JP6163796B2 - Perfluoropolyether group-containing silazane compound - Google Patents

Description

  The present invention relates to a silazane compound containing a perfluoropolyether group. The present invention also relates to a surface treatment agent using such a perfluoropolyether group-containing silazane 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.

International Publication No. 97/07155 International Publication No. 2011/060047 JP 2010-43251 A

  The surface treatment layer is required to have high durability in order to provide a desired function to the base material over a long period of time. 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. In particular, these applications are required to further improve the friction durability.

  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 friction durability.

Further, as another surface treatment agent used for providing water repellency, oil repellency, antifouling property, etc., a silazane having a perfluoropolyether portion and a portion represented by -Si (NH) _1.5 One containing perfluoropolyether-modified polysilazane consisting only of units and / or a partial hydrolysis condensate thereof is known (see Patent Document 3). However, such a perfluoropolyether-modified polysilazane is difficult to be dissolved in a solvent and difficult to be used as a surface treatment agent because it has a high molecular weight and thus is difficult to use as a surface treatment agent.

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

（これら式中、Ｒｆ^１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、
ａ、ｂ、ｃおよびｓはそれぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃおよびｓの和は少なくとも１であり、ａ、ｂ、ｃ、ｓ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り、
ｄおよびｆは０または１であり、
ｅおよびｇは０以上２以下の整数であり、
ｍおよびｌは１以上１０以下の整数であり、
Ｘは水素原子またはハロゲン原子を表し、
Ｙは水素原子または低級アルキル基を表し、
Ｚはフッ素原子または低級フルオロアルキル基を表し、
Ｔは−ＮＲ^２ _２または−ＮＨＲ^２（式中、Ｒ^２は、置換または非置換の炭素数１〜２２のアルキル基を表し、２つのＲ^２は互いに結合して環構造を形成してもよい）で表される置換アミノ基を表し、
Ｒ^１は炭素数１〜２２のアルキル基、炭素数１〜２２のアルコキシ基または水酸基を表し、
ｎは１以上３以下の整数である。）
なお、本発明を通じて、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 perfluoropolyether group-containing silazane compound represented by any one of the following general formulas (1a) and (1b).

(In these formulas, Rf ¹ represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms,
a, b, c and s are each independently an integer of 0 or more and 200 or less, the sum of a, b, c and s is at least 1, and a, b, c and s are attached in parentheses. The order of presence of each repeating unit is arbitrary in the formula,
d and f are 0 or 1,
e and g are integers of 0 or more and 2 or less,
m and l are integers of 1-10.
X represents a hydrogen atom or a halogen atom,
Y represents a hydrogen atom or a lower alkyl group,
Z represents a fluorine atom or a lower fluoroalkyl group,
T represents —NR ² ₂ or —NHR ² (wherein R ² represents a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms, and two R ² may be bonded to each other to form a ring structure) Represents a substituted amino group represented by
R ¹ represents an alkyl group having 1 to 22 carbon atoms, an alkoxy group having 1 to 22 carbon atoms or a hydroxyl group,
n is an integer of 1 or more and 3 or less. )
Throughout the present invention, when there are a plurality of the same symbols in a general formula, these can be selected independently of each other.

Said perfluoropolyether group-containing silazane compound of the present invention, the perfluoropolyether group _{(- (OC 4 F 8)} s - (OC 3 F 6) a - (OC 2 F 4) b - (OCF 2) c - a), and a substituent aminosilyl group ^{_{(-SiT n R 1 3-n}} ). The perfluoropolyether group contributes to water repellency and oil repellency and thus antifouling properties. Further, the substituted aminosilyl group contributes to friction durability. According to such a perfluoropolyether group-containing silazane compound, it is possible to form a layer having water repellency, oil repellency, antifouling property, surface slipperiness (for example, fingerprint wiping property) and high friction durability. It becomes possible.

In the general formulas (1a) and (1b), for example, Rf ¹ is a perfluoroalkyl group having 1 to 3 carbon atoms, and s = 0, b = 0, c = 0, d = 1, and f = 1. Yes, Z can be a fluorine atom.

  In the general formulas (1a) and (1b), n is preferably 3.

  According to another aspect of the present invention, there is also provided a surface treatment agent comprising the perfluoropolyether group-containing silazane compound. The surface treating agent of the present invention contains at least one of the perfluoropolyether group-containing silazane compound represented by the general formula (1a) and the perfluoropolyether group-containing silazane compound represented by the general formula (1b). Both of these may be included.

