JP6582652B2 - Surface treatment agent - Google Patents

Description

  The present invention relates to a surface treatment agent, specifically, a surface treatment agent comprising a perfluoro (poly) ether group-containing silane 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 “surface treatment layer”) is applied as a so-called functional thin film to various substrates such as glass, plastic, fiber, and building members. ing.

  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. It has been. For example, Patent Documents 1 and 2 describe a perfluoropolyether group-containing silane compound having a hydrolyzable group bonded to a Si atom at the molecular terminal or terminal part.

International Publication No. 97/07155 Special table 2008-534696 gazette

  When the perfluoropolyether group-containing silane compound as described above is applied to a substrate, the silane moiety of the perfluoropolyether group-containing silane compound is hydrolyzed and reacts with reactive groups present on the substrate surface. To do. As a result, a bond is formed between the perfluoropolyether group-containing silane compound and the substrate, and the perfluoropolyether group-containing silane compound is fixed on the substrate. However, the present inventors have found that when some silane sites are hydrolyzed during storage and the reactivity of the silane sites is lost due to bonding with other molecules, etc., when applied to the substrate surface, It has been found that there is a possibility that functions such as friction durability of the obtained surface treatment layer may be deteriorated without reacting with a reactive group on the material.

  An object of the present invention is to provide a surface treatment agent comprising a perfluoro (poly) ether group-containing silane compound having excellent storage stability.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by reducing the moisture in the surface treatment agent as much as possible, and a surface treatment comprising a perfluoro (poly) ether group-containing silane compound. It has been found that the storage stability of the surface treatment agent is improved by incorporating a silane compound that supplements moisture in the surface treatment agent into the agent, and the present invention has been completed.

［式中：
ＰＦＰＥは、各出現においてそれぞれ独立して、式：
−（ＯＣ_４Ｆ_８）_ａ−（ＯＣ_３Ｆ_６）_ｂ−（ＯＣ_２Ｆ_４）_ｃ−（ＯＣＦ_２）_ｄ−
（式中、ａ、ｂ、ｃおよびｄは、それぞれ独立して、０〜２００の整数であって、ａ、ｂ、ｃおよびｄの和は少なくとも１であり、添字ａ、ｂ、ｃまたはｄ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。）
で表される基であり；
Ｒｆは、各出現においてそれぞれ独立して、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；
Ｒ^１は、各出現においてそれぞれ独立して、水素原子または炭素数１〜２２のアルキル基を表し；
Ｒ^２は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
Ｒ^１１は、各出現においてそれぞれ独立して、水素原子またはハロゲン原子を表し；
Ｒ^１２は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
ｎは、（−ＳｉＲ^１ _ｎＲ^２ _３−ｎ）単位毎に独立して、０〜３の整数であり；
ただし、式（Ａ１）、（Ａ２）、（Ｂ１）および（Ｂ２）において、少なくとも１つのＲ^２が存在し；
Ｘ^１は、それぞれ独立して、単結合または２〜１０価の有機基を表し；
Ｘ^２は、各出現においてそれぞれ独立して、単結合または２価の有機基を表し；
ｔは、各出現においてそれぞれ独立して、１〜１０の整数であり；
αは、それぞれ独立して、１〜９の整数であり；
α’は、それぞれ独立して、１〜９の整数であり；
Ｘ^５は、それぞれ独立して、単結合または２〜１０価の有機基を表し；
βは、それぞれ独立して、１〜９の整数であり；
β’は、それぞれ独立して、１〜９の整数であり；
Ｘ^７は、それぞれ独立して、単結合または２〜１０価の有機基を表し；
γは、それぞれ独立して、１〜９の整数であり；
γ’は、それぞれ独立して、１〜９の整数であり；
Ｒ^ａは、各出現においてそれぞれ独立して、−Ｚ−ＳｉＲ^７１ _ｐＲ^７２ _ｑＲ^７３ _ｒを表し；
Ｚは、各出現においてそれぞれ独立して、酸素原子または２価の有機基を表し；
Ｒ^７１は、各出現においてそれぞれ独立して、Ｒ^ａ’を表し；
Ｒ^ａ’は、Ｒ^ａと同意義であり；
Ｒ^ａ中、Ｚ基を介して直鎖状に連結されるＳｉは最大で５個であり；
Ｒ^７２は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
Ｒ^７３は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
ｐは、各出現においてそれぞれ独立して、０〜３の整数であり；
ｑは、各出現においてそれぞれ独立して、０〜３の整数であり；
ｒは、各出現においてそれぞれ独立して、０〜３の整数であり；
ただし、一のＲ^ａにおいて、ｐ、ｑおよびｒの和は３であり、式（Ｃ１）および（Ｃ２）において、少なくとも１つのＲ^７２が存在し；
Ｒ^ｂは、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
Ｒ^ｃは、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
ｋは、各出現においてそれぞれ独立して、１〜３の整数であり；
ｌは、各出現においてそれぞれ独立して、０〜２の整数であり；
ｍは、各出現においてそれぞれ独立して、０〜２の整数であり；
ただし、γを付して括弧でくくられた単位において、ｋ、ｌおよびｍの和は３である。］
のいずれかで表される少なくとも１種のパーフルオロ（ポリ）エーテル基含有シラン化合物、
および
下記式（Ｓ）：
ＳｉＲ^５１ _ｎＲ^６１ _４−ｎ
［式中：
Ｒ^５１は、それぞれ独立して、水素原子または炭素数１〜２０の有機基であるか、あるいは２つのＲ^５１が、＝ＣＲ^５７ _２を構成してもよく；
Ｒ^５７は、それぞれ独立して、水素原子または炭素数１〜２０の有機基であり；
Ｒ^６１は、それぞれ独立して、加水分解性基であり；
ｎは０〜３の整数である。］
で表される少なくとも１種のシラン化合物を含む表面処理剤が提供される。 That is, according to the first aspect of the present invention, the following general formulas (A1), (A2), (B1), (B2), (C1) and (C2):

[Where:
PFPE has the formula:
_{- (OC 4 F 8) a} - (OC 3 F 6) b - (OC 2 F 4) c - (OCF 2) d -
Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d The order of existence of each repeating unit with parentheses attached with is arbitrary in the formula.)
A group represented by:
Rf represents each independently an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
R ² represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group;
R ¹¹ independently represents a hydrogen atom or a halogen atom at each occurrence;
R ¹² independently represents a hydrogen atom or a lower alkyl group at each occurrence;
n ^{_{is, (- SiR 1 n R 2}} 3-n) independently for each unit, an integer from 0 to 3;
Provided that in formulas (A1), (A2), (B1) and (B2), at least one R ² is present;
Each X ¹ independently represents a single bond or a divalent to 10-valent organic group;
X ² represents each independently a single bond or a divalent organic group at each occurrence;
t is independently an integer from 1 to 10 at each occurrence;
each α is independently an integer from 1 to 9;
α ′ is each independently an integer of 1 to 9;
X ⁵ each independently represents a single bond or a divalent to 10-valent organic group;
each β is independently an integer from 1 to 9;
each β ′ is independently an integer from 1 to 9;
X ⁷ each independently represents a single bond or a divalent to 10-valent organic group;
each γ is independently an integer of 1 to 9;
each γ ′ is independently an integer from 1 to 9;
R ^a independently represents —Z—SiR ⁷¹ _p R ⁷² _q R ⁷³ _r at each occurrence;
Z represents, independently at each occurrence, an oxygen atom or a divalent organic group;
R ⁷¹ independently represents R ^{a ′} at each occurrence;
R ^{a ′} is synonymous with R ^a ;
In R ^a , the maximum number of Si linearly linked via the Z group is 5;
R ⁷² independently represents at each occurrence a hydroxyl group or a hydrolyzable group;
R ⁷³ independently represents at each occurrence a hydrogen atom or a lower alkyl group;
p is independently an integer from 0 to 3 at each occurrence;
q is independently an integer from 0 to 3 at each occurrence;
r is independently an integer from 0 to 3 at each occurrence;
However, in one R ^a , the sum of p, q and r is 3, and in formulas (C1) and (C2), there is at least one R ⁷² ;
R ^b independently represents a hydroxyl group or a hydrolyzable group at each occurrence;
R ^c independently represents a hydrogen atom or a lower alkyl group at each occurrence;
k is independently an integer from 1 to 3 at each occurrence;
l is independently an integer from 0 to 2 at each occurrence;
m is independently an integer from 0 to 2 at each occurrence;
However, the sum of k, l, and m is 3 in the unit enclosed in parentheses with γ. ]
At least one perfluoro (poly) ether group-containing silane compound represented by any of the following:
And the following formula (S):
SiR ⁵¹ _n R ⁶¹ _4-n
[Where:
Each R ⁵¹ is independently a hydrogen atom or an organic group having 1 to 20 carbon atoms, or two R ^{51 s} may constitute = CR ⁵⁷ ₂ ;
Each of R ⁵⁷ is independently a hydrogen atom or an organic group having 1 to 20 carbon atoms;
Each R ⁶¹ is independently a hydrolyzable group;
n is an integer of 0-3. ]
The surface treating agent containing at least 1 sort (s) of silane compound represented by these is provided.

  According to the 2nd summary of this invention, the pellet containing the said surface treating agent is provided.

  According to the third aspect of the present invention, there is provided an article comprising a base material and a layer formed on the surface of the base material from the surface treatment agent.

  According to the present invention, by adding a silane compound having a hydrolyzable group to a surface treatment agent comprising a perfluoro (poly) ether group-containing silane compound, a surface treatment agent having excellent storage stability is obtained. Can be provided.

  Hereinafter, the surface treating agent of the present invention will be described.

  As used herein, “hydrocarbon group” refers to a group containing carbon and hydrogen, wherein one hydrogen atom is eliminated from a hydrocarbon. Such hydrocarbon group is not particularly limited, but may be a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by one or more substituents, such as an aliphatic hydrocarbon group, An aromatic hydrocarbon group etc. are mentioned. The “aliphatic hydrocarbon group” may be linear, branched or cyclic, and may be either saturated or unsaturated. The hydrocarbon group may also contain one or more ring structures. Such a hydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy and the like at its terminal or molecular chain.

As used herein, the substituent of the “hydrocarbon group” is not particularly limited, but includes, for example, a halogen atom; C _1-6 alkyl optionally substituted by one or more halogen atoms Group, C _2-6 alkenyl group, C _2-6 alkynyl group, C _3-10 cycloalkyl group, C _3-10 unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, 5-10 membered unsaturated heterocyclyl And one or more groups selected from a group, a C _6-10 aryl group and a 5-10 membered heteroaryl group.

  As used herein, “organic group” means a group containing carbon. The organic group is not particularly limited, but may be a hydrocarbon group. The “2 to 10 valent organic group” means a 2 to 10 valent group containing carbon. Although it does not specifically limit as this 2-10 valent organic group, The 2-10 valent group which further removed 1-9 hydrogen atoms from the hydrocarbon group is mentioned. For example, the divalent organic group is not particularly limited, and examples thereof include a divalent group in which one hydrogen atom is further eliminated from a hydrocarbon group.

のいずれかで表される少なくとも１種のパーフルオロ（ポリ）エーテル基含有シラン化合物を含む。 The surface treating agent of the present invention has the following formulas (A1), (A2), (B1), (B2), (C1) and (C2):

At least one perfluoro (poly) ether group-containing silane compound represented by any one of:

  The perfluoro (poly) ether group-containing silane compounds represented by the above formulas (A1), (A2), (B1), (B2), (C1) and (C2) will be described below.

Formulas (A1) and (A2):

In the above formula, PFPE is-(OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- (OC ₂ F ₄ ) _c- (OCF ₂ ) _d- and corresponds to a perfluoro (poly) ether group To do. Here, a, b, c and d are each independently 0 or an integer of 1 or more, and the sum of a, b, c and d is at least 1. Preferably, a, b, c and d are each independently an integer of 0 or more and 200 or less, for example, an integer of 1 to 200, more preferably an integer of 0 or more and 100 or less. Preferably, the sum of a, b, c and d is 5 or more, more preferably 10 or more, for example 10 or more and 100 or less. Further, the order of presence of each repeating unit with a, b, c or d 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 ))-. good, preferably _{- (OCF 2 CF 2 CF 2} ) - a. Further,-(OC ₂ F ₄ )-may be either-(OCF ₂ CF ₂ )-or-(OCF (CF ₃ ))-, preferably-(OCF ₂ CF ₂ )-. is there.

