KR20190113855A - Surface treatment agent containing a perfluoro (poly) ether group containing silane compound, pellets and articles using the same - Google Patents

Abstract

This invention provides the surface treating agent containing the perfluoro (poly) ether group containing silane compound and the compound containing the atom which has a lone pair in a molecular structure.

Description

Surface treatment agent containing a perfluoro (poly) ether group containing silane compound, pellets and articles using the same

This invention relates to the surface treating agent containing a perfluoro (poly) ether group containing silane compound, and the pellet and the article using the same.

It is known that some kinds of fluorine-containing compounds can provide excellent water repellency, oil repellency, antifouling properties, and the like when used for surface treatment of substrates. As such a fluorine-containing silane compound, the perfluoropolyether group containing silane compound which has a perfluoropolyether group in a molecular backbone, and has a hydrolysable group couple | bonded with Si atom in a molecule terminal or terminal part is known. For example, Patent Document 1 describes a perfluoropolyether group-containing silane compound having a hydrolyzable group bonded to a Si atom at a molecular terminal or at a terminal portion.

The layer (henceforth a "surface treatment layer") obtained from the surface treating agent containing the above-mentioned fluorine-containing silane compound is what is called a functional thin film, and is given to glass etc. In particular, since the surface treatment layer can exhibit the above functions even in a thin film, the surface treatment layer is applied to optical members such as glasses, touch panels, and operation screens of portable terminals that require light transparency or transparency.

Japanese Patent Publication No. 2013-117012

Such surface treatment layers are required to have good durability in order to impart desired functions to the surface of the substrate over a long period of time. However, it was found by the inventors that the surface treatment layer as described above may not have sufficient durability.

An object of the present invention is to provide a surface treatment agent suitable for obtaining a surface treatment layer having improved durability.

According to the first aspect of the present invention, formula (A1), formula (A ₂ ), formula (B1), formula (B2), formula (C1) or formula (C2):

[In meals:

PFPE, independently at each occurrence, is represented by the formula:

_{- (OC 6 F 12) a} - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -

(a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, the sum of a, b, c, d, e and f is at least 1, and a, b, c, d The order of the existence of each repeating unit, enclosed in parentheses, with e or f is arbitrary in the formula.)

A group represented by;

Each occurrence of Rf independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;

R ¹³ each independently represent a hydroxyl group or a hydrolyzable group;

R ¹⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms;

R ¹¹ each independently represent a hydrogen atom or a halogen atom;

R < ¹² > represents a hydrogen atom or a lower alkyl group each independently in each appearance,

n is an integer of 0 to 3, independently for each (-SiR ¹³ _n R ¹⁴ _3-n ) unit;

Provided that at least two Si bonded to a hydroxyl group or a hydrolyzable group are present in formulas (A1) and (A2);

Each X ¹ independently represents a single bond or a 2 to 10 valent organic group;

X ² in each occurrence independently represent a single bond or a divalent organic group,

t is an integer of 1-10 each independently in each occurrence;

α is an integer of 1 to 9 each independently at each occurrence;

α 'are each independently an integer of 1 to 9;

X <^3> represents a single bond or a 2-10 valent organic group each independently in each appearance;

β is an integer of 1 to 9 each independently at each occurrence;

β 'are each independently an integer of 1 to 9;

Each occurrence of R ^a independently represents -Z ¹ -SiR ¹ _p R ² _q R ³ _r ;

Z ¹ in each occurrence independently represents an oxygen atom or a divalent organic group;

R ¹ each independently represent R ^{a ′} in each occurrence;

R ^{a '} is synonymous with R ^a ;

Among R ^a , at most 5 Si is linearly connected through the Z ¹ group;

R ² in each occurrence independently represents a hydroxyl group or a hydrolyzable group;

R < ³ > represents a hydrogen atom or a lower alkyl group each independently in each appearance,

p is an integer of 0 to 3 each independently at each occurrence;

q is an integer of 0 to 3 each independently at each occurrence;

r is an integer of 0 to 3 each independently at each occurrence;

However, for each -Z ¹ -SiR ¹ _p R ² _q R ³ _r , the sum of p, q and r is 3, and in formulas (B1) and (B2), Si bonded to a hydroxyl group or a hydrolyzable group is represented by At least two are present;