（これら式中、Ｒｆ^１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、
ａ、ｂ、ｃおよびｓはそれぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃおよびｓの和は少なくとも１であり、ａ、ｂ、ｃ、ｓ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り、
ｄおよびｆは０または１であり、
ｅおよびｇは０以上２以下の整数であり、
ｍおよびｌは１以上１０以下の整数であり、
Ｘは水素原子またはハロゲン原子を表し、
Ｙは水素原子または低級アルキル基を表し、
Ｚはフッ素原子または低級フルオロアルキル基を表し、
Ｔ’は水酸基または加水分解可能な基（但し、置換アミノ基を除く）を表し、
Ｒ^３は水素原子または炭素数１〜２２のアルキル基を表し、
ｎは１以上３以下の整数である。）
で表されるパーフルオロポリエーテル基含有シラン化合物を更に含んでいてよい。 In addition, the surface treating agent of the present invention is any one of the following general formulas (2a) and (2b):

(In these formulas, Rf ¹ represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms,
a, b, c and s are each independently an integer of 0 or more and 200 or less, the sum of a, b, c and s is at least 1, and a, b, c and s are attached in parentheses. The order of presence of each repeating unit is arbitrary in the formula,
d and f are 0 or 1,
e and g are integers of 0 or more and 2 or less,
m and l are integers of 1-10.
X represents a hydrogen atom or a halogen atom,
Y represents a hydrogen atom or a lower alkyl group,
Z represents a fluorine atom or a lower fluoroalkyl group,
T ′ represents a hydroxyl group or a hydrolyzable group (excluding a substituted amino group),
R ³ represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms,
n is an integer of 1 or more and 3 or less. )
The perfluoropolyether group containing silane compound represented by these may be further included.

  Such a surface treatment agent of the present invention can impart water repellency, oil repellency, antifouling property, and friction durability 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, a substrate and a layer (surface treatment layer) formed from the perfluoropolyether group-containing silazane compound or the surface treatment agent on the surface of the substrate are included. An article is also provided. The layer in such an article has water repellency, oil repellency, antifouling properties and high friction durability.

  The article obtained by the present invention is not particularly limited, but may be, for example, an optical member. The optical member has a high demand for improvement in friction durability, 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 perfluoropolyether group-containing silazane compound is provided, and this compound has a perfluoropolyether group and a substituted aminosilyl group, thereby providing water repellency, oil repellency, antifouling properties. And a layer having high friction durability can be formed. Furthermore, according to the present invention, a surface treatment agent obtained by using such a perfluoropolyether group-containing silazane compound and an article to which the surface treatment agent is applied are also provided.

It is a graph which shows the friction durability of the surface treatment layer produced in Examples 1-3 of this invention and Comparative Examples 1-5.

  Hereinafter, although the perfluoropolyether group containing silazane 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.

-Perfluoropolyether group-containing silazane compound The perfluoropolyether group-containing silazane compound of the present invention is represented by any one of the following general formulas (1a) and (1b).

In these formulas, Rf ¹ represents 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 (for example, CF ₃ —, C ₂ F ₅ —, C ₃ F ₇ —).

In the above formula, the perfluoropolyether group is
_{- (OC 4 F 8) s} - (OC 3 F 6) a - (OC 2 F 4) b - (OCF 2) c -
It is a part represented by. a, b, c and s 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 or more and 200 or less, wherein a, b, c And the sum of s is at least 1, preferably 1-100. The order of presence of each repeating unit with subscripts a, b, c, and s 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.
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).

  In the above formula, d and f are 0 or 1. e and g are integers 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, and more preferably an iodine 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.

Although not limiting the present invention, Rf ¹ is a perfluoroalkyl group having 1 to 3 carbon atoms, s = 0, b = 0, c = 0, d = 1, f = 1, and Z is A fluorine atom is preferred. In this case, appropriate friction durability can be obtained. Moreover, it is more preferable that the repeating unit-(OC ₃ F ₆ )-attached with the subscript a and enclosed in parentheses is-(OCF ₂ CF ₂ CF ₂ )-. 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.

T and R ¹ are groups bonded to Si. n is an integer of 1 or more and 3 or less.

R ¹ represents an alkyl group having 1 to 22 carbon atoms, an alkoxy group having 1 to 22 carbon atoms or a hydroxyl group, preferably an alkyl group having 1 to 22 carbon atoms or an alkoxy group having 1 to 22 carbon atoms, more preferably a carbon number. It is a 1-3 alkyl group or a C1-C3 alkoxy group. The hydroxyl group is not particularly limited, but may be a product of hydrolysis of an alkoxy group having 1 to 22 carbon atoms.