In one embodiment, PFPE is — (OC ₃ F ₆ ) _b — (wherein b is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200). Preferably,-(OCF ₂ CF ₂ CF ₂ ) _b- (wherein b is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200) or-(OCF (CF ₃ ) CF ₂ ) _b — (wherein b is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200), more preferably — (OCF ₂ CF ₂ CF ₂ ) _b- (in the formula, b is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200).

In another embodiment, PFPE _{is, - (OC 4 F 8)} a - (OC 3 F 6) b - (OC 2 F 4) c - (OCF 2) d - ( wherein, a and b are each independently And c and d are each independently an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200, and the subscripts a, b, c or the order of the repeating units in parentheses are given the d is optional is in the formula), preferably _{- (OCF 2 CF 2 CF 2} CF 2) a - (OCF 2 CF 2 CF _{2) b - (OCF 2 CF} 2) c - (OCF 2) d - a. In one embodiment, PFPE _{is, - (OC 2 F 4)} c - (OCF 2) d - ( wherein, c and d are 1 to 200 independently, preferably 5 to 200, more preferably Is an integer of 10 or more and 200 or less, and the order of presence of each repeating unit in parentheses with the subscript c or d is arbitrary in the formula).

In one embodiment, the _{- (OC 4 F 8) a} - (OC 3 F 6) b - (OC 2 F 4) c - (OCF 2) d - in the ratio of c with respect to d (hereinafter, "c / The lower limit of “d ratio” is 0.2, preferably 0.3, and the upper limit of c / d ratio is 1.5, preferably 1.3, more preferably 1.1, still more preferably 0. .9. By setting the c / d ratio to 1.5 or less, the slipperiness and friction durability of the surface treatment layer obtained from this compound are further improved. The smaller the c / d ratio, the more the slipperiness and friction durability of the surface treatment layer are improved. On the other hand, when the c / d ratio is 0.2 or more, the stability of the compound can be further increased. The greater the c / d ratio, the better the compound stability.

In yet another embodiment, PFPE ^{_{is, - (OC 2 F 4 -R}} 8) n "-. A group represented in ^{formula, R} 8 _{is, OC 2 F 4, OC 3} F 6 and _OC 4 F ₈ is a group selected from, or independent of _{.OC 2 F 4, OC 3 F} 6 and _OC 4 _{F 8} is a combination of two or three groups independently selected from these groups Examples of the combination of 2 or 3 groups selected are not particularly limited, for example, _{-OC 2 F 4 OC 3 F 6} -, - OC 2 F 4 OC 4 F 8 -, - OC 3 F 6 OC 2 F 4 _{-, - OC 3 F 6 OC} 3 F 6 -, - OC 3 F 6 OC 4 F 8 -, - OC 4 F 8 OC 4 F 8 -, - OC 4 F 8 OC 3 F 6 -, - OC 4 F _{8 OC 2 F 4 -, -} OC 2 F 4 OC 2 F 4 OC _{F 6 -, - OC 2 F} 4 OC 2 F 4 OC 4 F 8 -, - OC 2 F 4 OC 3 F 6 OC 2 F 4 -, - OC 2 F 4 OC 3 F 6 OC 3 F 6 -, - _{OC 2 F 4 OC 4 F 8} OC 2 F 4 -, - OC 3 F 6 OC 2 F 4 OC 2 F 4 -, - OC 3 F 6 OC 2 F 4 OC 3 F 6 -, - OC 3 F 6 OC ₃ F ₆ OC ₂ F ₄ —, —OC ₄ F ₈ OC ₂ F ₄ OC ₂ F ₄ — and the like. The above n ″ is an integer of 2 to 100, preferably an integer of 2 to 50. In the above formula, OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ may be either linear or branched, preferably linear. In this embodiment, PFPE is _{preferably, - (OC 2 F 4 -OC} 3 F 6) n "- or _{- (OC 2 F 4 -OC 4} F 8) n" - is.

  In the above formula, Rf represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms.

  The “alkyl group having 1 to 16 carbon atoms” in the alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms may be linear or branched. Preferably, it is a linear or branched alkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, and more preferably a linear alkyl group having 1 to 3 carbon atoms.

Rf is preferably an alkyl group having 1 to 16 carbon atoms substituted by one or more fluorine atoms, more preferably a CF ₂ H—C _1-15 fluoroalkylene group, and still more preferably Is a C 1-16 perfluoroalkyl group.

The C 1-16 perfluoroalkyl group may be linear or branched, and is preferably linear or branched, having 1 to 6 carbon atoms, particularly 1 to 1 carbon atoms. 3 perfluoroalkyl group, more preferably a linear perfluoroalkyl group having 1 to 3 carbon atoms, specifically —CF ₃ , —CF ₂ CF ₃ , or —CF ₂ CF ₂ CF ₃ . .

In the above formula, each R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.

In the above formula, R ² independently represents a hydroxyl group or a hydrolyzable group at each occurrence.

The “hydrolyzable group” as used herein means a group capable of leaving from the main skeleton of a compound by a hydrolysis reaction. Examples of the hydrolyzable group include —OR, —OCOR, —O—N═CR ₂ , —NR ₂ , —NHR, halogen (in these formulas, R represents a substituted or unsubstituted carbon atom having 1 to 4 carbon atoms). And the like, preferably -OR (that is, an alkoxy group). Examples of R include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; substituted alkyl groups such as chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl 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 above formulas, R ¹¹ independently represents a hydrogen atom or a halogen atom at each occurrence. The halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom, more preferably a fluorine atom.

In the above formula, R ¹² each independently represents a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.

In the above formulas, ^{_{n, (- SiR 1 n R 2}} 3-n) independently for each unit, an integer of 0 to 3, preferably 0 to 2, more preferably 0. However, in the formula, all n are not 0 simultaneously. In other words, at least one R ² is present in the formula.

In the above formula, each X ¹ independently represents a single bond or a divalent to 10-valent organic group. The X ¹ is a perfluoropolyether part (ie, Rf-PFPE part or -PFPE part) mainly providing water repellency and surface slipperiness in the compounds represented by the formulas (A1) and (A2). And a silane moiety (that is, a group parenthesized with α) that provides the binding ability to the base material. Therefore, X ¹ may be any organic group as long as the compounds represented by formulas (A1) and (A2) can exist stably.

In said formula, (alpha) is an integer of 1-9 and (alpha) 'is an integer of 1-9. These α and α ′ can vary depending on the valence of X ¹ . In the formula (A1), the sum of α and α ′ is the same as the valence of X ¹ . For example, when X ¹ is a 10-valent organic group, the sum of α and α ′ is 10, for example, α is 9 and α ′ is 1, α is 5 and α ′ is 5, or α is 1 and α 'Can be nine. Further, when X ¹ is a divalent organic group, α and α ′ are 1. In formula (A2), alpha is a value obtained by subtracting 1 from the valence of X ^1.

X ¹ is preferably 2 to 7 valent, more preferably 2 to 4 valent, and still more preferably a divalent organic group.

In one embodiment, X ¹ is a divalent to tetravalent organic group, α is 1 to 3, and α ′ is 1.

In another embodiment, X ¹ is a divalent organic group, α is 1 and α ′ is 1. In this case, the formulas (A1) and (A2) are represented by the following formulas (A1 ′) and (A2 ′).

Examples of X ¹ are not particularly limited, but for example, the following formula:
_{^{- (R 31) p '-}} (X a) q' -
[Where:
R ³¹ represents a single bond, — (CH ₂ ) _{s ′} — or o-, m- or p-phenylene group, preferably — (CH ₂ ) _{s ′} —
s ′ is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and even more preferably 1 or 2.
X ^{a _{is, - (X b) l '}} - represents,
X ^b is independently at each occurrence, —O—, —S—, o—, m- or p-phenylene group, —C (O) O—, —Si (R ³³ ) ₂ —, — ( Si (R ³³ ) ₂ O) _{m ′} —Si (R ³³ ) ₂ —, —CONR ³⁴ —, —O—CONR ³⁴ —, —NR ³⁴ — and — (CH ₂ ) _{n ′} —. Represents a group,
R ³³ each independently represents a phenyl group, a C _1-6 alkyl group or a C _1-6 alkoxy group, preferably a phenyl group or a C _1-6 alkyl group, and more preferably a methyl group. And
R ³⁴ each independently represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group (preferably a methyl group) at each occurrence;
m ′ is independently an integer of 1 to 100, preferably an integer of 1 to 20, at each occurrence.
n 'is independently an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, at each occurrence.
l ′ is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3,
p ′ is 0 or 1;
q ′ is 0 or 1,
Here, at least one of p ′ and q ′ is 1, and the order of presence of each repeating unit in parentheses attached with p ′ or q ′ is arbitrary]
The bivalent group represented by these is mentioned. Here, R ³¹ and X ^a (typically ^a hydrogen atom of R ³¹ and X ^a ) are one or more selected from a fluorine atom, a C _1-3 alkyl group, and a C _1-3 fluoroalkyl group. It may be substituted with a substituent.

Preferably, X ¹ is — (R ³¹ ) _{p ′} — (X ^a ) _{q ′} —R ³² —. R ³² represents a single bond, — (CH ₂ ) _{t ′} — or o-, m- or p-phenylene group, preferably — (CH ₂ ) _{t ′} —. t ′ is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably an integer of 2 to 3. Here, R ³² (typically a hydrogen atom of R ³² ) is substituted with one or more substituents selected from a fluorine atom, a C _1-3 alkyl group and a C _1-3 fluoroalkyl group. It may be.

Preferably, X ¹ is
A C _1-20 alkylene group,
-R ³¹ -X ^c -R ³² - or ^-X d ^{-R 32,} -
[Wherein, R ³¹ and R ³² are as defined above. ]
It can be.

More preferably, said X ¹ is
A C _1-20 alkylene group,
_{- (CH 2) s' -X} c -,
_{- (CH 2) s '-X} c - (CH 2) t' -
-X ^d- , or -X ^d- (CH ₂ ) _{t '} -
[Wherein, s ′ and t ′ are as defined above]. ]
It is.

In the above formula, X ^c is
-O-,
-S-,
-C (O) O-,
-CONR ³⁴ -,
-O-CONR ³⁴ -,
-Si (R ³³ ) _2- ,
_{^{- (Si (R 33) 2}} O) m '-Si (R 33) 2 -,
_{-O- (CH 2) u '-} (Si (R 33) 2 O) m' -Si (R 33) 2 -,
_{-O- (CH 2) u '-Si} (R 33) 2 -O-Si (R 33) 2 -CH 2 CH 2 -Si (R 33) 2 -O-Si (R 33) 2 -,
_{-O- (CH 2) u '-Si} (OCH 3) 2 OSi (OCH 3) 2 -,
—CONR ³⁴ — (CH ₂ ) _{u ′} — (Si (R ³³ ) ₂ O) _{m ′} —Si (R ³³ ) ₂ —,
_{^{-CONR 34 - (CH 2) u}} '-N (R 34) -, or ^-CONR 34 - (o-, m- or p- _phenylene) -Si ^(R 33) ₂ -
[Wherein, R ³³ , R ³⁴ and m ′ are as defined above;
u ′ is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably an integer of 2 to 3. ]. X ^c is preferably —O—.

In the above formula, X ^d is
-S-,
-C (O) O-,
-CONR ³⁴ -,
—CONR ³⁴ — (CH ₂ ) _{u ′} — (Si (R ³³ ) ₂ O) _{m ′} —Si (R ³³ ) ₂ —,
_{^{-CONR 34 - (CH 2) u}} '-N (R 34) -, or ^-CONR 34 - (o-, m- or p- _phenylene) -Si ^(R 33) ₂ -
[Wherein each symbol is as defined above. ]
Represents.

More preferably, said X ¹ is
A C _1-20 alkylene group,
_{- (CH 2) s' -X} c - (CH 2) t '-, or _{^{-X d - (CH 2) t}} ' -
[Wherein each symbol is as defined above. ]
It can be.