Each occurrence of R ^b independently represents a hydroxyl group or a hydrolyzable group;

Each occurrence of R ^c independently represents a hydrogen atom or a lower alkyl group,

k1 is an integer of 0-3 each independently at each occurrence;

l1 is an integer of 0 to 2 each independently at each occurrence;

m1 is an integer of 0-2 each independently at each occurrence;

However, in every -SiR ^a _k1 R ^b _l1 R ^c _m1 , the sum of k1, l1 and m1 is 3,

X ⁴ in each occurrence independently represents a single bond or a 2 to 10 valent organic group;

γ is an integer of 1 to 9 each independently at each occurrence;

γ 'are each independently an integer of 1 to 9;

Each occurrence of R ^d independently represents -Z ² -CR ⁸¹ _p2 R ⁸² _q2 R ⁸³ _r2 ;

Z ² each independently represent an oxygen atom or a divalent organic group;

R ⁸¹ in each occurrence independently represents R ^{d ′} ;

R ^{d '} is synonymous with R ^d ;

Among R ^d , up to 5 C may be connected linearly through the Z ² group;

R ⁸² each independently represent —Y—SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 in each occurrence;

Y represents a divalent organic group each independently in each appearance;

R ⁸⁵ each independently represent a hydroxyl group or a hydrolyzable group;

R ⁸⁶ each independently at each occurrence represents a hydrogen atom or a lower alkyl group,

n2 is, (-Y-SiR ⁸⁵ R ⁸⁶ _{n2 3-n2)} independently for each unit, an integer of 0 to 3;

R ⁸³ at each occurrence independently represent a hydrogen atom or a lower alkyl group,

p2 is an integer of 0-3 each independently at each occurrence;

q2 is an integer of 0-3 each independently in each occurrence;

r2 is an integer of 0 to 3 each independently at each occurrence;

However, in every -Z ² -CR ⁸¹ _p2 R ⁸² _q2 R ⁸³ _r2 , p2, the sum of q2 and r2 is 3;

R ^e each independently represent —Y—SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 at each occurrence;

R ^f each independently represents a hydrogen atom or a lower alkyl group,

k2 is an integer of 0-3 each independently at each occurrence;

l2 is an integer of 0-3 each independently at each occurrence;

m2 is an integer of 0-3 each independently at each occurrence;

However, in each of (CR ^d _k2 R ^e _l2 R ^f _m2 ), the sum of k2, l2 and m2 is 3, and in the formulas (C1) and (C2), the group represented by -Y-SiR ⁸⁵ is 2 or more. exist.]

A surface treating agent is provided that contains a perfluoro (poly) ether group-containing silane compound represented by any of the above, and a compound containing an atom having a non-covalent electron pair in its molecular structure.

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

According to the 3rd summary of this invention, the article provided with a base material and the layer formed with the surface treating agent of this invention on the surface of this base material is provided.

According to this invention, the novel surface treating agent containing a perfluoro (poly) ether group (Hereinafter, it may be called "PFPE") containing silane compound is provided. The surface treatment agent of this invention is suitable for formation of the surface treatment layer which improved durability, especially the surface treatment layer which shows favorable durability also in presence of an acid or an alkali. Furthermore, according to this invention, the pellet containing the surface treating agent of this invention is provided. According to this invention, the article provided with the base material and the layer formed on the surface of this base material with the surface treating agent of this invention is provided.

When used in this specification, a "hydrocarbon group" is group containing carbon and hydrogen, and means the group which detached one hydrogen atom from a hydrocarbon. Although it does not specifically limit as such a hydrocarbon group, C1-C20 hydrocarbon group which may be substituted by one or more substituents, for example, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, etc. are mentioned. The said "aliphatic hydrocarbon group" may be linear, branched, or cyclic, or may be either saturated or unsaturated. In addition, the hydrocarbon group may contain one or more ring structures. Moreover, such a hydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. in the terminal or molecular chain.

When used in this specification, it is although it does not specifically limit as a substituent of a "hydrocarbon group", For example, Halogen atom; C _1-6 alkyl group, C _2-6 alkenyl group, C _2-6 alkynyl group, C _3-10 cycloalkyl group, C _3-10 unsaturated cycloalkyl group, which may be substituted by one or more halogen atoms, 5 to And one or more groups selected from a 10 membered heterocyclyl group, a 5 to 10 membered unsaturated heterocyclyl group, a C _6-10 aryl group and a 5 to 10 membered heteroaryl group.