T represents —NR ² ₂ or —NHR ² (wherein R ² represents a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms, and two R ² may be bonded to each other to form a ring structure) Represents a substituted amino group (typically an alkylamino group). Examples of the substituted amino group (-T) include a methylamino group, an ethylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a diisobutylamino group, a normal octylamino group, a pyrrolidino group, and a piperidino group. Preferably a dimethylamino group, a diethylamino group, a diisopropylamino group, and more preferably a dimethylamino group.

Therefore, in the above formula,
-SiT _n R ¹ _3-n
The portion represented by is a substituted aminosilyl group (typically an alkylaminosilyl group).
In the compound of the present invention, the substituted amino group (-T) bonded to Si can be bonded by reacting with the substrate and between the compounds, and the compound having such a group exhibits excellent friction durability. Can do.
In particular, n is preferably 3 (typically a tris (alkylamino) silyl group). In this case, the friction durability is further improved as compared with the case where n is 1.

  In the above formula, m and l are integers of 1 or more and 10 or less. m and l are preferably integers of 2 or more and 6 or less.

  The perfluoropolyether group-containing silazane compound represented by the general formulas (1a) and (1b) of the present invention has been described above. The perfluoropolyether group-containing silazane compound is not particularly limited, and may have an average molecular weight of 1000 to 12000, for example. Among these ranges, an average molecular weight of 2,000 to 10,000 is preferable from the viewpoint of friction durability. In the present invention, “average molecular weight” refers to a number average molecular weight.

  Such a perfluoropolyether group-containing silazane compound of the present invention can be produced by any appropriate method. For example, it can be manufactured by the following method, but is not limited thereto.

（式中、Ｘ’はハロゲン原子を表す）で表される少なくとも１種の化合物を準備する。かかる化合物は、例えば、以下の一般式（ｉａ）および（ｉｂ）のいずれか：

で表される少なくとも１種の化合物をハロゲン化（例えばヨウ素化）反応に付して得ることができるが、これに限定されない。 First, as a raw material, any one of the following general formulas (iii) and (iib):

At least one compound represented by the formula (wherein X ′ represents a halogen atom) is prepared. Such a compound is, for example, any of the following general formulas (ia) and (ib):

Although it can obtain by attaching | subjecting at least 1 type of compound represented by these to halogenation (for example, iodination) reaction, it is not limited to this.

で表される少なくとも１種の化合物を得る。かかる反応は、ジ−ｔｅｒｔ−ブチルパーオキシドなどのラジカル開始剤の存在下にて、例えば６０〜１４０℃で、簡便には常圧下で実施され得る。 At least one compound represented by any one of the general formulas (iii) and (iib) is represented by CH ₂ ═CY— (CH ₂ ) _i —SiX ″ _n R ¹ _3-n
(Wherein i is an integer of 0 or more and 2 or less, X ″ is a halogen atom, R ¹ is as described above, preferably an alkyl group having 1 to 22 carbon atoms, more preferably a carbon number. 1 to 3 alkyl groups.)
Any of the following general formulas (iii) and (iiib):

To obtain at least one compound represented by: Such a reaction can be carried out in the presence of a radical initiator such as di-tert-butyl peroxide, for example at 60 to 140 ° C., conveniently under normal pressure.

で表される少なくとも１種の化合物を得る。かかる反応は、例えば０〜８０℃で、簡便には常圧下で実施され得る。 Then, at least one compound represented by any one of the general formulas (iii) and (iiib) thus obtained is converted to NHR ² ₂ or NH ₂ R ^2.
The following general formulas (iva) and (ivb) are obtained by reacting with a substituted amine represented by the formula (a) and aminating the halogen atom X ″ bonded to Si of the silyl group with a substituted amino group: Or:

To obtain at least one compound represented by: Such a reaction can be carried out, for example, at 0 to 80 ° C., conveniently under normal pressure.

  Further, if necessary, the halogen atom X ′ may be replaced with a hydrogen atom, for example, with zinc powder. Such a reaction can be carried out, for example, at 0 to 80 ° C., conveniently under normal pressure.

  As described above, at least one perfluoropolyether group-containing silazane compound represented by any one of the general formulas (1a) and (1b) is obtained. In the present specification, symbols in each formula are the same as above unless otherwise specified.

  Any reaction may proceed without solvent or in a solvent. Examples of such solvents include perfluoroaliphatic hydrocarbons, m-xylene hexafluoride, and the like, and these can be used alone or in combination of two or more. Moreover, when a condensation reaction can occur, in order to suppress this, it is preferable to make it react under nitrogen stream.

  As described above, the perfluoropolyether group-containing silazane compound of the present invention has been described with reference to production examples. However, the perfluoropolyether group-containing silazane compound of the present invention is not limited to those produced by such examples. .

