JP5354125B1 - Surface treatment agent for optical member and optical member - Google Patents

Abstract

（式中、Ｒ^１〜Ｒ^７は、それぞれ独立してアルキル基またはアリール基であり、Ｒｆはフルオロポリエーテル基であり、Ｘは２価の有機基であり、ａは１以上１０，０００以下、ｂは０以上１００以下であり、ｂが０でないときは、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、かつ、Ｙ^１およびＹ^２は水酸基または加水分解可能な基であり、ｂが０であるときは、Ｙ^１はＲｆ−Ｘ−で表される基であり、Ｙ^２は水酸基または加水分解可能な基である。）
【選択図】なしTo provide a novel surface treating agent for optical members capable of forming a layer having water repellency, oil repellency, antifouling property and high surface slipperiness.
A surface treating agent for an optical member comprising a fluoropolyether group-containing silicone compound represented by formula (I).

Wherein R ^{1 to} R ⁷ are each independently an alkyl group or an aryl group, Rf is a fluoropolyether group, X is a divalent organic group, and a is 1 or more and 10,000 or less. , B is 0 or more and 100 or less, and when b is not 0, the order of presence of each of the repeating units enclosed in parentheses is arbitrary in the formula, and Y ¹ and Y ² are hydroxyl groups or hydrolyzable When b is 0, Y ¹ is a group represented by Rf—X—, and Y ² is a hydroxyl group or a hydrolyzable group.)
[Selection figure] None

Description

  The present invention relates to a surface treating agent for optical members. The present invention also relates to an optical member obtained using such a surface treatment agent.

  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 US Pat. No. 6,265,515 JP 2007-177079 A JP-A-8-109580

  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 surface treatment agent containing a conventional perfluoropolyether group-containing silane compound is no longer necessarily sufficient to meet the demand for increasing surface slipperiness for optical members.

  An object of this invention is to provide a novel surface treating agent as what is used for the surface treatment of an optical member. Moreover, an object of this invention is to provide the optical member obtained using this surface treating agent.

As a compound that can be used as an antifouling agent, a fluoroalkyl group-containing silicone compound having a siloxane skeleton in the molecular main chain and a group represented by CF ₃ — in the molecular side chain is known (patent) See references 3-4). However, such a compound is not sufficient in terms of water repellency, oil repellency and antifouling properties required for optical members.

  On the other hand, in the field of fiber treatment, an amino group-containing polysiloxane, a fluorinated carboxylic acid alkyl ester compound and / or a (meth) acrylic acid fluorinated alkyl ester compound (perfluoroalkyl group and / or perfluoropolyether group). A composition for fiber treatment containing a reaction product obtained by reacting as a main component is known (see Patent Document 5). However, it is not known at all that the reaction product, which is the main component of the fiber treatment composition, is used for the surface treatment of the optical member.

  The present inventors have a siloxane skeleton at the molecular main chain, a fluoropolyether group at the molecular side chain (or one end), and a reactive silyl group at both molecular ends (or one end). The inventors have uniquely found that a fluoroalkyl group-containing silicone compound is particularly suitable for the surface treatment of an optical member, and have completed the present invention.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６およびＲ^７は、それぞれ独立してアルキル基またはアリール基であり、Ｒｆはフルオロポリエーテル基であり、Ｘは２価の有機基であり、ａは１以上１０，０００以下、ｂは０以上１００以下であり、ｂが０でないときは、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、かつ、Ｙ^１およびＹ^２は水酸基または加水分解可能な基であり、ｂが０であるときは、Ｙ^１はＲｆ−Ｘ−で表される基であり、Ｙ^２は水酸基または加水分解可能な基である。）
で表されるフルオロポリエーテル基含有シリコーン化合物を含む、光学部材用表面処理剤が提供される。 According to one aspect of the present invention, the following general formula (I):

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently an alkyl group or an aryl group, Rf is a fluoropolyether group, and X is 2 A is 1 or more and 10,000 or less, b is 0 or more and 100 or less, and when b is not 0, the order of presence of each repeating unit enclosed in parentheses is arbitrary in the formula Y ¹ and Y ² are a hydroxyl group or a hydrolyzable group, and when b is 0, Y ¹ is a group represented by Rf—X—, and Y ² is a hydroxyl group or a hydrolyzable group. It is a basic group.
The surface treatment agent for optical members containing the fluoropolyether group containing silicone compound represented by these is provided.