In this specification, an alkyl group and a phenyl group may be unsubstituted and may be substituted, unless it mentions specially. Although it does not specifically limit as a substituent of such a group, For example, the 1 or more group chosen from a halogen atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _2-6 alkynyl group is mentioned.

When used in this specification, a "2- to 10-valent organic group" means a 2- to 10-valent group containing carbon. Although it does not specifically limit as such a 2-10 valent organic group, The 2-10 valent group which removed 1-9 hydrogen atoms again from a hydrocarbon group is mentioned.

[Surface Treatment]

Hereinafter, the surface treating agent of this invention is demonstrated.

The surface treating agent of this invention contains a PFPE containing silane compound and the compound containing the atom which has a lone pair in a molecular structure.

(PFPE-containing silane compound)

The said PFPE containing silane compound is a compound represented by any of Formula (A1), Formula (A2), Formula (B1), Formula (B2), Formula (C1), or Formula (C2).

The PFPE-containing silane compound is preferably 0.01 to 100 parts by mass, and more preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the surface treating agent.

The PFPE-containing silane compound is not particularly limited, but may have a number average molecular weight of 5 × 10 ² to 1 × 10 ⁵ . Among these ranges, those having a number average molecular weight of 2,000 to 30,000, more preferably 2,500 to 12,000, are preferred from the viewpoint of friction durability. In addition, in this invention, a number average molecular weight is taken as the value measured by ¹⁹ F-NMR.

In one embodiment, the PFPE-containing silane compound of the present invention may have a number average molecular weight of 1,000 to 40,000, preferably 1,000 to 32,000, more preferably 1,000 to 20,000, even more preferably 1,000 to 12,000. .

Hereinafter, the PFPE containing silane compound represented by said Formula (A1), (A2), (B1), (B2), (C1), and (C2) is demonstrated.

Formulas (A1) and (A2):

In said formula, Rf represents the C1-C16 alkyl group which may be substituted by one or more fluorine atoms independently in each appearance.

"The C1-C16 alkyl group" in the C1-C16 alkyl group which may be substituted by the said 1 or more fluorine atom may be linear, branched chain, Preferably it is a linear or branched carbon number. It is 1-6, especially a C1-C3 alkyl group, More preferably, it is a linear C1-C3 alkyl group.

Rf is preferably an alkyl group having 1 to 16 carbon atoms substituted by one or more fluorine atoms, more preferably CF ₂ HC _1-15 perfluoroalkylene group or C _1-16 perfluoro It is an alkyl group, More preferably, it is a C _1-16 perfluoroalkyl group.

The C1-C16 perfluoroalkyl group may be linear or branched, Preferably it is a C1-C6, especially C1-C3 perfluoroalkyl group of a linear or branched chain, More preferably, it is a linear chain. And a C 1 to C 3 perfluoroalkyl group, specifically -CF ₃ , -CF ₂ CF ₃ , or -CF ₂ CF ₂ CF ₃ .

In said formula, PFPE is independent in each appearance,

Is represented by. In formula, a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1. Preferably, a, b, c, d, e and f are each independently an integer of 0 or more and 100 or less. Preferably, the sum of a, b, c, d, e and f is 5 or more, more preferably 10 or more. Preferably, the sum of a, b, c, d, e and f is 200 or less, More preferably, it is 100 or less, For example, 10 or more and 200 or less, More specifically, it is 10 or more and 100 or less. In addition, the order of existence of each repeating unit a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula.