For example, a raw material in which a compound represented by the general formula (ia) and a compound represented by the general formula (iib) are mixed (in this raw material, a fluorine-containing oil represented by the general formula Rf ¹ -F described later) May be further mixed). In such a case, in the resulting reaction mixture, the perfluoropolyether group-containing silazane represented by the general formula (1a) and the perfluoropolyether group-containing silazane compound represented by the general formula (1b) It will be mixed.

  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 of this invention should just contain the perfluoro polyether group containing silazane compound of this invention mentioned above. That is, at least one of the perfluoropolyether group-containing silazane compound represented by the general formula (1a) and the perfluoropolyether group-containing silazane compound represented by the general formula (1b) is included, and both of these are included. You may go out. When these are used in combination, the compound represented by the general formula (1a) and the compound represented by the general formula (1b) may exist in a mass ratio of 10: 1 to 1: 1, for example. It is not limited to.

  The surface treatment agent only needs to contain a perfluoropolyether group-containing silazane compound as a main component or an active component. 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 perfluoropolyether group-containing silazane compound, and forms a surface treatment layer having water repellency, oil repellency, antifouling properties and high friction durability. Therefore, it is suitably used as an antifouling coating agent.

  The composition of the surface treatment agent (or surface treatment composition) of the present invention may be appropriately selected according to the function desired for the surface treatment layer.

  For example, the surface treatment agent may contain a perfluoropolyether group-containing silane compound in addition to the above-mentioned perfluoropolyether group-containing silazane 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 treating agent of the present invention, the perfluoropolyether group-containing silane compound is contained in an amount of, for example, 0 to 300 parts by mass, preferably 50 to 200 parts by mass with respect to 100 parts by mass of the perfluoropolyether group-containing silazane compound. obtain.

これら式中、
Ｔ’は水酸基または加水分解可能な基（但し、置換アミノ基を除く）を表す。加水分解可能な基の例としては、−ＯＡ、−ＯＣＯＡ、−Ｏ−Ｎ＝Ｃ（Ａ）_２、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^３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。
その他の記号は、一般式（１ａ）および（１ｂ）中におけるものと同様であり、上述した説明が同様に当て嵌まる。 Examples of the perfluoropolyether group-containing silane compound include compounds represented by any one of the following general formulas (2a) and (2b) (may be one kind or a mixture of two or more kinds).

In these formulas
T ′ represents a hydroxyl group or a hydrolyzable group (excluding a substituted amino group). Examples of hydrolyzable groups include —OA, —OCOA, —O—N═C (A) ₂ , halogen (in these formulas, A represents a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms. For example). The hydroxyl group is not particularly limited, but may be a group produced by hydrolysis of a hydrolyzable group.
R ³ 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.
Other symbols are the same as those in the general formulas (1a) and (1b), and the above description applies similarly.

In the general formulas (2a) and (2b), Rf ¹ is a perfluoroalkyl group having 1 to 3 carbon atoms, and s = 0, b = 0, c = 0, d = 1, and f = 1. Z is preferably a fluorine atom. Moreover, it is more preferable that the repeating unit-(OC ₃ F ₆ )-attached with the subscript a and enclosed in parentheses is-(OCF ₂ CF ₂ CF ₂ )-.

  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.

  In addition to the perfluoropolyether group-containing silazane compound, the surface treatment agent of the present invention may contain a fluoropolyether compound that can be understood as a fluorinated oil, preferably a perfluoropolyether compound ( Hereinafter, it is referred to as “fluorinated oil” for the purpose of distinguishing from the perfluoropolyether group-containing silazane compound of the present invention). The fluorine-containing oil contributes to improving the surface slipperiness of the surface treatment layer.

  In the surface treatment agent, the fluorine-containing oil is, for example, 0 to 300 parts by mass with respect to 100 parts by mass of the perfluoropolyether group-containing silazane compound (in the case of two or more kinds, the total thereof, the same applies hereinafter), preferably It may be included at 50 to 200 parts by mass.

Examples of such fluorine-containing oils include compounds represented by the following general formula (3) (perfluoropolyether compounds).
^{_{R 21 - (OC 4 F 8}} ) s '- (OC 3 F 6) a' - (OC 2 F 4) b '- (OCF 2) c' -R 22 ··· (3)
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, 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.
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 It is the C1-C3 alkyl group which may be made. 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 s ′ 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, The sum of ', b', c 'and s' is at least 1, preferably 1-100. The order of existence of each repeating unit with subscripts a ′, b ′, c ′, s ′ and parenthesized 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 (3), it may be a compound represented by any one of the following general formulas (3a) and (3b) (one kind or a mixture of two or more kinds). ).
^{_{R 21 - (OCF 2 CF 2}} CF 2) a '' -R 22 ··· (3a)
^{_{R 21 - (OCF 2 CF 2}} CF 2 CF 2) s '' - (OCF 2 CF 2 CF 2) a '' - (OCF 2 CF 2) b '' - (OCF 2) c '' -R 22 · .. (3b)
In these formulas, R ²¹ and R ²² are as described above; in formula (3a), a ″ is an integer of 1 to 100; in formula (3b), s ″ and a ″ are respectively Are independently an integer of 1 to 30, and b ″ and c ″ are each independently an integer of 1 to 300. In these formulas, the order of presence of each repeating unit with subscripts s ″, a ″, b ″ or c ″ and enclosed in parentheses is arbitrary in the formulas.