Even more preferably, said X ¹ is
A C _1-20 alkylene group,
_{- (CH 2) s '-O-} (CH 2) t' -,
_{- (CH 2) s' -} (Si (R 33) 2 O) m '-Si (R 33) 2 - (CH 2) t' -,
_{- (CH 2) s '-O-} (CH 2) u' - (Si (R 33) 2 O) m '-Si (R 33) 2 - (CH 2) t' -, or - _(CH 2) _{s' -O- (CH 2) t} '-Si (R 33) 2 - (CH 2) u' -Si (R 33) 2 - (C v H 2v) -
[Wherein, R ³³ , m ′, s ′, t ′ and u ′ are as defined above, and v is an integer of 1-20, preferably an integer of 2-6, more preferably 2-3]. It is an integer. ]
It is.

In the above formula, — (C _v H _2v ) — may be linear or branched. For example, —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH It may be (CH ₃ ) —, —CH (CH ₃ ) CH ₂ —.

The X ¹ group is substituted with one or more substituents selected from a fluorine atom, a C _1-3 alkyl group and a C _1-3 fluoroalkyl group (preferably a C _1-3 perfluoroalkyl group). May be.

［式中、Ｒ^４１は、それぞれ独立して、水素原子、フェニル基、炭素数１〜６のアルキル基、またはＣ_１−６アルコキシ基、好ましくはメチル基であり；
Ｄは、
−ＣＨ_２Ｏ（ＣＨ_２）_２−、
−ＣＨ_２Ｏ（ＣＨ_２）_３−、
−ＣＦ_２Ｏ（ＣＨ_２）_３−、
−（ＣＨ_２）_２−、
−（ＣＨ_２）_３−、
−（ＣＨ_２）_４−、
−ＣＯＮＨ−（ＣＨ_２）_３−、
−ＣＯＮ（ＣＨ_３）−（ＣＨ_２）_３−、
−ＣＯＮ（Ｐｈ）−（ＣＨ_２）_３−（式中、Ｐｈはフェニルを意味する）、および

（式中、Ｒ^４２は、それぞれ独立して、水素原子、Ｃ_１−６のアルキル基またはＣ_１−６のアルコキシ基、好ましくはメチル基またはメトキシ基、より好ましくはメチル基を表す。）
から選択される基であり、
Ｅは、−（ＣＨ_２）_ｎ−（ｎは２〜６の整数）であり、
Ｄは、分子主鎖のＰＦＰＥに結合し、Ｅは、ＰＦＰＥと反対の基に結合する。］ In another embodiment, examples of X ¹ groups include the following groups:

[Wherein, R ⁴¹ each independently represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C _1-6 alkoxy group, preferably a methyl group;
D is
_{-CH 2 O (CH 2) 2} -,
_{-CH 2 O (CH 2) 3} -,
_{-CF 2 O (CH 2) 3} -,
- _{(CH 2)} 2 -,
- _{(CH 2)} 3 -,
- _{(CH 2)} 4 -,
-CONH- _{(CH 2)} 3 -,
_{-CON (CH 3) - (CH} 2) 3 -,
_{-CON (Ph) - (CH 2} ) 3 - ( wherein, Ph means phenyl), and

(In the formula, each R ⁴² independently represents a hydrogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group.)
A group selected from
E is, - _{(CH 2)} n - is (n is an integer of from 2 to 6),
D binds to PFPE of the molecular backbone, and E binds to the opposite group of PFPE. ]

などが挙げられる。 Specific examples of X ¹ include, for example:
_{-CH 2 O (CH 2) 2} -,
_{-CH 2 O (CH 2) 3} -,
_{-CH 2 O (CH 2) 6} -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 3 Si (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 10 Si (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 3) 2 (CH 2) 2 -,
-CH ₂ OCF ₂ CHFOCF ₂ -,
_{-CH 2 OCF 2 CHFOCF 2 CF 2} -,
_{-CH 2 OCF 2 CHFOCF 2 CF 2} CF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF 2 CF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF 2 CF 2 CF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF (CF 3) CF 2 OCF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF (CF 3) CF 2 OCF 2 CF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF (CF 3) CF 2 OCF 2 CF 2 CF 2 -,
_{-CH 2 OCH 2 CHFCF 2 OCF 2} -,
_{-CH 2 OCH 2 CHFCF 2 OCF 2} CF 2 -,
_{-CH 2 OCH 2 CHFCF 2 OCF 2} CF 2 CF 2 -,
_{-CH 2 OCH 2 CHFCF 2 OCF (} CF 3) CF 2 OCF 2 -,
_{-CH 2 OCH 2 CHFCF 2 OCF (} CF 3) CF 2 OCF 2 CF 2 -,
_{-CH 2 OCH 2 CHFCF 2 OCF (} CF 3) CF 2 OCF 2 CF 2 CF 2 -
_{-CH 2 OCH 2 (CH 2)} 7 CH 2 Si (OCH 3) 2 OSi (OCH 3) 2 (CH 2) 2 Si (OCH 3) 2 OSi (OCH 3) 2 (CH 2) 2 -,
_{-CH 2 OCH 2 CH 2 CH 2} Si (OCH 3) 2 OSi (OCH 3) 2 (CH 2) 3 -,
- _{(CH 2)} 2 -,
- _{(CH 2)} 3 -,
- _{(CH 2)} 4 -,
- _{(CH 2)} 6 -,
-CONH- _{(CH 2)} 3 -,
_{-CON (CH 3) - (CH} 2) 3 -,
_{-CON (Ph) - (CH 2} ) 3 - ( wherein, Ph means phenyl),
-CONH- _{(CH 2)} 6 -,
_{-CON (CH 3) - (CH} 2) 6 -,
_{-CON (Ph) - (CH 2} ) 6 - ( wherein, Ph means phenyl),
_{-CONH- (CH 2) 2 NH (} CH 2) 3 -,
_{-CONH- (CH 2) 6 NH (} CH 2) 3 -,
_{-CH 2 O-CONH- (CH 2} ) 3 -,
_{-CH 2 O-CONH- (CH 2} ) 6 -,
-S- _{(CH 2)} 3 -,
_{- (CH 2) 2 S (} CH 2) 3 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 3 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 10 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 3) 2 (CH 2) 2 -
_{-C (O) O- (CH 2} ) 3 -,
_{-C (O) O- (CH 2} ) 6 -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 - (CH 2) 2 -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 -CH (CH 3) -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 - (CH 2) 3 -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 -CH (CH 3) -CH 2 -,

Etc.

In still another embodiment, X ¹ is a group represented by the formula: — (R ¹⁶ ) _x — (CFR ¹⁷ ) _y — (CH ₂ ) _z —. In the formula, x, y and z are each independently an integer of 0 to 10, the sum of x, y and z is 1 or more, and the order in which each repeating unit enclosed in parentheses is in the formula Is optional.

In the above formula, R ¹⁶ is each independently an oxygen atom, phenylene, carbazolylene, —NR ²⁶ — (wherein R ²⁶ represents a hydrogen atom or an organic group) or a divalent organic group. is there. Preferably, R ¹⁶ is an oxygen atom or a divalent polar group.

The “divalent polar group” is not particularly limited, but —C (O) —, —C (═NR ²⁷ ) —, and —C (O) NR ²⁷ — (in these formulas, R ²⁷ is Represents a hydrogen atom or a lower alkyl group). The “lower alkyl group” is, for example, an alkyl group having 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, and these may be substituted with one or more fluorine atoms.

In the above formula, R ¹⁷ is each independently a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, preferably a fluorine atom, at each occurrence. The “lower fluoroalkyl group” is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, A pentafluoroethyl group, more preferably a trifluoromethyl group.

In this embodiment, X ¹ is preferably of the formula: — (O) _x — (CF ₂ ) _y — (CH ₂ ) _z — (wherein x, y and z are as defined above and brackets The order in which each repeating unit is included is arbitrary in the formula).

As the group represented by the above formula: — (O) _x — (CF ₂ ) _y — (CH ₂ ) _z —, for example, — (O) _{x ′} — (CH ₂ ) _{z ″} —O — [(CH _{2) z '''-O-]} z "", and _{- (O) x' - (} CF 2) y "- (CH 2) z" -O - [(CH 2) z '''-O- _{Z ″ ″} (wherein x ′ is 0 or 1, y ″, z ″ and z ′ ″ are each independently an integer of 1 to 10, and z ″ ″ is 0 or 1) These groups are bonded at the left end to the PFPE side.

In another preferred embodiment, X ¹ is —O—CFR ¹³ — (CF ₂ ) _e —.

Each R ¹³ independently 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.

  Each e is independently 0 or 1.

In one embodiment, R ¹³ is a fluorine atom and e is 1.

［式中、
Ｒ^４１は、それぞれ独立して、水素原子、フェニル基、炭素数１〜６のアルキル基、またはＣ_１−６アルコキシ基好ましくはメチル基であり；
各Ｘ^１基において、Ｔのうち任意のいくつかは、分子主鎖のＰＦＰＥに結合する以下の基：
−ＣＨ_２Ｏ（ＣＨ_２）_２−、
−ＣＨ_２Ｏ（ＣＨ_２）_３−、
−ＣＦ_２Ｏ（ＣＨ_２）_３−、
−（ＣＨ_２）_２−、
−（ＣＨ_２）_３−、
−（ＣＨ_２）_４−、
−ＣＯＮＨ−（ＣＨ_２）_３−、
−ＣＯＮ（ＣＨ_３）−（ＣＨ_２）_３−、
−ＣＯＮ（Ｐｈ）−（ＣＨ_２）_３−（式中、Ｐｈはフェニルを意味する）、または

［式中、Ｒ^４２は、それぞれ独立して、水素原子、Ｃ_１−６のアルキル基またはＣ_１−６のアルコキシ基、好ましくはメチル基またはメトキシ基、より好ましくはメチル基を表す。］
であり、別のＴのいくつかは、分子主鎖のＰＦＰＥと反対の基（即ち、式（Ａ１）および（Ａ２）においては炭素原子、また、下記する式（Ｂ１）、（Ｂ２）、（Ｃ１）および（Ｃ２）においてはＳｉ原子）に結合する−（ＣＨ_２）_ｎ”−（ｎ”は２〜６の整数）であり、存在する場合、残りは、それぞれ独立して、メチル基、フェニル基またはＣ_１−６アルコキシ基である。 In yet another embodiment, examples of X ¹ groups include the following groups:

[Where:
Each of R ⁴¹ is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C _1-6 alkoxy group, preferably a methyl group;
In each X ¹ group, any some of T are attached to the PFPE of the molecular backbone:
_{-CH 2 O (CH 2) 2} -,
_{-CH 2 O (CH 2) 3} -,
_{-CF 2 O (CH 2) 3} -,
- _{(CH 2)} 2 -,
- _{(CH 2)} 3 -,
- _{(CH 2)} 4 -,
-CONH- _{(CH 2)} 3 -,
_{-CON (CH 3) - (CH} 2) 3 -,
_{-CON (Ph) - (CH 2} ) 3 - ( wherein, Ph means phenyl), or

[Wherein, R ⁴² independently represents a hydrogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group. ]
And some of other Ts are groups opposite to PFPE of the molecular main chain (that is, carbon atoms in formulas (A1) and (A2), and formulas (B1), (B2), ( C1) and (C2) are bonded to Si atoms) in _{- (CH 2) n "-} (n" is an integer of 2-6), if present, the remainder are each independently a methyl group, A phenyl group or a C _1-6 alkoxy group.

In this embodiment, X ¹ , X ⁵ and X ⁷ can each independently be a trivalent to 10 valent organic group.

  In said formula, t is an integer of 1-10 each independently. In a preferred embodiment, t is an integer from 1-6. In another preferred embodiment, t is an integer from 2 to 10, preferably an integer from 2 to 6.

In the above formula, X ² each independently represents a single bond or a divalent organic group at each occurrence. X ² is preferably an alkylene group having 1 to 20 carbon atoms, and more preferably — (CH ₂ ) _u — (wherein u is an integer of 0 to 2).