Although these repeating units may be linear or branched, they are linear. For example,-(OC ₆ F ₁₂ )-is-(OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ )-,-(OCF (CF ₃ ) CF ₂ CF ₂ CF ₂ CF ₂ )-,- (OCF ₂ CF (CF ₃ ) CF ₂ CF ₂ CF ₂ )-,-(OCF ₂ CF ₂ CF (CF ₃ ) CF ₂ CF ₂ )-,-(OCF ₂ CF ₂ CF ₂ CF (CF ₃ ) CF ₂ )-,-(OCF ₂ CF ₂ CF ₂ CF ₂ CF (CF ₃ ))-and the like may be used, but preferably-(OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ )-. -(OC ₅ F ₁₀ )-is-(OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ )-,-(OCF (CF ₃ ) CF ₂ CF ₂ CF ₂ )-,-(OCF ₂ CF (CF ₃ ) CF ₂ CF ₂ )-,-(OCF ₂ CF ₂ CF (CF ₃ ) CF ₂ )-,-(OCF ₂ CF ₂ CF ₂ CF (CF ₃ ))-, etc. may be used, but preferably-(OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ )-. -(OC ₄ F ₈ )-is-(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 )-. -(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 ))- Preferably-(OCF ₂ CF ₂ CF ₂ )-. In _{addition, - (OC 2 F 4)} - is, - (OCF ₂ CF ₂₎ - and _{- (OCF (CF 3))} - which is even but, preferably - (OCF ₂ CF ₂₎ - a.

In one embodiment, the PFPE is-(OC ₃ F ₆ ) _d- (wherein d is 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less) . Preferably, PFPE is-(OCF ₂ CF ₂ CF ₂ ) _d- (wherein d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less) or- (OCF (CF ₃ ) CF ₂ ) _d − (wherein d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less). More preferably, PFPE is-(OCF ₂ CF ₂ CF ₂ ) _d- (wherein d is 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less) .

In another embodiment, the PFPE is-(OC ₄ F ₈ ) _c- (OC ₃ F ₆ ) _d- (OC ₂ F ₄ ) _e- (OCF ₂ ) _f- (wherein c and d are each Are independently integers of 0 or more and 30 or less, and e and f are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, and c, d, e and f The sum of is at least 5, preferably at least 10, and the order of existence of each repeating unit enclosed in parentheses with the subscripts c, d, e or f is arbitrary in the formula). Preferably, PFPE is-(OCF ₂ CF ₂ CF ₂ CF ₂ ) _c- (OCF ₂ CF ₂ CF ₂ ) _d- (OCF ₂ CF ₂ ) _e- (OCF ₂ ) _f- . In one embodiment, the PFPE is-(OC ₂ F ₄ ) _e- (OCF ₂ ) _f- (wherein e and f are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more Preferably, it is an integer of 10 or more and 200 or less, and the order of existence of each repeating unit enclosed in parentheses with the subscript e or f may be arbitrary in a formula).

In one embodiment, the PFPE is-(OC ₂ F ₄ ) _e- (OCF ₂ ) _f- (wherein e and f are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more Preferably, it is an integer of 10 or more and 200 or less, and the order of existence of each repeating unit enclosed in parentheses with the subscript e or f may be arbitrary in a formula).

In said formula, in PFPE, ratio of e to f (henceforth "e / f ratio") is 0.1 or more and 10 or less, Preferably it is 0.2 or more and 5.0 or less, More preferably, it is 0.2 or more and 2.0 It is below, More preferably, it is 0.2 or more and 1.5 or less. By setting the e / f ratio in the above range, the water repellency, oil repellency, and chemical resistance (for example, durability against saline, acid or basic aqueous solution, acetone, oleic acid or hexane) of the cured product obtained from this compound can be further improved. Can be. The smaller the e / f ratio, the better the water repellency, oil repellency, and chemical resistance of the cured product. On the other hand, stability of a compound can be improved further by making e / f ratio into 0.1 or more. The larger the e / f ratio, the better the stability of the compound.

In another embodiment, PFPE is a group represented by-(R ⁶ -R ⁷ ) _j- . In the formula, R ⁶ is a OCF ₂ or OC ₂ F _4, preferably OC ₂ F _4. Wherein R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or two or three groups independently selected from these groups It is a combination. Preferably, R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ , or is selected from OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ Or a combination of two or three groups selected independently from these groups. The combination of two or three groups independently selected from OC ₂ F ₄ , OC ₃ F _6, and OC ₄ F ₈ is not particularly limited, but 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 ₃ 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- , and -OC ₄ F ₈ OC ₂ F ₄ OC ₂ F ₄ -and the like. The j is 2 or more, preferably 3 or more, more preferably 5 or more, and 100 or less, preferably an integer of 50 or less. In the formula, OC ₂ F _4, OC ₃ F _6, OC ₄ F _8, F ₁₀ OC ₅ and OC ₆ F ₁₂ is, it may be any of linear or branched, preferably a straight chain. In this embodiment, the PFPE is preferably-(OC ₂ F ₄ -OC ₃ F ₆ ) _j -or-(OC ₂ F ₄ -OC ₄ F ₈ ) _j- .