  The compound represented by the general formula (3a) and the compound represented by the general formula (3b) may be used alone or in combination. When these are used in combination, it is preferable to use the compound represented by the general formula (3a) and the compound represented by the general formula (3b) 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 ¹ -F (wherein Rf ¹ is as described above). The compound represented by Rf ¹ -F is preferable in that high affinity is obtained with the compound represented by any one of the general formulas (1a) and (1b).

  The fluorine-containing oil may have an average molecular weight of 1000 to 30000. Thereby, high surface slipperiness can be obtained. Typically, in the case of the compound represented by the general formula (3a), the compound preferably has an average molecular weight of 2000 to 6000, and in the case of the compound represented by the general formula (3b), 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.

  Further, the surface treatment agent of the present invention may contain a silicone compound (hereinafter referred to as “silicone oil”) that can be understood as a silicone oil, in addition to the above-mentioned perfluoropolyether group-containing silazane compound. Silicone oil contributes to improving the surface slipperiness of the surface treatment layer.

  In the surface treatment agent, the silicone oil may be contained in an amount of, for example, 0 to 300 parts by mass, preferably 50 to 200 parts by mass with respect to 100 parts by mass of the perfluoropolyether group-containing silazane compound.

  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.

  In addition to the above-mentioned perfluoropolyether group-containing silazane compound, the surface treatment agent of the present invention comprises a perfluoropolyether group-containing silane compound and a compound that is non-reactive with the substrate (for example, fluorine-containing oil and And / or silicone oil). In this case, in the surface treatment agent of the present invention, the perfluoropolyether group-containing silane compound is, for example, 0 to 300 parts by mass, preferably 50 to 200 parts by mass with respect to 100 parts by mass of the perfluoropolyether group-containing silazane compound. The compound that is non-reactive with respect to the substrate may be contained, for example, in an amount of 0 to 300 parts by mass, preferably 50 to 200 parts by mass.

-Article Next, an article obtained using such a surface treating agent will be described. The article of the present invention comprises a substrate, a perfluoropolyether group-containing silazane compound represented by the above general formula (1a) and / or (1b) on the surface of the substrate, or a surface treatment agent (hereinafter referred to as these). And a layer (surface treatment layer) formed from a surface treatment agent. 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.

  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, the substituted amino group bonded to Si of the perfluoropolyether group-containing silazane compound in the surface treatment agent (and Si of the perfluoropolyether group-containing silane compound, if present) It is considered that water can act on the hydrolyzable group bonded to the compound to rapidly hydrolyze the compound.

  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, hydrolyzed Si-bonded groups quickly dehydrated between perfluoropolyether group-containing silazane compounds (and perfluoropolyether group-containing silane compounds, if present). To do. 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, if present, the fluorine-containing oil and / or the silicone oil are mixed between the compounds bonded in this way.) As a result, the perfluoropolyether group-containing silazane compound (and the case where it exists) , A bond is formed between the perfluoropolyether group-containing silane compound), and a bond is formed between the compound and the substrate (and fluorine oil and / or silicone if present). Oil is retained or trapped by affinity for perfluoropolyether group-containing silazane 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 moisture content on the surface of the precursor film is decreased, 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 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 perfluoropolyether group-containing silazane compound of the present invention, the surface treatment agent and the article obtained by using the same will be described in more detail through the following examples, but the present invention is limited to these examples. is not.

(Synthesis example)
Two perfluoropolyether group-containing silazane compounds were synthesized according to the procedures of Synthesis Examples 1 to 3.

（式中、ｍは１〜６の整数である。） Synthesis example 1
In a 200 mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, a par. Represented by an average composition CF ₃ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₂₀ CF ₂ CF ₂ -I 45 g of fluoropolyether-modified iodine, 45 g of m-xylene hexafluoride, and 5.1 g of vinyltrichlorosilane were charged and stirred at room temperature for 30 minutes in a nitrogen stream. Subsequently, 0.91 g of di-tert-butyl peroxide was added, the temperature was raised to 120 ° C., and the mixture was stirred at this temperature for 12 hours. Then, 42 g of the following perfluoropolyether group-containing silane compound (A) having iodine at the terminal was obtained by distilling off volatile components under reduced pressure.