The fluoropolyether group-containing silicone compound represented by the general formula (I) includes a siloxane skeleton and a fluoropolyether group (Rf-) bonded to Si atoms forming the siloxane skeleton (via a divalent organic group X). ) and has a directly to the Si atom constituting the ends of the siloxane skeleton bonded hydroxyl group or a hydrolyzable group (at least -Y ² of -Y ¹ and -Y ^2). 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, directly to the Si atom bonded hydroxyl group or a hydrolyzable group (at least -Y ² of -Y ¹ and -Y ²⁾ contributes to the friction durability. Since the surface treating agent for optical members of the present invention contains such a fluoropolyether group-containing silicone compound and is used for surface treatment of optical members, it has water repellency, oil repellency and antifouling properties. In addition, a layer (surface treatment layer) having high surface slipperiness and friction durability can be applied to the optical member (more specifically, the base material). Furthermore, the surface treating agent for an optical member of the present invention can exhibit these functions even in a thin film, and substantially maintains the light transmittance or transparency of the optical member (more specifically, its base material). Can do.

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 8 - (OC 4 F 8}} ) k - (OC 3 F 6) l - (OC 2 F 4) m - (OCF 2) n -
Wherein R ⁸ 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 The following integers, 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 perfluoropolyether group represented by these may be sufficient.
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 -
(In the formula, l ′ is an integer of 1 to 200.)
The perfluoropolyether group represented by these may be sufficient.

In the above general formula (I), X represents the following formula:
_{- (CH 2) s -CONH- (} CH 2) t -
(In the formula, s is an integer of 0 to 10, and t is an integer of 2 to 10.)
It may be a group represented by

  According to still another aspect of the present invention, there is also provided an optical member comprising a base material and a layer (surface treatment layer) formed from the surface treatment agent for an optical member on the surface of the base material. . The layer in such an optical member has water repellency, oil repellency, antifouling properties, and high surface slipperiness.

  In the optical member of the present invention, the substrate may be glass or transparent plastic, for example. In the present invention, “transparent” may be anything that can be generally recognized as transparent, but for example, it means a haze value of 3% or less.

  According to the present invention, a novel surface treatment agent is provided for use in the surface treatment of an optical member, and the compound contained in the surface treatment agent contains a siloxane skeleton and Si atoms constituting the siloxane skeleton (indirectly). (Ii) having a bonded fluoropolyether group and a hydroxyl group or a hydrolyzable group directly bonded to the Si atom at the end of the siloxane skeleton, thereby having water repellency, oil repellency, antifouling property, In addition, a layer (surface treatment layer) having high surface slipperiness and friction durability can be applied to the optical member, and the optical transparency (more specifically, the base material) of the optical member (its base material) is improved. Can be substantially maintained. Furthermore, according to the present invention, an optical member to which such a surface treatment agent is applied is also provided.

  Hereinafter, although the surface treatment agent for optical members of this invention and the optical member obtained by applying this are explained in full detail, this invention is not limited to this.

-Fluoropolyether group containing silicone compound The surface treating agent for optical members of this invention contains the fluoropolyether group containing silicone compound represented by the following general formula (I).

In the general formula (I), R ^{1 to} R ⁷ 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 ⁷ 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.

  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 8 - (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 ⁸ is a C1-C16 (eg linear or branched alkyl group optionally substituted by one or more fluorine atoms, preferably one or A linear or branched alkyl group having 1 to 3 carbon atoms which may be substituted with more fluorine atoms, preferably, may be substituted with one or more fluorine atoms. The alkyl group is a fluoroalkyl group in which the terminal carbon atom is CF ₂ H— and all other carbon atoms are completely substituted with fluorine, or a perfluoroalkyl group, more preferably a perfluoroalkyl group (CF _{3 -, C 2 F 5 -,} C 3 F 7 - a).
k, l, m and n each represent the number of four types of repeating units of perfluoropolyether constituting the main skeleton of the polymer, and are each independently an integer of 0 to 200, 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) -, - (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 ))-. 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 -
The perfluoropolyether group represented by these may be sufficient. 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) s -CONH- (} CH 2) t -
It may be a group represented by In this formula, s is 0 or an integer of 1 to 10, preferably 0, and t is an integer of 2 to 10. 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 Rf is bonded, and the right end of the formula is bonded to Si).