In one embodiment, in the above formula, PFPE is independently at each occurrence,

_{- (OC 6 F 12) a} - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -

It is a group represented by and also has at least one branch structure in PFPE. That is, in this embodiment, the PFPE has at least one CF ₃ terminal (specifically, -CF ₃ , -C ₂ F _5, etc., more specifically -CF ₃ ). By having the PFPE of such a structure, the ultraviolet durability, water repellency, oil repellency, antifouling property (for example, fingerprints, etc.) of the layer (for example, the surface treatment layer) formed using the surface treatment agent of the present invention can be prevented. Prevention), chemical resistance, hydrolysis resistance, slip resistance, high friction durability, heat resistance, moisture resistance, and the like can be better.

In the above aspect, a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1. Preferably, a, b, c, d, e and f are each independently an integer of 0 or more and 100 or less. Preferably, the sum of a, b, c, d, e and f is 5 or more, more preferably 10 or more. Preferably, the sum of a, b, c, d, e and f is 200 or less, More preferably, it is 100 or less, For example, 10 or more and 200 or less, More specifically, it is 10 or more and 100 or less. In addition, the order of existence of each repeating unit a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula.

In the above aspect, the PFPE preferably has at least five branched structures, more preferably ten, and particularly preferably twenty.

In the above aspect, the number of repeating units having a branching structure is 40 or more with respect to 100 of the total number of repeating units (for example, the sum of a, b, c, d, e and f) in the PFPE structure. It is preferable, it is more preferable that it is 60 or more, and it is especially preferable that it is 80 or more. In the PFPE structure, the number of repeating units having a branched structure may be 100 or less, for example, 90 or less, with respect to the total number 100 of the repeating unit numbers.

In the above aspect, the number of repeating units having a branching structure is preferably in the range of 40 to 100, and more preferably in the range of 60 to 100 with respect to the total number 100 of repeating units in the PFPE structure. In addition, it is especially preferable to exist in the range of 80-100.

In the above aspect, CF ₃ may be mentioned as the branched chain in the branched structure.

In the above aspect, as a repeating unit having a branched structure, for example,-(OC ₆ F ₁₂ )-,-(OCF (CF ₃ ) CF ₂ CF ₂ CF ₂ CF ₂ )-,-(OCF ₂ CF ( CF ₃ ) CF ₂ CF ₂ CF ₂ )-,-(OCF ₂ CF ₂ CF (CF ₃ ) CF ₂ CF ₂ )-,-(OCF ₂ CF ₂ CF ₂ CF (CF ₃ ) CF ₂ )-,-( OCF ₂ CF ₂ CF ₂ CF ₂ CF (CF ₃ ))-and the like. As-(OC ₅ F ₁₀ )-,-(OCF (CF ₃ ) CF ₂ CF ₂ CF ₂ )-,-(OCF ₂ CF (CF ₃ ) CF ₂ CF ₂ )-,-(OCF ₂ CF ₂ CF ( CF ₃ ) CF ₂ )-,-(OCF ₂ CF ₂ CF ₂ CF (CF ₃ ))-and the like. As-(OC ₄ F ₈ )-,-(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 ))-. Examples of-(OC ₃ F ₆ )-include-(OCF (CF ₃ ) CF ₂ )-and-(OCF ₂ CF (CF ₃ ))-. Examples of-(OC ₂ F ₄ )-include-(OCF (CF ₃ ))-.

In the above aspect, the PFPE may include a linear repeating unit together with a repeating unit having a branched structure. As a linear repeating unit,-(OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ )-,-(OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ )-,-(OCF ₂ CF ₂ CF ₂ CF ₂ ) -,-(OCF ₂ CF ₂ CF ₂ )-, and-(OCF ₂ CF ₂ )-.

In the above aspect, Preferably, in the PFPE, repeating units-(OC ₆ F ₁₂ )-,-(OC ₅ F ₁₀ )-,-(OC ₄ F ₈ )-, and-(OC ₃ F ₆ )- Has a branching structure.