(In the formula, m is an integer of 1 to 6.)

（式中、ｍは１〜６の整数である。） Synthesis example 2
In a 200 mL four-necked flask equipped with a reflux condenser, a thermometer, and a stirrer, 30 g of a perfluoropolyether group-containing silane compound (A) having iodine at the end synthesized in Synthesis Example 1 and 77 g of perfluorohexane were added. The mixture was stirred and stirred at 5 ° C. for 30 minutes under a nitrogen stream. Subsequently, 5.0 g of dimethylamine was added, and the mixture was stirred at 5 ° C. for 3 hours while refluxing. Thereafter, the temperature is raised to room temperature, and the operation of washing with tetrahydrofuran in a separatory funnel (more specifically, maintaining the fluoro compound in the perfluorohexane phase (fluorus phase) and the non-fluoro compound in the tetrahydrofuran phase (organic phase)) The operation of separating and removing was performed 3 times. Subsequently, volatile matter was distilled off under reduced pressure to obtain 27 g of the following perfluoropolyether group-containing silazane compound (B) having iodine at the terminal.

(In the formula, m is an integer of 1 to 6.)

（式中、ｍは１〜６の整数である。） Synthesis example 3
In a 200 mL four-necked flask equipped with a reflux condenser, a thermometer, and a stirrer, 20 g of perfluoropolyethersilazane compound (B) having iodine at the end synthesized in Synthesis Example 2, 20 g of perfluorohexane, tert- 20 g of butyl alcohol and 1.0 g of zinc powder were charged and stirred at 45 ° C. for 7 hours under a nitrogen stream. Thereafter, the temperature was lowered to room temperature, and the washing operation with tetrahydrofuran was performed three times with a separatory funnel. Subsequently, the volatile matter was distilled off under reduced pressure to obtain 16 g of the following perfluoroether group-containing silazane compound (C) having hydrogen at the terminal.

(In the formula, m is an integer of 1 to 6.)

Example 1
-Preparation of surface treatment agent and formation of surface treatment layer The compound (B) obtained in Synthesis Example 2 was dissolved in hydrofluoroether (manufactured by 3M, Novec HFE7200) so as to have a concentration of 20 wt%. Treatment agent 1 was prepared.
The surface treating agent 1 prepared above was vacuum-deposited on chemically strengthened glass (Corning, “Gorilla” glass, thickness 0.7 mm). The processing conditions for vacuum deposition were a pressure of 3.0 × 10 ⁻³ Pa, and 2 mg of each surface treatment agent was deposited per chemically strengthened glass (55 mm × 100 mm). Thereafter, the chemically strengthened glass with a deposited film was allowed to stand for 24 hours in an atmosphere of a temperature of 20 ° C. and a humidity of 65%. Thereby, a vapor deposition film hardened and a surface treatment layer was formed.

(Example 2)
A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 1 except that the compound (C) obtained in Synthesis Example 3 was used instead of the compound (B).

（式中、ｍは１〜６の整数である。） (Example 3)
In place of the compound (B), the surface treating agent was treated in the same manner as in Example 1 except that a composition in which the compound (B) and the following control compound 1 were mixed at a mass ratio of 1: 1 was used. Prepared and formed a surface treatment layer.
Control compound 1

(In the formula, m is an integer of 1 to 6.)