  However, X is not limited to this, 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), Y ¹ and Y ² are a hydroxyl group or a hydrolyzable group (except when b described later is zero). 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 12 carbon atoms, preferably 1 to 12 carbon atoms, and -OA (alkoxy group) is preferable. 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 and bromomethyl 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.
In the compound of the present invention, the hydroxyl group or hydrolyzable group (Y ¹ and Y ² ) bonded to Si at the end of the siloxane skeleton can be bonded by reacting with the substrate and between the compounds. A compound having a group can exhibit excellent friction durability (for example, compared with silicone oil and fluorine-containing oil described later).

In the general formula (I), a is 1 or more and 10,000 or less, preferably 1 or more and 1000 or less, and b is 0 or more and 100 or less, preferably 0 or more and 50 or less, for example 1 or more and 50 or less. Focusing on only one compound, a and b are integers, but the surface treating agent for optical members of the present invention may contain a mixture of a plurality of compounds represented by the above general formula (I). In some cases, a and b may be real numbers representing the average composition of such a mixture. In addition, for convenience, the order of existence of each of the repeating units with parentheses a and b is described in a specific order in the formula, but the order of bonding of these repeating units is not limited to this, and is arbitrary. It is.
Such a compound having a siloxane skeleton can exhibit excellent surface slipperiness (or lubricity, for example, wiping of dirt such as fingerprints, and excellent touch feeling to fingers).

In the general formula (I), when b is zero, either Y ¹ or Y ² (Y ¹ ) is a group represented by Rf—X—, and the other (Y ² ) is a hydroxyl group or Any group capable of hydrolysis can be used. Such a compound is also directly bonded to the siloxane skeleton, the fluoropolyether group (Rf-) bonded to the Si atom forming the siloxane skeleton (via the divalent organic group X), and the Si atom forming the terminal of the siloxane skeleton. And a hydroxyl group or a hydrolyzable group (—Y ² ).

  The fluoropolyether group-containing silicone compound represented by the general formula (I) has been described above. Such a compound preferably has an average molecular weight of 1000 to 20000, 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 can be produced by any appropriate method.

（式中、Ｒ^１〜Ｒ^７、ａ、ｂ、ｔ、Ｙ^１、Ｙ^２は上記の通りである（但し、ｂがゼロである場合はＹ^１はＨである）。）で表される化合物を、以下の一般式（ＩＩＩ）：
Ｒｆ−（ＣＨ_２）_ｓ−ＣＯＯＲ^９ ・・・（ＩＩＩ）
（式中、Ｒｆおよびｓは上記の通りであり、Ｒ^９は水素原子または炭素数１〜５のアルキル基である。）で表される化合物とアミド結合形成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）_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）で表される基となる。 For example, the fluoropolyether group-containing silicone compound represented by the general formula (I) is represented by the following general formula (II):

(Wherein R ^{1 to} R ⁷ , a, b, t, Y ¹ and Y ² are as described above (provided that b is zero, Y ¹ is H)). The compound is represented by the following general formula (III):
^{_{Rf- (CH 2) s -COOR 9}} ··· (III)
(Wherein, Rf and s are as described above, R ⁹ is hydrogen atom or an alkyl group having 1 to 5 carbon atoms.) Can be obtained by subjecting a compound represented by the amide bond forming reaction .
Regarding the fluoropolyether group-containing silicone compound obtained by this example, in general formula (I), X represents 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).

  This amide bond formation reaction may proceed without a solvent or in a solvent. Examples of such solvents include perfluoroaliphatic hydrocarbons, aromatic hydrocarbons having a fluorine-containing substituent (for example, 1,3-bis (trifluoromethyl) benzene), hydrofluoroethers, and the like. Or in combination of two or more. The amide bond forming reaction can be carried out, for example, at 20 to 130 ° C., conveniently under normal pressure. When carrying out the amide bond forming reaction, it is preferable to add a perfluoropolyether compound dropwise to the silicone compound from the viewpoint of suppressing the generation of by-products.

  The fluoropolyether group-containing silicone compound represented by the general formula (I) has been described with reference to one production example, but the fluoropolyether group-containing silicone compound usable in the present invention is produced by this example. It is not limited to the ones.

  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 for optical members The surface treatment agent for optical members of the present invention (or a surface treatment composition, hereinafter also simply referred to as a surface treatment agent) may be any as long as it contains the above-described fluoropolyether group-containing silicone compound. .

  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 a surface treatment layer can be formed, it is suitably used as an antifouling coating agent for optical members.

  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 four types of repeating units of perfluoropolyether constituting the main skeleton of the polymer, each independently an integer of 0 to 300, For example, it is an integer of 1 to 300, and the sum of k ″, l ″, m ″ and n ″ is at least 1, preferably 1 to 100. The order of presence of each repeating unit with the subscript k ″, l ″, m ″ or 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. The order of presence of each repeating unit in parentheses with subscripts 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, more preferably 3000 to 30000. Thereby, high surface slipperiness can be obtained.

