^{R 13 - (OC 4 F 8}} ) k - (OC 3 F 6) l - (OC 2 F 4) m - (OCF 2) n -
Wherein R ¹³ is an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms, and k, l, m and n are each independently 0 or more and 200 A perfluoropolyether group represented by the following integer, wherein the sum of k, l, m and n is at least 1 and the order of presence of each repeating unit in parentheses is arbitrary in the formula: The fluoropolyether group-containing silicone compound according to claim 1, wherein In the general formula (I), Rf is the following formula:
_{CF 3 CF 2 CF 2 - (} OCF 2 CF 2 CF 2) l '-OCF 2 CF 2 -
The fluoropolyether group-containing silicone compound according to claim 2, which is a perfluoropolyether group represented by the formula (wherein l 'is an integer of 1 to 200). In the general formula (I), Z represents the following formula:
-SiT _x R ¹⁴ _3-x
(Wherein T is a hydroxyl group or a hydrolyzable group, R ¹⁴ 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 3. In the general formula (I), X represents the following formula:
_{- (CH 2) p -O- (} CH 2) q -
The fluoropolyether group according to any one of claims 1 to 4 , wherein p is an integer of 1 or more and 20 or less, and q is an integer of 2 or more and 20 or less. Containing silicone compound. In the general formula (I), X represents the following formula:
_{- (CH 2) s -CONH- (} CH 2) t -
(In the formula, s is an integer of 0 or more and 10 or less, and t is an integer of 2 or more and 10 or less.) The fluoropolyether group according to any one of claims 1 to 4. Containing silicone compound. In the general formula (I), Y represents the following formula:
- _{(CH 2) r} -
The fluoropolyether group-containing silicone compound according to any one of claims 1 to 6 , which is a group represented by the formula (wherein r is an integer of 2 or more and 20 or less). In Rf of the formula (I), R ¹³ is a perfluoroalkyl group having 1 to 16 carbon atoms, perfluoropolyether group-containing silicone compound according to any one of claims 2-7. Fluoropolyether group containing containing a silicone compound, a surface treatment agent according to any one of claims 1-8. The surface treating agent according to claim 9 , which is used as an antifouling coating agent. An article comprising a substrate and a layer formed from the fluoropolyether group-containing silicone compound according to any one of claims 1 to 8 or the surface treatment agent according to claim 9 or 10 on the surface of the substrate. . 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.