［式中：
ＰＦＰＥは、それぞれ独立して、式：
−（ＯＣ_４Ｆ_８）_ａ−（ＯＣ_３Ｆ_６）_ｂ−（ＯＣ_２Ｆ_４）_ｃ−（ＯＣＦ_２）_ｄ−
（式中、ａ、ｂ、ｃおよびｄは、それぞれ独立して、０〜２００の整数であって、ａ、ｂ、ｃおよびｄの和は少なくとも１であり、添字ａ、ｂ、ｃまたはｄ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。）
で表される基であり；
Ｒｆは、各出現においてそれぞれ独立して、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；
Ｒ^１は、各出現においてそれぞれ独立して、水素原子または炭素数１〜２２のアルキル基を表し；
Ｒ^２は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
Ｒ^１１は、各出現においてそれぞれ独立して、水素原子またはハロゲン原子を表し；
Ｒ^１２は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
ｎは、０〜２の整数であり、好ましくは０であり；
Ｘ^１は、−Ｏ−ＣＦＲ^１３−（ＣＦ_２）_ｅ−であり；
Ｒ^１３は、フッ素原子または低級フルオロアルキル基であり；
ｅは、０または１であり；
Ｘ^２は、−（ＣＨ_２）_ｕ−であり；
ｕは、０〜２の整数であり；
ｔは、１〜１０の整数である。］
で表される化合物である。 Preferred compounds represented by formulas (A1) and (A2) are represented by the following formulas (A1 ′) and (A2 ′):

[Where:
Each PFPE is independently of the formula:
_{- (OC 4 F 8) a} - (OC 3 F 6) b - (OC 2 F 4) c - (OCF 2) d -
Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d The order of existence of each repeating unit with parentheses attached with is arbitrary in the formula.)
A group represented by:
Rf represents each independently an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
R ² represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group;
R ¹¹ independently represents a hydrogen atom or a halogen atom at each occurrence;
R ¹² independently represents a hydrogen atom or a lower alkyl group at each occurrence;
n is an integer from 0 to 2, preferably 0;
X ¹ is —O—CFR ¹³ — (CF ₂ ) _e —;
R ¹³ is a fluorine atom or a lower fluoroalkyl group;
e is 0 or 1;
X ² is — (CH ₂ ) _u —;
u is an integer from 0 to 2;
t is an integer of 1-10. ]
It is a compound represented by these.

Formulas (B1) and (B2):

In the above formulas (B1) and (B2), Rf, PFPE, R ¹ , R ² and n are as defined in the above formulas (A1) and (A2).

In said formula, X < ⁵ > represents a single bond or a 2-10 valent organic group each independently. The ^{X 5} are the formula (B1) and in the compounds represented by (B2), mainly perfluoropolyether unit for providing water repellency and surface slipperiness, etc. (Rf-PFPE unit or -PFPE- parts) It is understood as a linker that connects a silane moiety (specifically, —SiR ¹ _n R ² _3-n ) that provides the binding ability to the substrate. Therefore, X ⁵ may be any organic group as long as the compounds represented by formulas (B1) and (B2) can exist stably.

Β in the above formula is an integer of 1 to 9, and β ′ is an integer of 1 to 9. These β and β ′ are determined according to the valence of X ³ , and in the formula (B1), the sum of β and β ′ is the same as the valence of X ⁵ . For example, when X ⁵ is a 10-valent organic group, the sum of β and β ′ is 10, for example, β is 9 and β ′ is 1, β is 5 and β ′ is 5, or β is 1 and β 'Can be nine. When X ⁵ is a divalent organic group, β and β ′ are 1. In formula (B2), beta is a value obtained by subtracting 1 from the valence of the value of X ^5.

X ⁵ is preferably a 2-7 valent, more preferably a 2-4 valent, and even more preferably a divalent organic group.

In one embodiment, X ⁵ is a divalent to tetravalent organic group, β is 1 to 3, and β ′ is 1.

In another embodiment, X ⁵ is a divalent organic group, β is 1 and β ′ is 1. In this case, the formulas (B1) and (B2) are represented by the following formulas (B1 ′) and (B2 ′).

Examples of X ⁵ are not particularly limited, and examples thereof include those similar to those described for X ¹ .

などが挙げられる。 Among these, preferable specific X ⁵ is
_{-CH 2 O (CH 2) 2} -,
_{-CH 2 O (CH 2) 3} -,
_{-CH 2 O (CH 2) 6} -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 3 Si (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 10 Si (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 3) 2 (CH 2) 2 -,
-CH ₂ OCF ₂ CHFOCF ₂ -,
_{-CH 2 OCF 2 CHFOCF 2 CF 2} -,
_{-CH 2 OCF 2 CHFOCF 2 CF 2} CF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF 2 CF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF 2 CF 2 CF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF (CF 3) CF 2 OCF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF (CF 3) CF 2 OCF 2 CF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF (CF 3) CF 2 OCF 2 CF 2 CF 2 -,
_{-CH 2 OCH 2 CHFCF 2 OCF 2} -,
_{-CH 2 OCH 2 CHFCF 2 OCF 2} CF 2 -,
_{-CH 2 OCH 2 CHFCF 2 OCF 2} CF 2 CF 2 -,
_{-CH 2 OCH 2 CHFCF 2 OCF (} CF 3) CF 2 OCF 2 -,
_{-CH 2 OCH 2 CHFCF 2 OCF (} CF 3) CF 2 OCF 2 CF 2 -,
_{-CH 2 OCH 2 CHFCF 2 OCF (} CF 3) CF 2 OCF 2 CF 2 CF 2 -
_{-CH 2 OCH 2 (CH 2)} 7 CH 2 Si (OCH 3) 2 OSi (OCH 3) 2 (CH 2) 2 Si (OCH 3) 2 OSi (OCH 3) 2 (CH 2) 2 -,
_{-CH 2 OCH 2 CH 2 CH 2} Si (OCH 3) 2 OSi (OCH 3) 2 (CH 2) 3 -,
- _{(CH 2)} 2 -,
- _{(CH 2)} 3 -,
- _{(CH 2)} 4 -,
- _{(CH 2)} 6 -,
-CONH- _{(CH 2)} 3 -,
_{-CON (CH 3) - (CH} 2) 3 -,
_{-CON (Ph) - (CH 2} ) 3 - ( wherein, Ph means phenyl),
-CONH- _{(CH 2)} 6 -,
_{-CON (CH 3) - (CH} 2) 6 -,
_{-CON (Ph) - (CH 2} ) 6 - ( wherein, Ph means phenyl),
_{-CONH- (CH 2) 2 NH (} CH 2) 3 -,
_{-CONH- (CH 2) 6 NH (} CH 2) 3 -,
_{-CH 2 O-CONH- (CH 2} ) 3 -,
_{-CH 2 O-CONH- (CH 2} ) 6 -,
-S- _{(CH 2)} 3 -,
_{- (CH 2) 2 S (} CH 2) 3 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 3 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 10 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 3) 2 (CH 2) 2 -
_{-C (O) O- (CH 2} ) 3 -,
_{-C (O) O- (CH 2} ) 6 -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 - (CH 2) 2 -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 -CH (CH 3) -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 - (CH 2) 3 -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 -CH (CH 3) -CH 2 -,

Etc.

［式中：
ＰＦＰＥは、それぞれ独立して、式：
−（ＯＣ_４Ｆ_８）_ａ−（ＯＣ_３Ｆ_６）_ｂ−（ＯＣ_２Ｆ_４）_ｃ−（ＯＣＦ_２）_ｄ−
（式中、ａ、ｂ、ｃおよびｄは、それぞれ独立して、０〜２００の整数であって、ａ、ｂ、ｃおよびｄの和は少なくとも１であり、添字ａ、ｂ、ｃまたはｄ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。）
で表される基であり；
Ｒｆは、各出現においてそれぞれ独立して、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；
Ｒ^１は、各出現においてそれぞれ独立して、水素原子または炭素数１〜２２のアルキル基を表し；
Ｒ^２は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
ｎは、０〜２の整数であり、好ましくは０であり；
Ｘ^５は、−ＣＨ_２Ｏ（ＣＨ_２）_２−、−ＣＨ_２Ｏ（ＣＨ_２）_３−または−ＣＨ_２Ｏ（ＣＨ_２）_６−である］
で表される化合物である。 Preferred compounds represented by formulas (B1) and (B2) are represented by the following formulas (B1 ′) and (B2 ′):

[Where:
Each PFPE is independently of the formula:
_{- (OC 4 F 8) a} - (OC 3 F 6) b - (OC 2 F 4) c - (OCF 2) d -
Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d The order of existence of each repeating unit with parentheses attached with is arbitrary in the formula.)
A group represented by:
Rf represents each independently an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
R ² represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group;
n is an integer from 0 to 2, preferably 0;
X ⁵ is —CH ₂ O (CH ₂ ) ₂ —, —CH ₂ O (CH ₂ ) ₃ — or —CH ₂ O (CH ₂ ) ₆ —.
It is a compound represented by these.

Formulas (C1) and (C2):

  In the above formulas (C1) and (C2), Rf and PFPE are the same as those described for the above formulas (A1) and (A2).

In the above formulas, X ⁷ each independently represents a single bond or a divalent to 10-valent organic group. The ^{X 7} is a formula (C1) and in the compounds represented by (C2), mainly perfluoropolyether unit for providing water repellency and surface slipperiness, etc. (Rf-PFPE unit or -PFPE- parts) _{^{(specifically, -SiR a k R b l R}} c m group) silane unit that provides a binding capability to a substrate is understood as a linker linking. Therefore, X ⁷ may be any organic group as long as the compounds represented by formulas (C1) and (C2) can exist stably.

Γ in the above formula is an integer of 1 to 9, and γ ′ is an integer of 1 to 9. These γ and γ ′ are determined according to the valence of X ⁷ , and in the formula (C1), the sum of γ and γ ′ is the same as the valence of X ⁷ . For example, when X ⁷ is a 10-valent organic group, the sum of γ and γ ′ is 10, for example, γ is 9 and γ ′ is 1, γ is 5 and γ ′ is 5, or γ is 1 and γ. 'Can be nine. Further, when X ⁷ is a divalent organic group, γ and γ ′ are 1. In formula (C1), gamma is a value obtained by subtracting 1 from the valence of the values of X ^7.

X ⁷ is preferably a 2-7 valent, more preferably a 2-4 valent, and even more preferably a divalent organic group.

In one embodiment, X ⁷ is a divalent to tetravalent organic group, γ is 1 to 3, and γ ′ is 1.

In another embodiment, X ⁷ is a divalent organic group, γ is 1 and γ ′ is 1. In this case, the formulas (C1) and (C2) are represented by the following formulas (C1 ′) and (C2 ′).

Examples of X ⁷ are not particularly limited, and examples thereof include those similar to those described for X ¹ .