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

  In the surface treatment agent of the present invention, the perfluoropolyether group-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４種の繰り返し単位数をそれぞれ表し、互いに独立して０以上２００以下の整数、例えば１以上２００以下の整数であって、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または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, 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 four types of repeating units of perfluoropolyether constituting the main skeleton of the polymer, and are each independently an integer of 0 to 200, for example, an integer of 1 to 200 And the sum of k, l, m and n is at least 1, preferably 1-100. The order of presence of each repeating unit with the subscripts k, l, m or 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４種の繰り返し単位数をそれぞれ表し、互いに独立して０以上２００以下の整数、例えば１以上２００以下の整数であって、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または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 four types of repeating units of perfluoropolyether constituting the main skeleton of the polymer, and are each independently an integer of 0 to 200, for example, an integer of 1 to 200 And the sum of k, l, m and n is at least 1, preferably 1-100. The order of presence of each repeating unit with the subscripts k, l, m or 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 ′} −
(In the formula, l ′ is an integer of 1 to 200, preferably an integer of 1 to 100.)
Or _{- (OCF 2 CF 2 CF 2} CF 2) k '- (OCF 2 CF 2 CF 2) l' - (OCF 2 CF 2) m '- (OCF 2) n' -
(Wherein k ′ and l ′ are integers of 1 or more and 30 or less, m ′ and n ′ are integers of 1 or more and 300 or less, and subscripts k ′, l ′, m ′ or n ′ are added. The order of presence of each repeating unit in parentheses is arbitrary in the formula.)
It may be.
Further, typically, Z ′ is a fluorine atom and 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.

-Optical member Next, the optical member obtained using this surface treating agent is demonstrated. The optical member of the present invention includes a substrate and a layer (surface treatment layer) formed from the surface treatment agent on the surface of the substrate. This optical member can be manufactured as follows, for example.

First, a base material is prepared. Regarding the base material usable in the present invention, the material constituting the surface of the base material may be an optical member material such as glass or transparent plastic. Further, 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 optical member is an optical glass component for a touch panel, a thin film using a transparent electrode, for example, indium tin oxide (ITO) or indium zinc oxide is provided on a part of the surface of the base material (glass). Also good. 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 may be appropriately determined according to the use and specific specifications of the optical member 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 a material include glass, and a material on which a natural oxide film or a thermal oxide film is formed on the surface. 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. Note that when Y ¹ and Y ² of the compound represented by the general formula (I) are all hydroxyl groups, the 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, the groups (or hydroxyl groups) bonded to Si after hydrolysis are rapidly exchanged between the fluoropolyether group-containing silicone compounds (and perfluoropolyether group-containing silane compounds, if present). To dehydrate. Moreover, between such a compound and a base material, it reacts rapidly between the group (or hydroxyl group) bonded to Si after hydrolysis of the compound and a reactive group present on the surface of the base material. When the reactive group present on the surface is a hydroxyl group, it undergoes dehydration condensation. (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 the friction durability, but is not essential for producing the optical member 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 optical member 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.

  Examples of optical members include: lenses such as eyeglasses; front protective plates, antireflection plates, polarizing plates, and antiglare plates for displays such as PDP and LCD; for devices such as mobile phones and portable information terminals. Touch panel sheet; Disc surface of an optical disc such as a Blu-ray (registered trademark) disc, DVD disc, CD-R, MO;

  The thickness of the surface treatment layer is not particularly limited. The thickness of the surface treatment layer in the optical member 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.

  The optical member obtained by using the surface treating agent for an optical member of the present invention has been described in detail above. In addition, the usage method of the surface treating agent for optical members of this invention, the manufacturing method of an optical member, etc. are not limited to what was illustrated above.

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

(Example)
As Examples 1 to 3, fluoropolyether group-containing silicone compounds were synthesized in the following Synthesis Examples 1 to 3, respectively, and surface treatment agents for optical members were prepared using the compounds obtained from these, A surface treatment layer was formed.