（式中、ｍは１〜６の整数である。）
・対照化合物２
CF₃CF₂CF₂O(CF₂CF₂CF₂O)₂₀CF₂CF₂CH₂OCH₂CH₂CH₂Si(OCH₃)₃
・対照化合物３
(CH₃O)₃SiCH₂CH₂CH₂OCH₂CF₂O(CF₂CF₂O)_p(CF₂O)_qCF₂CH₂OCH₂CH₂CH₂Si(OCH₃)₃
（式中、ｐは１０〜３０の整数であり、ｑは１０〜３０の整数である。）
・対照化合物４
CF₃CF₂CF₂O(CF₂CF₂CF₂O)₂₀CF₂CF₂CH₂OCH₂CH₂CH₂Si[N(CH₃)₂]₃
なお、対照化合物４は、置換アミノシリル基を有するパーフルオロポリエーテル基含有シラザン化合物であるが、その主鎖に−ＣＨ_２ＯＣＨ_２−を有する点で、本発明の置換アミノシリル基を有するパーフルオロポリエーテル基含有シラザン化合物と相違する。かかる対照化合物４は、特許文献２に開示されている化合物に相当する。
・対照化合物５
[N(CH₃)₂]₃SiCH₂CH₂CH₂OCH₂CF₂O(CF₂CF₂O)_p(CF₂O)_qCF₂CH₂OCH₂CH₂CH₂Si[N(CH₃)₂]₃
（式中、ｐは１０〜３０の整数であり、ｑは１０〜３０の整数である。）
なお、対照化合物５も、対照化合物４と同様に、その主鎖に−ＣＨ_２ＯＣＨ_２−を有する点で、本発明の置換アミノシリル基を有するパーフルオロポリエーテル基含有シラザン化合物と相違する。かかる対照化合物５は、特許文献２に記載の片末端に−Ｃ（＝Ｏ）Ｆを有する一般式（ｉ）で表される化合物を、両末端に−Ｃ（＝Ｏ）Ｆを有する化合物に代えて、実質的に特許文献２に記載の方法に従って製造することができる。具体的には、
FC(=O)-CF₂O(CF₂CF₂O)_p(CF₂O)_qCF₂-C(=O)F
で表わされる化合物を還元して、
HOCH₂-CF₂O(CF₂CF₂O)_p(CF₂O)_qCF₂-CH₂OH
で表わされる化合物を得、これを、
Hal-CH₂CH=CH₂
で表わされる化合物と反応させて、
CH₂=CHCH₂-OCH₂-CF₂O(CF₂CF₂O)_p(CF₂O)_qCF₂-CH₂O-CH₂CH=CH₂
で表わされる化合物を得、さらにこれを、
H-SiCl₃
で表わされる化合物と反応させて、
Cl₃SiCH₂CH₂CH₂-OCH₂-CF₂O(CF₂CF₂O)_p(CF₂O)_qCF₂-CH₂O-CH₂CH₂CH₂SiCl₃
で表わされる化合物を得、さらにこれを、
HN(CH₃)₂
で表せされる化合物と反応させることにより得ることができる（上記式中、ｐは１０〜３０の整数であり、ｑは１０〜３０の整数であり、Ｈａｌはハロゲンである）。 (Comparative Examples 1-5)
A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 1 except that the following control compounds 1 to 5 were used in place of the compound (B).
Control compound 1

(In the formula, m is an integer of 1 to 6.)
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
Control compound 3
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ OCH ₂ CF ₂ O (CF ₂ CF ₂ O) _p (CF ₂ O) _q CF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
(In the formula, p is an integer of 10 to 30, and q is an integer of 10 to 30.)
Control compound 4
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 [N (CH ₃ ) ₂ ] ₃
In addition, although the control compound 4 is a perfluoropolyether group-containing silazane compound having a substituted aminosilyl group, it has a substituted aminosilyl group of the present invention in that it has —CH ₂ OCH ₂ — in its main chain. Different from ether group-containing silazane compounds. Such a control compound 4 corresponds to the compound disclosed in Patent Document 2.
Control compound 5
[N (CH ₃ ) ₂ ] ₃ SiCH ₂ CH ₂ CH ₂ OCH ₂ CF ₂ O (CF ₂ CF ₂ O) _p (CF ₂ O) _q CF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ Si [N (CH ₃ ) ₂ ] ₃
(In the formula, p is an integer of 10 to 30, and q is an integer of 10 to 30.)
In addition, the control compound 5 is also different from the perfluoropolyether group-containing silazane compound having a substituted aminosilyl group of the present invention in that it has —CH ₂ OCH ₂ — in the main chain, like the control compound 4. Such a control compound 5 is a compound represented by the general formula (i) having —C (═O) F at one end described in Patent Document 2 and a compound having —C (═O) F at both ends. Instead, it can be produced substantially according to the method described in Patent Document 2. In particular,
FC (= O) -CF ₂ O (CF ₂ CF ₂ O) _p (CF ₂ O) _q CF ₂ -C (= O) F
The compound represented by
HOCH ₂ -CF ₂ O (CF ₂ CF ₂ O) _p (CF ₂ O) _q CF ₂ -CH ₂ OH
To obtain a compound represented by
Hal-CH ₂ CH = CH ₂
Is reacted with a compound represented by
CH ₂ = CHCH ₂ -OCH ₂ -CF ₂ O (CF ₂ CF ₂ O) _p (CF ₂ O) _q CF ₂ -CH ₂ O-CH ₂ CH = CH ₂
To obtain a compound represented by
H-SiCl ₃
Is reacted with a compound represented by
Cl ₃ SiCH ₂ CH ₂ CH ₂ -OCH ₂ -CF ₂ O (CF ₂ CF ₂ O) _p (CF ₂ O) _q CF ₂ -CH ₂ O-CH ₂ CH ₂ CH ₂ SiCl ₃
To obtain a compound represented by
HN (CH ₃ ) ₂
(In the above formula, p is an integer of 10 to 30, q is an integer of 10 to 30, and Hal is a halogen).