などが挙げられる。 Among these, preferable specific X ⁵ is —CH ₂ O (CH ₂ ) ₂ —,
_{-CH 2 O (CH 2) 3} -,
_{-CH 2 O (CH 2) 6} -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 3 Si (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 10 Si (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 3) 2 (CH 2) 2 -,
-CH ₂ OCF ₂ CHFOCF ₂ -,
_{-CH 2 OCF 2 CHFOCF 2 CF 2} -,
_{-CH 2 OCF 2 CHFOCF 2 CF 2} CF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF 2 CF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF 2 CF 2 CF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF (CF 3) CF 2 OCF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF (CF 3) CF 2 OCF 2 CF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF (CF 3) CF 2 OCF 2 CF 2 CF 2 -,
_{-CH 2 OCH 2 CHFCF 2 OCF 2} -,
_{-CH 2 OCH 2 CHFCF 2 OCF 2} CF 2 -,
_{-CH 2 OCH 2 CHFCF 2 OCF 2} CF 2 CF 2 -,
_{-CH 2 OCH 2 CHFCF 2 OCF (} CF 3) CF 2 OCF 2 -,
_{-CH 2 OCH 2 CHFCF 2 OCF (} CF 3) CF 2 OCF 2 CF 2 -,
_{-CH 2 OCH 2 CHFCF 2 OCF (} CF 3) CF 2 OCF 2 CF 2 CF 2 -
_{-CH 2 OCH 2 (CH 2)} 7 CH 2 Si (OCH 3) 2 OSi (OCH 3) 2 (CH 2) 2 Si (OCH 3) 2 OSi (OCH 3) 2 (CH 2) 2 -,
_{-CH 2 OCH 2 CH 2 CH 2} Si (OCH 3) 2 OSi (OCH 3) 2 (CH 2) 3 -,
- _{(CH 2)} 2 -,
- _{(CH 2)} 3 -,
- _{(CH 2)} 4 -,
- _{(CH 2)} 6 -,
-CONH- _{(CH 2)} 3 -,
_{-CON (CH 3) - (CH} 2) 3 -,
_{-CON (Ph) - (CH 2} ) 3 - ( wherein, Ph means phenyl),
-CONH- _{(CH 2)} 6 -,
_{-CON (CH 3) - (CH} 2) 6 -,
_{-CON (Ph) - (CH 2} ) 6 - ( wherein, Ph means phenyl),
_{-CONH- (CH 2) 2 NH (} CH 2) 3 -,
_{-CONH- (CH 2) 6 NH (} CH 2) 3 -,
_{-CH 2 O-CONH- (CH 2} ) 3 -,
_{-CH 2 O-CONH- (CH 2} ) 6 -,
-S- _{(CH 2)} 3 -,
_{- (CH 2) 2 S (} CH 2) 3 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 3 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 10 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 3) 2 (CH 2) 2 -
_{-C (O) O- (CH 2} ) 3 -,
_{-C (O) O- (CH 2} ) 6 -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 - (CH 2) 2 -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 -CH (CH 3) -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 - (CH 2) 3 -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 -CH (CH 3) -CH 2 -,

Etc.

In the above formula, R ^a represents —Z—SiR ⁷¹ _p R ⁷² _q R ⁷³ _r independently at each occurrence.

  In the formula, Z represents an oxygen atom or a divalent organic group independently at each occurrence.

Z is preferably a divalent organic group, and forms a siloxane bond with the Si atom (Si atom to which R ^a is bonded) at the end of the molecular main chain in formula (C1) or formula (C2). Does not include things.

Z is preferably a C _1-6 alkylene group, — (CH ₂ ) _g —O— (CH ₂ ) _h — (wherein g is an integer of 1 to 6, and h is 1 to 6 Or -phenylene- (CH ₂ ) _i- (wherein i is an integer of 0 to 6), more preferably a C _1-3 alkylene group. These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _2-6 alkynyl group. .

In the formula, R ⁷¹ represents R ^{a ′} independently at each occurrence. R ^{a ′} has the same meaning as R ^a .

During R ^a, Si is connected to the linear through the Z group is a five at the maximum. That is, in the above R ^a , when at least one R ⁷¹ is present, there are two or more Si atoms linearly linked via a Z group in R ^a , The maximum number of Si atoms connected in a chain is five. The "number of Si atoms linearly linked via a Z group in R ^a" is equal to -Z-Si- repeating number of which is connected to a linear during R ^a.

For example, an example in which Si atoms are linked through a Z group in R ^a is shown below.

In the above formula, * means a site bonded to Si of the main chain, and ... means that a predetermined group other than ZSi is bonded, that is, all three bonds of Si atoms are ... In this case, it means the end point of ZSi repetition. The number on the right shoulder of Si means the number of appearances of Si connected in a straight line through the Z group counted from *. That is, the chain in which ZSi repeat is completed in Si ² has “the number of Si atoms linearly linked through the Z group in ^Ra ”, and similarly, Si ³ , Si ⁴ And the chain in which the ZSi repetition is completed in Si ⁵ has “number of Si atoms linearly linked through the Z group in R ^a ” being 3, 4 and 5, respectively. As is apparent from the above equation, is in the R ^a, but ZSi chain there are multiple, they need not be all the same length, each may be of any length.

In a preferred embodiment, as shown below, “the number of Si atoms connected linearly via the Z group in R ^a ” is one (left formula) or two (right formula) in all chains. Formula).

In one embodiment, the number of Si atoms connected in a straight chain via a Z group in R ^a is 1 or 2, preferably 1.

In the formula, R ⁷² independently represents a hydroxyl group or a hydrolyzable group at each occurrence.

The “hydrolyzable group” as used herein means a group capable of undergoing a hydrolysis reaction. Examples of hydrolyzable groups include —OR, —OCOR, —O—N═C (R) ₂ , —N (R) ₂ , —NHR, halogen (in these formulas, R is substituted or unsubstituted) Represents an alkyl group having 1 to 4 carbon atoms, preferably -OR (alkoxy group). Examples of R include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; substituted alkyl groups such as chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, but may be a group produced by hydrolysis of a hydrolyzable group.

Preferably, R ⁷² is —OR (wherein R represents a substituted or unsubstituted C _1-3 alkyl group, more preferably a methyl group).

In the formula, R ⁷³ independently represents a hydrogen atom or a lower alkyl group at each occurrence. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.

  Where p is independently an integer from 0 to 3 at each occurrence; q is independently an integer from 0 to 3 at each occurrence; and r is independently at each occurrence. And an integer of 0 to 3. However, the sum of p, q and r is 3.

In a preferred embodiment, ^{'(if R a'} is absent, ^{R a)} terminal of ^{R a} in ^{R a} in the above q is preferably 2 or more, for example 2 or 3, more preferably 3.

In the above formulas (C1) and (C2), at least one R ⁷² is present.

In the above formula, R ^b independently represents a hydroxyl group or a hydrolyzable group at each occurrence.

R ^b is preferably a hydroxyl group, —OR, —OCOR, —O—N═C (R) ₂ , —N (R) ₂ , —NHR, halogen (in these formulas, R is substituted or unsubstituted) Represents an alkyl group having 1 to 4 carbon atoms, preferably -OR. R includes an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and a substituted alkyl group such as a chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, but may be a group produced by hydrolysis of a hydrolyzable group. More preferably, R ^c is —OR (wherein R represents a substituted or unsubstituted C _1-3 alkyl group, more preferably a methyl group).

In the above formula, R ^c independently represents a hydrogen atom or a lower alkyl group at each occurrence. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.

  Wherein k is independently an integer from 0 to 3 at each occurrence; l is independently an integer from 0 to 3 at each occurrence; and m is independently at each occurrence. And an integer of 0 to 3. However, the sum of k, l and m is 3.

  The compound represented by the formulas (A1), (A2), (B1), (B2), (C1) and (C2) can be appropriately produced by those skilled in the art using techniques known in the art. it can.

  For example, the compounds represented by the formulas (A1) and (A2) can be synthesized by the method described in Patent Document 1.

  For example, the compounds represented by the formulas (B1) and (B2) can be synthesized by the method described in Patent Document 2.

  For example, the compounds represented by formulas (C1) and (C2) can be synthesized by the method described in JP-A No. 2014-218639.

  The number average molecular weight of the perfluoro (poly) ether group-containing silane compound contained in the surface treatment agent of the present invention is preferably 5,000 or more, more preferably 6,000 or more, and preferably 100,000 or less. Preferably it is 30,000 or less, More preferably, it is 10,000 or less.

  The number average molecular weight of the PFPE moiety in the perfluoro (poly) ether group-containing silane compound contained in the surface treatment agent of the present invention is not particularly limited, but is preferably 4,000 to 30,000, more preferably It can be 5,000 to 10,000.

  In the present invention, the “number average molecular weight” is measured by GPC (gel permeation chromatography) analysis.

The surface treatment agent of the present invention further includes the following formula (S):
SiR ⁵¹ _n R ⁶¹ _4-n (S)
The surface treating agent containing at least 1 sort (s) of silane compound represented by these is included.

R ⁵¹ may be each independently a hydrogen atom or an organic group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Further, two R ⁵¹ out of R ⁵¹ may constitute = CR ⁵⁷ ₂ .

R ⁵⁷ is each independently a hydrogen atom or an organic group having 1 to 20 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms may be linear or branched, and is preferably an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group or a propyl group, and more preferably a methyl group. preferable. R ⁵⁷ is more preferably each independently a hydrogen atom or a methyl group.

In one embodiment, each R ⁵¹ is independently of the formula:
^{R 52 -R 53 -R 54 -R 55} -
It is group represented by these.

である。 In the formula, R ⁵² represents CH ₃ —, CH ₂ = CR ⁵⁸ —, NR ⁵⁸ ₂ —, SR ⁵⁸ —,

It is.

h and i are each independently an integer of 0 to 3, preferably h and i are 1. R ⁵⁸ is each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group.

R ⁵³ is a single bond or an alkylene group having 1 to 6 carbon atoms. Such an alkylene group having 1 to 6 carbon atoms may be linear or branched, but is preferably linear. A preferable alkylene group having 1 to 6 carbon atoms is —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ — or —CH ₂ —.

R ⁵⁴ is a single bond, —O—, —CO—, —O—CO—, —CO—O—, —NR ⁵⁶ —, —NR ⁵⁶ —CO— or —NR ⁵⁶ —CO—.

R ⁵⁶ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group.

R ⁵⁵ is a single bond or an alkylene group having 1 to 6 carbon atoms. Such an alkylene group having 1 to 6 carbon atoms may be linear or branched, but is preferably linear. A preferable alkylene group having 1 to 6 carbon atoms is —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ — or —CH ₂ —.

である。 In a preferred embodiment, R ⁵¹ represents an alkyl group having 1 to 6 carbon atoms (preferably an ethyl group or a methyl group, more preferably a methyl group), CH ₂ ═CH—, HSCH ₂ CH ₂ CH ₂ , H ₂ NCH ₂ CH. ₂ NHCH ₂ CH ₂ CH ₂ , CH ₂ = C (CH ₃ ) C (O) OCH ₂ CH ₂ CH ₂ ,

It is.

In the above formula, each R ⁶¹ is independently a hydrolyzable group. Such hydrolyzable groups are not particularly limited, and include —OR ⁶² , —OCOR ⁶² , —O—N═CR ⁶² ₂ , —ONR ₂ , —NR ⁶² ₂ or —NR ⁶² —CO—R ^62. .

^R62 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Such an alkyl group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 3 carbon atoms, such as a methyl group, an ethyl group or an alkyl group. R ⁶² is preferably a methyl group or an ethyl group, and more preferably a methyl group.

  In said formula, n is an integer of 0-3, Preferably it is 1 or 2, More preferably, it is 1.

Examples of the silane compound represented by the formula (S) are not particularly limited, and examples thereof include the following compounds:
Si (OC ₂ H ₅ ) ₄ ,
CH ₂ = CHSi (OCH ₃ ) ₃ ,
CH ₂ = CHCH ₂ Si (OCH ₃ ) ₃ ,
HSCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (CH ₃ ) (OCH ₃ ) ₂ ,
_{CH 2 = C (CH 3)} C (O) OCH 2 CH 2 CH 2 Si (OCH 3) 3,
_{CH 2 = C (CH 3)} C (O) OCH 2 CH 2 CH 2 Si (OCH 2 CH 2 OCH 2) 3,

  The surface treatment agent of the present invention can impart water repellency, oil repellency, antifouling property, waterproofness and high friction durability to a substrate, and is not particularly limited. It can be suitably used as an agent or a waterproof coating agent.

  In one embodiment, in the surface treatment agent of the present invention, (1) perfluoro represented by any one of formulas (A1), (A2), (B1), (B2), (C1) and (C2) A poly) ether group-containing silane compound (hereinafter also referred to as “perfluoro (poly) ether group-containing silane compound (1)”), and (2) a fluorine-containing compound represented by formula (S) (hereinafter referred to as “silane compound”). The mass ratio (also referred to as “(2)”) is not particularly limited, but is preferably 10: 1 to 100,000: 1, more preferably. Is 100: 1 to 10000: 1. By increasing the ratio of the perfluoro (poly) ether group-containing silane compound (1), functions such as water repellency and oil repellency can be further enhanced, and by increasing the ratio of the silane compound (2), preservation is achieved. Stability can be further improved.

  The surface treating agent of the present invention may contain a solvent. Such a solvent is not particularly limited, but a fluorine-containing organic solvent is preferable.