In the above aspect, more preferably, the PFPE consists of a repeating unit OC ₆ F ₁₂ , OC ₅ F ₁₀ , OC ₄ F ₈ , and OC ₃ F ₆ having a branched structure.

In one embodiment, the PFPE is-(OC ₃ F ₆ ) _d- (wherein d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less) , PFPE has at least one branching structure.

In the above aspect, the PFPE may further include a linear repeating unit-(OCF ₂ CF ₂ CF ₂ )-.

In the above aspect, the PFPE preferably comprises a repeating unit OC ₃ F ₆ having a branched structure. More preferably, the PFPE is represented by the formula:-(OCF ₂ CF (CF ₃ )) _d . In said formula, d is 1 or more and 200 or less, Preferably it is 5 or more and 200 or less, More preferably, it is an integer of 10 or more and 200 or less.

In another embodiment, the PFPE is-(OC ₄ F ₈ ) _c- (OC ₃ F ₆ ) _d- (OC ₂ F ₄ ) _e- (OCF ₂ ) _f- (wherein c and d are each Are independently integers of 0 or more and 30 or less, and e and f are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, and c, d, e and f The sum of at least 5, preferably at least 10, the order of the presence of each repeating unit enclosed in parentheses with the subscripts c, d, e or f is arbitrary in the formula) and at least one branch structure in the PFPE Has

In another embodiment, PFPE is a group represented by-(R ⁶ -R ⁷ ) _j -and has a branched structure of at least one of PFPE. In the formula, R ⁶ is a OCF ₂ or OC ₂ F _4, preferably OC ₂ F _4. Wherein R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or two or three groups independently selected from these groups It is a combination. Preferably, R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ , or is selected from OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ Or a combination of two or three groups selected independently from these groups. The combination of two or three groups independently selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ is not particularly limited, and examples thereof include -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 ₃ 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- , and -OC ₄ F ₈ OC ₂ F ₄ OC ₂ F ₄ -and the like. The j is 2 or more, preferably 3 or more, more preferably 5 or more, and 100 or less, preferably an integer of 50 or less. In the _{formula, OC 2 F 4, OC 3} F 6, OC 4 F 8, OC 5 F 10 and F ₁₂ OC ₆ preferably has a branched structure.

In a more preferably, the aspect, PFPE is composed of repeating units of branched structure, _{OC 6 F 12, OC 5 F} 10, OC 4 F 8, and OC ₃ F _6.

The average molecular weight of the Rf-PFPE- moiety is not particularly limited, but is 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,000 to 10,000.

In another embodiment, the number average molecular weight of the Rf-PFPE moiety is 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000.

In another embodiment, the number average molecular weight of the Rf-PFPE- moiety or -PFPE- moiety can be 4,000 to 30,000, preferably 5,000 to 10,000.

In said formula, R <^13> represents a hydroxyl group or a group which can be hydrolyzed at each occurrence independently.

When used in this specification, said "hydrolyzable group" means the group which can receive a hydrolysis reaction, ie, the group which can be detached from the main skeleton of a compound by a hydrolysis reaction. Examples of the hydrolyzable group include -OR, -OCOR, -ON = CR ₂ , -NR ₂ , -NHR, a halogen atom (wherein R represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms), and the like. These are mentioned, Preferably it is -OR (ie, 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 a chloromethyl group, are contained. Among them, an alkyl group, particularly an unsubstituted alkyl group, is preferable, and a methyl group or an ethyl group is more preferable. Although the said "hydroxyl group" is not specifically limited, The group which can be hydrolyzed may generate | occur | produce by hydrolysis.

In said formula, R <^14> shows a hydrogen atom or a C1-C22 alkyl group, Preferably, a C1-C4 alkyl group each independently in each appearance.

In said formula, R <^11> represents a hydrogen atom or a halogen atom each independently in each appearance. The halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom, and more preferably a fluorine atom.

In said formula, R < ¹² > represents a hydrogen atom or a lower alkyl group each independently in each appearance. 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 formula, n is, independently for each ^{_{(-SiR 13 n R 14 3-}} n) unit, an integer from 0 to 3, and preferably 1 to 3, more preferably 3. However, in Formula (A1) and (A2), at least two Si couple | bonded with the hydroxyl group or the hydrolyzable group exists. That is, in formulas (A1) and (A2), at least two structures of SiR ¹³ are present.