（式中、ａは７であり、ｂは２である。）で表されるアミノ基含有ポリシロキサン５．９ｇを撹拌下に窒素ガスを導入しながら１時間で滴下した。滴下終了後、更に８０℃で２時間攪拌し、続いて減圧下で溶媒などを留去して、以下の式で表される化合物１を得た。

（式中、ａは７であり、ｂは２である。） Synthesis example 1
An average composition CF ₃ CF ₂ CF ₂ O- (CF ₂ CF ₂ CF ₂ O) ₁₀ -CF was added to a 200 mL four-necked flask equipped with a reflux condenser, a thermometer, a stirrer, a dropping funnel and a nitrogen gas inlet tube. 10 g of perfluoropolyether-modified alkyl ester represented by ₂ CF ₂ —COOCH ₂ CH ₃ and 30 g of m-xylene hexafluoride (solvent) were charged. After heating up to 80 ° C, the following average composition

(In the formula, a is 7 and b is 2.) 5.9 g of an amino group-containing polysiloxane represented by the formula was added dropwise over 1 hour while introducing nitrogen gas with stirring. After completion of the dropwise addition, the mixture was further stirred at 80 ° C. for 2 hours, and then the solvent and the like were distilled off under reduced pressure to obtain Compound 1 represented by the following formula.

(Wherein a is 7 and b is 2)

（式中、ａは７であり、ｂは２である。） Synthesis example 2
An average composition of CF ₃ CF ₂ CF ₂ O- (CF ₂ CF ₂ CF ₂ O) ₂₄ -CF was added to a 200 mL four-necked flask equipped with a reflux condenser, thermometer, stirrer, dropping funnel and nitrogen gas inlet tube. 20.5 g of a perfluoropolyether-modified alkyl ester represented by ₂ CF ₂ —COOCH ₂ CH ₃ and 60 g of m-xylene hexafluoride (solvent) were charged. After the temperature was raised to 80 ° C., 3.9 g of the same amino group-containing polysiloxane used in Synthesis Example 1 was added dropwise thereto over 1 hour while introducing nitrogen gas with stirring. After completion of the dropwise addition, the mixture was further stirred at 80 ° C. for 3 hours, and then the solvent and the like were distilled off under reduced pressure to obtain Compound 2 represented by the following formula.

(Wherein a is 7 and b is 2)

（式中、ａは７であり、ｂは２である。） Synthesis example 3
An average composition of CF ₃ CF ₂ CF ₂ O- (CF ₂ CF ₂ CF ₂ O) ₃₅ -CF was added to a 200 mL four-necked flask equipped with a reflux condenser, thermometer, stirrer, dropping funnel and nitrogen gas inlet tube. A perfluoropolyether-modified alkyl ester 31 g represented by ₂ CF ₂ —COOCH ₂ CH ₃ and 60 g of m-xylene hexafluoride (solvent) were charged. After the temperature was raised to 80 ° C., 7.6 g of the same amino group-containing polysiloxane used in Synthesis Example 1 was added dropwise thereto over 1 hour while introducing nitrogen gas with stirring. After completion of the dropwise addition, the mixture was further stirred at 80 ° C. for 5 hours, and then the solvent and the like were distilled off under reduced pressure to obtain Compound 3 represented by the following formula.

(Wherein a is 7 and b is 2)

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

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

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

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

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

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

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

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

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

  The present invention is used to form a surface treatment layer on the surface of an optical member (more specifically, its base material).

Claims (6)

The following general formula (I):

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently an alkyl group or an aryl group, Rf is a fluoropolyether group, and X is 2 A is 1 or more and 10,000 or less, b is 0 or more and 100 or less, and when b is not 0, the order of presence of each repeating unit enclosed in parentheses is arbitrary in the formula Y ¹ and Y ² are a hydroxyl group or a hydrolyzable group, and when b is 0, Y ¹ is a group represented by Rf—X—, and Y ² is a hydroxyl group or a hydrolyzable group. It is a basic group.
The surface treatment agent for optical members containing the fluoropolyether group containing silicone compound represented by these. In the general formula (I), Rf is the following formula:
_{^{R 8 - (OC 4 F 8}} ) k - (OC 3 F 6) l - (OC 2 F 4) m - (OCF 2) n -
Wherein R ⁸ 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 The following integers, 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 surface treating agent according to claim 1, which is a perfluoropolyether group represented by: 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 -
(In the formula, l ′ is an integer of 1 to 200.)
The surface treating agent according to claim 2, which is a perfluoropolyether group represented by the formula: 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 to 10, and t is an integer of 2 to 10.)
The surface treating agent in any one of Claims 1-3 which is group represented by these.   The optical member containing a base material and the layer formed from the surface treating agent for optical members in any one of Claims 1-4 on the surface of this base material.   The optical member according to claim 5, wherein the base material is glass or transparent plastic.