Examples of the fluorine-containing organic solvent include:
Perfluorocarbon: perfluorohexane, perfluorooctane, perfluorodimethylcyclohexane, perfluorodecane Hydrofluorocarbon: 1,1,2,2,3,4,4-heptafluorocyclopentane (Zeorolla H (trade name)), 1 , 1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane (Asahiclin AC6000 (trade name)), CF ₃ CH ₂ CF ₂ CH ₃ , CF ₃ CHFCHFC ₂ F ₅ , 1,3-bistrifluoromethylbenzene, Freon 134a, 1,1,1,4,4,4-hexafluoro-2-butene Hydrochlorofluorocarbon: HCFC-225 (Asahiclin AK-225 (Product Name), etc.), CF ₃ CF ₂ CHCl ₂ , 1,1-dichloro-2,3,3,3 -Tetrafluoro-1-propene, 1,2-dichloro-1,3,3,3-tetrafluoro-1-propene, 1,2-dichloro-3,3,3-trifluoro-1-propene, 1, 1-dichloro-3,3,3-trifluoro-1-propene, 1,1,2-trichloro-3,3,3-trifluoro-1-propene hydrofluoroether: C ₄ F ₉ OCH ₃ (for example, Novec HFE-7100 (trade name)), C ₄ F ₉ OC ₂ H ₅ (for example, Novec HFE-7200 (trade name)), CF ₃ CH ₂ OCF ₂ CHF ₂
Perfluoroalkyl ether: perfluorobutyltetrahydrofuran Perfluoroalkylamine: perfluorotriethylamine, perfluorotripropylamine, perfluorotributylamine fluorinated alcohol: perfluoroalkylethanol, trifluoroethanol, HCF ₂ CF ₂ CH ₂ OH, penta Fluoropropanol, hexafluoroisopropanol Perfluoropolyether: Krytox (trade name), demnum (trade name), Fomblin (trade name), etc. Perfluoroalkylethylene Others: perfluoroalkyl bromide, perfluoroalkyl iodide, methacrylic acid 2- (perfluoroalkyl) ethyl,
2- (perfluoroalkyl) ethyl acrylate, hexafluoropropene oligomer, xylene hexafluoride,
And a solvent selected from the group consisting of methylpentadecafluoroheptyl ketone. These solvents can be used alone or as a mixture of two or more.

  Of these, hydrofluoroethers are preferred because of their high solubility in the silane compound (2).

  The silane compound represented by the formula (S) is not particularly limited, but is 0.0001% by mass to 1% by mass, preferably 0.001% by mass to 0.1% by mass, more preferably in the entire surface treatment agent. It exists at a concentration of 0.002% to 0.1% by weight. By existing at such a concentration, the storage stability can be further improved.

  The surface treating agent of the present invention may contain other components in addition to the perfluoro (poly) ether group-containing silane compound (1) and the silane compound (2). Such other components are not particularly limited. For example, (non-reactive) fluoropolyether compounds, preferably perfluoro (poly) ether compounds (hereinafter referred to as “containing”) that can be understood as fluorine-containing oils. (Referred to as “fluorine oil”), (non-reactive) silicone compounds that can be understood as silicone oil (hereinafter referred to as “silicone oil”), catalysts, and the like.

Although it does not specifically limit as said fluorine-containing oil, For example, the compound (perfluoro (poly) ether compound) represented by the following General formula (3) is mentioned.
^{_{Rf 1 - (OC 4 F 8}} ) a '- (OC 3 F 6) b' - (OC 2 F 4) c '- (OCF 2) d' -Rf 2 ··· (3)
In the formula, Rf ¹ represents a C _1-16 alkyl group (preferably a C _1-16 perfluoroalkyl group) optionally substituted by one or more fluorine atoms, and Rf ² represents _Represents a C _1-16 alkyl group (preferably a C _1-16 perfluoroalkyl group) optionally substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom, Rf ¹ and Rf ² Are more preferably each independently a C _1-3 perfluoroalkyl group.
a ′, b ′, c ′ and d ′ each represent the number of four types of repeating units of perfluoro (poly) ether constituting the main skeleton of the polymer, and are each independently an integer of 0 to 300, , A ′, b ′, c ′ and d ′ are at least 1, preferably 1 to 300, more preferably 20 to 300. The order of presence of each repeating unit in parentheses with subscripts a ′, b ′, c ′ or d ′ 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.

As an example of the perfluoro (poly) ether compound represented by the general formula (3), a compound represented by any one of the following general formulas (3a) and (3b) (one kind or a mixture of two or more kinds) may be used. May be included).
Rf ^1- (OCF ₂ CF ₂ CF ₂ ) _{b ″} -Rf ² (3a)
_{^{Rf 1 - (OCF 2 CF 2}} CF 2 CF 2) a '' - (OCF 2 CF 2 CF 2) b '' - (OCF 2 CF 2) c '' - (OCF 2) d '' -Rf 2 · .. (3b)
In these formulas, Rf ¹ and Rf ² are as described above; in formula (3a), b ″ is an integer of 1 to 100; in formula (3b), a ″ and b ″ are Each independently represents an integer of 0 or more and 30 or less, for example, 1 or more and 30 or less, and c ″ and d ″ are each independently an integer of 1 or more and 300 or less. The order of existence of each repeating unit with subscripts a ″, b ″, c ″, d ″ and parentheses is arbitrary in the formula.

  The fluorine-containing oil may have an average molecular weight of 1,000 to 30,000. Thereby, high surface slipperiness can be obtained.

  In the surface treatment agent of the present invention, the fluorine-containing oil is based on a total of 100 parts by mass of the perfluoro (poly) ether group-containing silane compound (in the case of two or more, respectively, the same applies to the following). For example, 0 to 500 parts by mass, preferably 0 to 400 parts by mass, more preferably 5 to 300 parts by mass.

  The compound represented by the general formula (3a) and the compound represented by the general formula (3b) may be used alone or in combination. It is preferable to use the compound represented by the general formula (3b) rather than the compound represented by the general formula (3a) because higher surface slip properties can be obtained. When these are used in combination, the mass ratio of the compound represented by the general formula (3a) and the compound represented by the general formula (3b) is preferably 1: 1 to 1:30, and 1: 1 to 1 : 10 is more preferable. According to such a mass ratio, a surface treatment layer having an excellent balance between surface slipperiness and friction durability can be obtained.

  In one embodiment, the fluorine-containing oil contains one or more compounds represented by the general formula (3b). In such an embodiment, the mass ratio of the sum of the perfluoro (poly) ether group-containing silane compounds in the surface treatment agent to the compound represented by the formula (3b) is preferably 4: 1 to 1: 4. .

  In a preferred embodiment, when the surface treatment layer is formed by a vacuum vapor deposition method, the average molecular weight of the fluorine-containing oil may be larger than the average molecular weight of the perfluoro (poly) ether group-containing silane compound. By setting such an average molecular weight, more excellent friction durability and surface slipperiness can be obtained.

From another viewpoint, the fluorine-containing oil may be a compound represented by the general formula Rf ³ -F (wherein Rf ³ is a C _5-16 perfluoroalkyl group). Moreover, a chlorotrifluoroethylene oligomer may be sufficient. The compound represented by Rf ³ -F and the chlorotrifluoroethylene oligomer are a compound represented by a fluorine-containing compound having a carbon-carbon unsaturated bond at the molecular end, the terminal of which is a C _1-16 perfluoroalkyl group. This is preferable in that high affinity can be obtained.

  The fluorine-containing oil contributes to improving the surface slipperiness of the surface treatment layer.

  As the silicone oil, for example, a linear or cyclic silicone oil having a siloxane bond of 2,000 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 the surface treatment agent of the present invention, the silicone oil is, for example, 0 with respect to 100 parts by mass in total of the perfluoro (poly) ether group-containing silane compound (in the case of 2 or more types, these are the same; It can be contained at ~ 300 parts by mass, preferably 0-200 parts by mass.

  Silicone oil contributes to improving the surface slipperiness of the surface treatment layer.

  Examples of the catalyst include acids (eg, acetic acid, trifluoroacetic acid, etc.), bases (eg, ammonia, triethylamine, diethylamine, etc.), transition metals (eg, Ti, Ni, Sn, etc.), and the like.

  The catalyst promotes the hydrolysis and dehydration condensation of the perfluoro (poly) ether group-containing silane compound and promotes the formation of the surface treatment layer.

  The surface treatment agent of the present invention can be made into pellets by impregnating a porous material such as a porous ceramic material or metal fiber such as steel wool hardened in a cotton form. The pellet can be used for, for example, vacuum deposition.

  Next, the article of the present invention will be described.

  The article of the present invention includes a substrate and a layer (surface treatment layer) formed on the surface of the substrate from the surface treatment agent of the present invention. This article can be manufactured, for example, as follows.

  First, a base material is prepared. Substrates that can be used in the present invention include, for example, glass, sapphire glass, resin (natural or synthetic resin, such as a general plastic material, and may be a plate, film, or other form), metal ( It may be a single metal such as aluminum, copper, iron or a composite of an alloy, etc.), ceramics, semiconductor (silicon, germanium, etc.), fiber (woven fabric, non-woven fabric, etc.), fur, leather, wood, ceramics, stone, etc. It can be composed of any suitable material, such as a building member. Preferably, the substrate is glass or sapphire glass.

As the glass, soda lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, and quartz glass are preferable, chemically strengthened soda lime glass, chemically strengthened alkali aluminosilicate glass, and chemical bond Particularly preferred is borosilicate glass.
As the resin, acrylic resin and polycarbonate are preferable.

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. Further, 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). Further, 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 a monomolecular film by the LB method (Langmuir-Blodgett method) or chemical adsorption method. There is a method of forming in a form 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 above-described surface treatment agent of the present invention is formed on the surface of the substrate, and this film is post-treated as necessary, thereby forming a surface treatment layer from the surface treatment agent of the present invention. To do.

  The film formation of the surface treatment agent of the present invention can be carried out 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 vapor deposition (usually vacuum vapor deposition), sputtering, CVD and similar methods. Specific examples of the vapor deposition method (usually vacuum vapor deposition method) include resistance heating, high-frequency heating using an electron beam, microwave, and the like, an 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 the wet coating method is used, the surface treatment agent of the present invention can be applied to the substrate surface after being diluted with a solvent. From the viewpoint of the stability of the surface treatment agent of the present invention and the volatility of the solvent, the following solvents are preferably used: C _5-12 perfluoroaliphatic hydrocarbons (eg, perfluorohexane, perfluoromethylcyclohexane and Perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (eg bis (trifluoromethyl) benzene); polyfluoroaliphatic hydrocarbons (eg C ₆ F ₁₃ CH ₂ CH ₃ (eg Asahi Glass) ASAHIKLIN (registered trademark) AC-6000 manufactured by Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, ZEOLOR (registered trademark) H manufactured by Nippon Zeon Co., Ltd.); Hydrofluorocarbon (HFC) (for example, 1,1,1,3,3-pentafluorobutane (HFC-365 fc)); hydrochlorofluorocarbon (e.g., HCFC-225 (ASAHIKLIN (TM) AK225)); hydrofluoroether (HFE) (e.g., perfluoropropyl methyl ether _{(C 3 F 7 OCH 3)} ( e.g., Sumitomo Novec (trade name) 7000) manufactured by 3M Corporation, perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) (for example, Novec (trade name) 7100 manufactured by Sumitomo 3M Limited), perfluorobutyl ethyl ether (C _{4 F 9 OC 2 H 5)} ( e.g., Sumitomo 3M Limited of Novec (TM) 7200), perfluorohexyl methyl ether _{(C 2 F 5 CF (OCH} 3) C 3 F 7) ( e.g., Sumitomo Novec (trade name) 73 manufactured by Co., Ltd. 0) alkyl perfluoroalkyl ethers (such as perfluoroalkyl groups and the alkyl group may be straight or branched), or _{CF 3 CH 2 OCF 2 CHF 2} ( e.g., Asahi Glass ASAHIKLIN Co., Ltd. ( (Registered trademark) AE-3000)), 1,2-dichloro-1,3,3,3-tetrafluoro-1-propene (for example, Vertrel (registered trademark) Scion manufactured by Mitsui DuPont Fluorochemical Co., Ltd.), etc. These solvents can be used alone or in combination as a mixture of two or more, for example, adjusting the solubility of the perfluoro (poly) ether group-containing silane compound (1) and silane compound (2). For example, it can be mixed with another solvent.