(Evaluation)
The static contact angle of water was measured for the surface treatment layer formed on the substrate surface in the above Examples and Comparative Examples. The static contact angle of water was measured with 1 μL of water using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd.).

  First, as an initial evaluation, after the surface treatment layer was formed, the static contact angle of water was measured with nothing touching the surface yet (the number of frictions was zero).

  Then, steel wool friction durability evaluation was implemented as friction durability evaluation. Specifically, the base material on which the surface treatment layer is formed is horizontally arranged, steel wool (count # 0000, dimensions 10 mm × 10 mm × 5 mm) is brought into contact with the exposed upper surface of the surface treatment layer, and a load of 1000 gf is applied thereon. After that, steel wool was reciprocated at a speed of 140 mm / sec with a load applied. The static contact angle (degree) of water was measured every 1000 reciprocations (the evaluation was stopped when the measured contact angle value was less than 100 degrees).

The results are shown in Table 1 and FIG. 1 (in the table, the symbol “-” is not measured).

As understood from Table 1 and FIG. 1, in Examples 1 to 3 using the perfluoropolyether group-containing silazane compound of the present invention having a substituted aminosilyl group, the perfluoropolyether group-containing silane having a methoxysilyl group Comparative Examples 4 and 5 using a perfluoropolyether group-containing silazane compound having a substituted aminosilyl group but having —CH ₂ OCH ₂ — in the main chain as compared with Comparative Examples 1 to 3 using the compound It was confirmed that the friction durability was remarkably improved as compared with.

  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 (10)

Any of the following general formulas (1a) and (1b):

(In these formulas, Rf ¹ represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms,
a, b, c and s are each independently an integer of 0 or more and 200 or less, the sum of a, b, c and s is at least 1, and a, b, c and s are attached in parentheses. The order of presence of each repeating unit is arbitrary in the formula,
d and f are 0 or 1,
e and g are integers of 0 or more and 2 or less,
m and l are integers of 1-10.
X represents a hydrogen atom or a halogen atom,
Y represents a hydrogen atom or a lower alkyl group,
Z represents a fluorine atom or a lower fluoroalkyl group,
T represents a dimethylamino group, a diethylamino group, or a diisopropylamino group ,
R ¹ represents an alkyl group having 1 to 22 carbon atoms, an alkoxy group having 1 to 22 carbon atoms or a hydroxyl group,
n is an integer of 1 or more and 3 or less. )
A perfluoropolyether group-containing silazane compound represented by: The perfluoropolyether group-containing silazane compound according to claim 1, wherein Rf ¹ is a C 1-16 perfluoroalkyl group. In the general formulas (1a) and (1b), Rf ¹ is a perfluoroalkyl group having 1 to 3 carbon atoms, and s = 0, b = 0, c = 0, d = 1, and f = 1. The perfluoropolyether group-containing silazane compound according to claim 1 or 2, wherein Z is a fluorine atom.   The perfluoropolyether group-containing silazane compound according to any one of claims 1 to 3, wherein n is 3 in the general formulas (1a) and (1b).   The surface treating agent containing the perfluoro polyether group containing silazane compound in any one of Claims 1-4. Any of the following general formulas (2a) and (2b):

(In these formulas, Rf ¹ represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms,
a, b, c and s are each independently an integer of 0 or more and 200 or less, the sum of a, b, c and s is at least 1, and a, b, c and s are attached in parentheses. The order of presence of each repeating unit is arbitrary in the formula,
d and f are 0 or 1,
e and g are integers of 0 or more and 2 or less,
m and l are integers of 1-10.
X represents a hydrogen atom or a halogen atom,
Y represents a hydrogen atom or a lower alkyl group,
Z represents a fluorine atom or a lower fluoroalkyl group,
T ′ represents a hydroxyl group or a hydrolyzable group (excluding a substituted amino group),
R ³ represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms,
n is an integer of 1 or more and 3 or less. )
The surface treatment agent according to claim 5, further comprising a perfluoropolyether group-containing silane compound represented by:   The surface treatment agent according to claim 5 or 6, which is used as an antifouling coating agent.   A layer formed on the surface of the substrate and the perfluoropolyether group-containing silazane compound according to any one of claims 1 to 4 or the surface treatment agent according to any one of claims 5 to 7 on the surface of the substrate. And articles containing.   The article according to claim 8, wherein the article is an optical member.   The article according to claim 8 or 9, wherein the substrate is glass or transparent plastic.

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