  When the dry coating method is used, the surface treatment agent of the present invention may be directly subjected to the dry coating method, or may be diluted with the above-described solvent and then subjected to the dry coating method.

  The film formation is preferably carried out so that the surface treatment agent of the present invention is present in the film together with a catalyst for hydrolysis and dehydration condensation. For simplicity, in the case of the wet coating method, the catalyst may be added to the diluted solution of the surface treatment agent of the present invention immediately after the surface treatment agent of the present invention is diluted with a solvent and applied to the substrate surface. In the case of the dry coating method, the surface treatment agent of the present invention to which the catalyst is added is directly vapor-deposited (usually vacuum deposition), or the surface treatment agent of the present invention to which a catalyst is added to a metal porous body such as iron or copper. Vapor deposition (usually vacuum deposition) may be performed using a pellet-like material impregnated with.

  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 of the present invention is formed on the substrate surface as described above, moisture is supplied to this film (hereinafter also referred to as “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, water acts on the hydrolyzable group bonded to Si of the perfluoro (poly) ether group-containing silane compound in the surface treatment agent of the present invention, and the compound is rapidly removed. It is thought that it can be hydrolyzed.

  The supply of moisture is, for example, 0 to 250 ° C., preferably 60 ° C. or higher, more preferably 100 ° C. or higher, preferably 180 ° C. or lower, more preferably 150 ° 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 higher than 60 ° C., preferably higher than 100 ° C., for example, 250 ° C. or lower, preferably 180 ° C. or lower. What is necessary is just to arrange | position in the atmosphere of saturated water vapor pressure. Although the pressure at this time is not specifically limited, it can be simply a normal pressure.

  Under such an atmosphere, between the PFPE-containing silane compounds of the present invention, groups bonded to Si after hydrolysis rapidly undergo dehydration condensation. 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. As a result, a bond is formed between the perfluoro (poly) ether group-containing silane compound and the substrate.

  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. In the present invention, from the viewpoint of suppressing the decomposition of the perfluoro (poly) ether group-containing silane compound, superheated steam at 250 ° C. or lower, preferably 180 ° C. or lower is preferably used for water supply and drying heating. When the substrate on which the precursor film is formed is exposed to superheated water vapor, first, dew condensation occurs on the surface of the precursor film due to the temperature difference between the superheated water vapor and the relatively low temperature precursor film. Moisture is supplied to the membrane. Eventually, as the temperature difference between the superheated steam and the precursor film becomes smaller, the moisture on the surface of the precursor film is vaporized in a dry atmosphere by the superheated steam, and the moisture content on the surface of the precursor film gradually decreases. While the amount of moisture on the surface of the precursor film is reduced, that is, while the precursor film is in a dry atmosphere, the precursor film on the surface of the substrate comes into contact with the superheated steam, thereby the temperature of the superheated steam ( It will be heated to a temperature exceeding 100 ° C. under normal pressure. Therefore, if superheated steam is used, moisture supply and drying heating can be carried out continuously only by exposing the substrate on which the precursor film is formed to superheated steam.

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

  As described above, the surface treatment layer derived from the film of the surface treatment agent of the present invention is formed on the surface of the substrate, and the article of the present invention is manufactured. The surface treatment layer obtained by this has high friction durability. In addition to high friction durability, this surface treatment layer has water repellency, oil repellency, antifouling properties (for example, preventing adhesion of dirt such as fingerprints), depending on the composition of the surface treatment agent used. As a functional thin film, it can be waterproof (to prevent water from entering electronic parts, etc.), surface slippery (or lubricity, for example, wiping off dirt such as fingerprints, and excellent touch to fingers). It can be suitably used.

  The article having a surface treatment layer obtained by the present invention is not particularly limited, but may be an optical member. Examples of the optical member include the following optical members: For example, a cathode ray tube (CRT: eg, TV, personal computer monitor), liquid crystal display, plasma display, organic EL display, inorganic thin film EL dot matrix display, rear projection type Display, display such as fluorescent display tube (VFD), field emission display (FED), or front protective plate, antireflection plate, polarizing plate, antiglare plate, or antireflection film treatment on the surface of these displays A lens such as glasses; a touch panel sheet of a device such as a mobile phone or a personal digital assistant; a disc surface of an optical disc such as a Blu-ray (registered trademark) disc, a DVD disc, a CD-R, or an MO; Optical fa Bar; the display surface of the watch, such as.

  Other articles having a surface treatment layer obtained by the present invention may include ceramic products, coated surfaces, fabric products, leather products, medical products, plasters, and the like.

  Further, the other article having the surface treatment layer obtained by the present invention may be a medical device or a medical material.

  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 in the range of 1 to 50 nm, preferably 1 to 30 nm, more preferably 1 to 15 nm. Optical performance, surface slipperiness, friction durability and antifouling properties From the point of view, it is preferable.

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

  The surface treatment agent of the present invention will be described more specifically through the following examples, but the present invention is not limited to these examples. In this example, all the chemical formulas shown below show average compositions.

（式中、ｌは２０〜３０の整数であり、ｍは１〜６の整数であり、平均分子量は約４０００である（^１９Ｆ−ＮＭＲ値）。）

化合物Ｂ：

（式中、ｌは２０〜３０の整数であり、平均分子量は約４０００である（^１９Ｆ−ＮＭＲ値）。）

化合物Ｃ：

（式中、Ｒｆａは−ＣＦ_２（ＯＣ_２Ｆ_４）_ｐ（ＯＣＦ_２）_ｑ−ＯＣＦ_２−であり、ｐ／ｑは０．９であり、ｐ＋ｑは約４５であり、ｎは３である。尚、添字ｐまたはｑ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任意である。）
Example As the perfluoro (poly) ether group-containing silane compound 1, the following three kinds of compounds were prepared.

Compound A:

(In the formula, l is an integer of 20 to 30, m is an integer of 1 to 6, and the average molecular weight is about 4000 ( ¹⁹ F-NMR value).)

Compound B:

(In the formula, l is an integer of 20 to 30, and the average molecular weight is about 4000 ( ¹⁹ F-NMR value).)

Compound C:

Where Rfa is —CF ₂ (OC ₂ F ₄ ) _p (OCF ₂ ) _q —OCF ₂ —, p / q is 0.9, p + q is about 45, and n is 3. Note that the order of existence of each repeating unit with parentheses p or q attached in parentheses is arbitrary.)

Moreover, the following three types of compounds were prepared as the silane compound 2 represented by the formula (S).

Compound _{O: CH 2 = CHSi (OCH} 3) 3
Compound P: CH ₂ ═CHSi (OCOCH ₃ ) ₃
Compound _{Q: CH 2 = CHCH 2 Si} (OCH 3) 3

  The above compounds 1 and 2 were mixed at the ratio shown in Table 1, 1-No. 18 surface treatment compositions were obtained. At this time, Novec (trade name) 7200 manufactured by Sumitomo 3M Limited was used as the diluent solvent. No. 1 to 15 are examples of the present invention. 16-18 are comparative examples.

  No. above. 1-No. 18 g of the surface treatment composition of 18 was put in a sample bottle, 0.1 g of ion-exchanged water was added to each sample, stored in a thermostat at 70 ° C. ± 5 ° C. for 7 days, returned to 25 ° C., and the appearance was visually observed. The results are shown in Table 2.

  As apparent from the above results, the surface treatment composition of the present invention to which the silane compound represented by the formula (S) is added is compared with the surface treatment composition not containing the silane compound represented by the formula (S). It was confirmed that the storage stability was improved.

  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 (33)

The following general formulas (A1), (B1), and (C1) :

[Where:
PFPE has the formula:
_{- (OC 4 F 8) a} - (OC 3 F 6) b - (OC 2 F 4) c - (OCF 2) d -
Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d The order of existence of each repeating unit with parentheses attached with is arbitrary in the formula.)
A group represented by:
Rf represents each independently an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence;
R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
R ² represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group;
R ¹¹ independently represents a hydrogen atom or a halogen atom at each occurrence;
R ¹² independently represents a hydrogen atom or a lower alkyl group at each occurrence;
n ^{_{is, (- SiR 1 n R 2}} 3-n) independently for each unit, an integer from 0 to 3;
However, the formula (A1), and (B1) in Oite, at least one ^{R 2} is present;
Each X ¹ independently represents a single bond or a divalent to 10-valent organic group;
X ² represents each independently a single bond or a divalent organic group at each occurrence;
t is independently an integer from 1 to 10 at each occurrence;
each α is independently an integer from 1 to 9;
α ′ is each independently an integer of 1 to 9;
X ⁵ each independently represents a single bond or a divalent to 10-valent organic group;
each β is independently an integer from 1 to 9;
each β ′ is independently an integer from 1 to 9;
X ⁷ each independently represents a single bond or a divalent to 10-valent organic group;
each γ is independently an integer of 1 to 9;
each γ ′ is independently an integer from 1 to 9;
R ^a independently represents —Z—SiR ⁷¹ _p R ⁷² _q R ⁷³ _r at each occurrence;
Z represents, independently at each occurrence, an oxygen atom or a divalent organic group;
R ⁷¹ independently represents R ^{a ′} at each occurrence;
R ^{a ′} is synonymous with R ^a ;
In R ^a , the maximum number of Si linearly linked via the Z group is 5;
R ⁷² independently represents at each occurrence a hydroxyl group or a hydrolyzable group;
R ⁷³ independently represents at each occurrence a hydrogen atom or a lower alkyl group;
p is independently an integer from 0 to 3 at each occurrence;
q is independently an integer from 0 to 3 at each occurrence;
r is independently an integer from 0 to 3 at each occurrence;
However, in one R ^a , the sum of p, q and r is 3, and in formula (C1) , at least one R ⁷² is present;
R ^b independently represents a hydroxyl group or a hydrolyzable group at each occurrence;
R ^c independently represents a hydrogen atom or a lower alkyl group at each occurrence;
k is independently an integer from 1 to 3 at each occurrence;
l is independently an integer from 0 to 2 at each occurrence;
m is independently an integer from 0 to 2 at each occurrence;
However, the sum of k, l, and m is 3 in the unit enclosed in parentheses with γ. ]
At least one perfluoro (poly) ether group-containing silane compound represented by any of the following:
And the following formula (S):
SiR ⁵¹ _n R ⁶¹ _4-n (S)
[Where:
R ⁵¹ each independently represents CH ₂ ═CH—, CH ₂ ═CHCH ₂ —, HSCH ₂ CH ₂ CH ₂ , H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ , CH ₂ = C (CH ₃ ). _{C (O) OCH 2 CH 2} CH 2,

Is;
Each R ⁶¹ is independently a hydrolyzable group;
n is an integer of 0-3. ]
In looking it contains at least one silane compound represented,
The surface treating agent whose mass ratio of the said perfluoro (poly) ether group containing silane compound and the silane compound represented by said Formula (S) is 100: 1-10000: 1 .   The surface treating agent according to claim 1, wherein Rf is a C 1-16 perfluoroalkyl group. PFPE is one of the following formulas (i) to (iv):
_{- (OCF 2 CF 2 CF 2} ) b - (i)
[Wherein, b is an integer of 1 to 200. ]
_{- (OCF (CF 3) CF} 2) b - (ii)
[Wherein, b is an integer of 1 to 200. ]
_{- (OCF 2 CF 2 CF 2} CF 2) a - (OCF 2 CF 2 CF 2) b - (OCF 2 CF 2) c - (OCF 2) d - (iii)
[Wherein, a and b are each independently 0 or an integer of 1 to 30, c and d are each independently an integer of 1 to 200, and the subscripts a, b, c, or d] The order of presence of each repeating unit in parentheses with an is optional in the formula. ]
Or _{^{- (OC 2 F 4 -R 8}} ) n "- (iv)
[Wherein R ⁸ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ ;
_{n ″} is an integer of 2 to 100.]
The surface treating agent according to claim 1 or 2, which is a group represented by the formula: PFPE has the following formula (iii):
_{- (OCF 2 CF 2 CF 2} CF 2) a - (OCF 2 CF 2 CF 2) b - (OCF 2 CF 2) c - (OCF 2) d - (iii)
[Wherein, a and b are each independently 0 or an integer of 1 to 30, c and d are each independently an integer of 1 to 200, and the c / d ratio is 0.00. The order of existence of each repeating unit which is 2 or more and 1.5 or less and is attached with the subscript a, b, c or d in parentheses is arbitrary in the formula. ]
The surface treating agent in any one of Claims 1-3 which is group represented by these. X ¹ , X ⁵ and X ⁷ are each independently a divalent to tetravalent organic group, α, β and γ are each independently 1 to 3, α ′, β ′ and γ The surface treating agent according to any one of claims 1 to 4, wherein 'is 1. X ¹ , X ⁵ and X ⁷ are divalent organic groups, α, β and γ are 1, and α ′, β ′ and γ ′ are 1. Surface treatment agent. X ¹ , X ⁵ and X ⁷ are each independently-(R ³¹ ) _{p '} -(X ^a ) _q'-
[Where:
R ³¹ represents a single bond, — (CH ₂ ) _{s ′} — (wherein s ′ is an integer of 1 to 20) or an o-, m-, or p-phenylene group;
^Xa represents-( ^Xb ) _l'- (wherein l 'is an integer of 1 to 10);
X ^b is independently at each occurrence, —O—, —S—, o—, m- or p-phenylene group, —C (O) O—, —Si (R ³³ ) ₂ —, — ( Si (R ³³ ) ₂ O) _{m ′} —Si (R ³³ ) ₂ — (wherein m ′ is an integer of 1 to 100), —CONR ³⁴ —, —O—CONR ³⁴ —, —NR ³⁴ —. And represents a group selected from the group consisting of — (CH ₂ ) _{n ′} — (wherein n ′ is an integer of 1 to 20);
R ³³ independently represents a phenyl group, a C _1-6 alkyl group or a C _1-6 alkoxy group at each occurrence;
R ³⁴ each independently represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group at each occurrence;
p ′ is 0 or 1;
q ′ is 0 or 1;
Wherein at least one of p ′ and q ′ is 1, and the order of presence of each repeating unit in parentheses with p ′ or q ′ is arbitrary in the formula;
R ³¹ and X ^a may be substituted with one or more substituents selected from a fluorine atom, a C _1-3 alkyl group, and a C _1-3 fluoroalkyl group. ]
The surface treating agent of Claim 6 which is group represented by these. X ¹ , X ⁵ and X ⁷ are each independently:
_{-CH 2 O (CH 2) 2} -,
_{-CH 2 O (CH 2) 3} -,
_{-CH 2 O (CH 2) 6} -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 3 Si (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 10 Si (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 3) 2 (CH 2) 2 -,
-CH ₂ OCF ₂ CHFOCF ₂ -,
_{-CH 2 OCF 2 CHFOCF 2 CF 2} -,
_{-CH 2 OCF 2 CHFOCF 2 CF 2} CF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF 2 CF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF 2 CF 2 CF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF (CF 3) CF 2 OCF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF (CF 3) CF 2 OCF 2 CF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF (CF 3) CF 2 OCF 2 CF 2 CF 2 -,
_{-CH 2 OCH 2 CHFCF 2 OCF 2} -,
_{-CH 2 OCH 2 CHFCF 2 OCF 2} CF 2 -,
_{-CH 2 OCH 2 CHFCF 2 OCF 2} CF 2 CF 2 -,
_{-CH 2 OCH 2 CHFCF 2 OCF (} CF 3) CF 2 OCF 2 -,
_{-CH 2 OCH 2 CHFCF 2 OCF (} CF 3) CF 2 OCF 2 CF 2 -,
_{-CH 2 OCH 2 CHFCF 2 OCF (} CF 3) CF 2 OCF 2 CF 2 CF 2 -
_{-CH 2 OCH 2 (CH 2)} 7 CH 2 Si (OCH 3) 2 OSi (OCH 3) 2 (CH 2) 2 Si (OCH 3) 2 OSi (OCH 3) 2 (CH 2) 2 -,
_{-CH 2 OCH 2 CH 2 CH 2} Si (OCH 3) 2 OSi (OCH 3) 2 (CH 2) 3 -,
- _{(CH 2)} 2 -,
- _{(CH 2)} 3 -,
- _{(CH 2)} 4 -,
- _{(CH 2)} 6 -,
-CONH- _{(CH 2)} 3 -,
_{-CON (CH 3) - (CH} 2) 3 -,
_{-CON (Ph) - (CH 2} ) 3 - ( wherein, Ph means phenyl),
-CONH- _{(CH 2)} 6 -,
_{-CON (CH 3) - (CH} 2) 6 -,
_{-CON (Ph) - (CH 2} ) 6 - ( wherein, Ph means phenyl),
_{-CONH- (CH 2) 2 NH (} CH 2) 3 -,
_{-CONH- (CH 2) 6 NH (} CH 2) 3 -,
_{-CH 2 O-CONH- (CH 2} ) 3 -,
_{-CH 2 O-CONH- (CH 2} ) 6 -,
-S- _{(CH 2)} 3 -,
_{- (CH 2) 2 S (} CH 2) 3 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 3 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 10 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 3) 2 (CH 2) 2 -
_{-C (O) O- (CH 2} ) 3 -,
_{-C (O) O- (CH 2} ) 6 -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 - (CH 2) 2 -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 -CH (CH 3) -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 - (CH 2) 3 -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 -CH (CH 3) -CH 2 -,

The surface treating agent according to claim 6 or 7, which is selected from the group consisting of: X ¹ is —O—CFR ¹³ — (CF ₂ ) _e —,
R ¹³ represents a fluorine atom or a lower fluoroalkyl group,
e is 0 or 1;
The surface treating agent according to claim 1. X ² is — (CH ₂ ) _s —,
s is an integer from 0 to 2,
The surface treating agent according to any one of claims 1 to 9. The surface treating agent according to claim 1, wherein k is 3 and q is 3 in ^Ra . The surface treating agent according to any one of claims 1 to 4, wherein X ¹ , X ⁵ and X ⁷ are each independently a trivalent to trivalent organic group. X ¹ , X ⁵ and X ⁷ are each independently:

[Wherein, in each group, at least one of T is the following group bonded to PFPE in formulas (A1), (B1), and (C1) :
_{-CH 2 O (CH 2) 2} -,
_{-CH 2 O (CH 2) 3} -,
_{-CF 2 O (CH 2) 3} -,
- _{(CH 2)} 2 -,
- _{(CH 2)} 3 -,
- _(CH 2) ₄ -,
-CONH- _{(CH 2)} 3 -,
_{-CON (CH 3) - (CH} 2) 3 -,
_{-CON (Ph) - (CH 2} ) 3 - ( wherein, Ph means phenyl), and

And
At least one of another T has the formula (A1), (B1), and attached to a carbon atom or Si atom in _{(C1) - (CH 2)} n - (n is an integer of from 2 to 6) be The rest are each independently a methyl group, a phenyl group or an alkoxy group having 1 to 6 carbon atoms,
Each of R ⁴¹ is independently a hydrogen atom, a phenyl group, an alkoxy group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms;
R ⁴² each independently represents a hydrogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group. ]
The surface treating agent according to claim 12, which is selected from the group consisting of: The surface treating agent according to any one of claims 1 to 13, wherein the perfluoro (poly) ether group-containing silane compound is at least one compound represented by the formula (A1 ) . The surface treating agent according to any one of claims 1 to 13, wherein the perfluoro (poly) ether group-containing silane compound is at least one compound represented by the formula (B1 ) . The surface treating agent according to any one of claims 1 to 13, wherein the perfluoro (poly) ether group-containing silane compound is at least one compound represented by the formula (C1 ) . Each R ⁶¹ is independently —OR ⁶² , —OCOR ⁶² , —O—N═CR ⁶² ₂ , —ONR ₂ , —NR ⁶² ₂ or —NR ⁶² —CO—R ⁶² ;
R ⁶² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
n is 1 or 2;
The surface treating agent according to any one of claims 1 to 16. The silane compound represented by the formula (S) is the following compound:
Si (OC ₂ H ₅ ) ₄ ,
CH ₂ = CHSi (OCH ₃ ) ₃ ,
CH ₂ = CHSi (OCOCH ₃ ) ₃ ,
HSCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (CH ₃ ) (OCH ₃ ) ₂ ,
_{CH 2 = C (CH 3)} C (O) OCH 2 CH 2 CH 2 Si (OCH 3) 3,
_{CH 2 = C (CH 3)} C (O) OCH 2 CH 2 CH 2 Si (OCH 2 CH 2 OCH 2) 3,

Pressurized et is selected, a surface treatment agent according to any one of claims 1 to 17.   Furthermore, the surface treating agent in any one of Claims 1-18 containing a solvent.   The surface treating agent according to claim 19, wherein the solvent is a hydrofluoroether solvent. Hydrofluoroether solvent _is a _{C 4 F 9 OCH 3, C} 4 F 9 OC 2 H 5 or _{CF 3 CH 2 OCF 2 CHF 2} , a surface treatment agent according to claim 20.   The surface treatment agent according to any one of claims 1 to 21, wherein the concentration of the silane compound represented by the formula (S) is 0.0001 mass% to 1 mass% in the entire surface treatment agent.   The surface treating agent according to any one of claims 1 to 22, further comprising one or more other components selected from fluorine-containing oils, silicone oils, and catalysts. The fluorine-containing oil has the formula (3):
^{_{R 21 - (OC 4 F 8}} ) a '- (OC 3 F 6) b' - (OC 2 F 4) c '- (OCF 2) d' -R 22
... (3)
[Where:
R ²¹ represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;
R ²² represents an alkyl group having 1 to 16 carbon atoms, a fluorine atom or a hydrogen atom, which may be substituted with one or more fluorine atoms;
a ′, b ′, c ′ and d ′ each represent the number of four types of repeating units of perfluoro (poly) ether constituting the main skeleton of the polymer, and are each independently an integer of 0 to 300, , A ′, b ′, c ′ and d ′ are at least 1 and the order of presence of each repeating unit in parentheses with the subscript a ′, b ′, c ′ or d ′ is given by the formula Is optional. ]
The surface treating agent according to claim 23, which is one or more compounds represented by: The fluorine-containing oil has the formula (3a) or (3b):
^{_{R 21 - (OCF 2 CF 2}} CF 2) b '' -R 22 ··· (3a)
^{_{R 21 - (OCF 2 CF 2}} CF 2 CF 2) a '' - (OCF 2 CF 2 CF 2) b '' - (OCF 2 CF 2) c '' - (OCF 2) d '' -R 22 · .. (3b)
[Where:
R ²¹ represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;
R ²² represents an alkyl group having 1 to 16 carbon atoms, a fluorine atom or a hydrogen atom, which may be substituted with one or more fluorine atoms;
In formula (3a), b ″ is an integer of 1 to 100;
In formula (3b), a ″ and b ″ are each independently an integer of 0 or more and 30 or less, and c ″ and d ″ are each independently an integer of 1 or more and 300 or less;
The order of presence of each repeating unit in parentheses with the suffix a ″, b ″, c ″ or d ″ is arbitrary in the formula. ]
The surface treating agent according to claim 23 or 24, which is one or more compounds represented by the formula:   The surface treatment agent according to any one of claims 1 to 25, which is used as an antifouling coating agent or a waterproof coating agent.   The surface treating agent according to any one of claims 1 to 26, which is used for vacuum deposition.   The pellet containing the surface treating agent in any one of Claims 1-27.   An article comprising a substrate and a layer formed from the surface treatment agent according to any one of claims 1 to 27 on a surface of the substrate.   30. The article of claim 29, wherein the substrate is glass or sapphire glass.   32. The article of claim 30, wherein the glass is a glass selected from the group consisting of soda lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass and quartz glass.   The article according to any one of claims 29 to 31, wherein the article is an optical member.   The article according to any of claims 29 to 32, wherein the article is a display.