In said formula, X <^1> represents a single bond or 2-10 valent organic group each independently. In the compounds represented by the formulas (A1) and (A2), X ¹ is a perfluoropolyether moiety (that is, an Rf-PFPE moiety or a -PFPE moiety) that mainly provides water repellency and surface slipperiness and the like. Is interpreted as a linker that connects the silane moieties (ie, groups with α and parentheses) that provide the binding capacity of the substrate. Therefore, as long as the compound represented by Formula (A1) and (A2) can exist stably, said X <_1> may be any organic group.

In another embodiment, X ¹ represents X ^e . X ^e represents a single bond or a 2- to 10-valent organic group, and preferably a single bond or -C ₆ H _4- (that is, -phenylene-. Hereinafter, represents a phenylene group), -CO- (carbonyl group) And -10 to 10-valent organic groups having at least one selected from the group consisting of -NR ⁴ -and -SO _2- . Each of R ^{4 's} independently represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group (preferably a methyl group), and preferably a hydrogen atom or a methyl group. The one _{-C 6 H 4 -, -CO-,} -NR 4 - or -SO ₂ -, it is preferably included in the molecular main chain of the PFPE-containing silane compound. Here, the molecular main chain refers to a binding chain containing the longest PFPE among the molecules of the PFPE-containing silane compound.

X ^e is more preferably a single bond or -C ₆ H _4- , -CONR ^4- , -CONR ⁴ -C ₆ H _4- , -CO-, -CO-C ₆ H _4- , -SO ₂ NR ^4- , -SO ₂ NR ⁴ -C ₆ H _4- , -SO _2- , and -SO ₂ -C ₆ H ₄ -It represents a 2 to 10 valent organic group having at least one selected from the group consisting of. -C ₆ H _4- , -CONR ^4- , -CONR ⁴ -C ₆ H _4- , -CO-, -CO-C ₆ H _4- , -SO ₂ NR ^4- , -SO ₂ NR ^4- C ₆ H _4- , -SO _2- , or -SO ₂ -C ₆ H ₄ -are preferably included in the molecular backbone of the PFPE-containing silane compound.

In said formula, (alpha) is an integer of 1-9, and (alpha) 'is an integer of 1-9. These α and α 'may be changed depending on the valence of X ¹ . In Formula (A1), the sum of (alpha) and (alpha) '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 'may be 9. Further, X ¹ in this case a divalent organic group, α and α 'is 1. In Formula (A2), α 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, 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, formulas (A1) and (A2) are represented by the following formulas (A1 ') and (A2').

Although it does not specifically limit as an example of said X <^1> , For example, the following formula:

[In meals:

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 1-20, Preferably it is an integer of 1-6, More preferably, it is an integer of 1-3, More preferably, it is 1 or 2,

X ^a represents-(X ^b ) _{l '} -

X ^b is, at each occurrence, independently, -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'} - is selected from the group consisting of Represents a group,

R ³³ in each occurrence 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, more preferably a methyl group,

R ³⁴ in each occurrence independently represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group (preferably a methyl group),

m 'is each independently an integer of 1 to 100, preferably an integer of 1 to 20, in each occurrence.

n 'is each independently an integer of 1-20, Preferably it is an integer of 1-6, More preferably, it is an integer of 1-3,

l 'is an integer of 1-10, Preferably it is an integer of 1-5, More preferably, it is an integer of 1-3,

p 'is 0 or 1,

q 'is 0 or 1,

Wherein at least one of p 'and q' is 1, and the order of existence of each repeating unit appended with p 'or q' and enclosed in parentheses is arbitrary]

And divalent groups represented by. R ³¹ and X ^a (typically hydrogen atoms of R ³¹ and X ^a ) are each substituted with one or more substituents selected from fluorine atoms, C _1-3 alkyl groups and C _1-3 fluoroalkyl groups. It may be substituted.

Preferably, X ^{1 is-} (R ³¹ ) _{p '} -(X ^a ) _q' -R ^32- . R ³² is a single bond, - (CH _{2) t '-} or o-, m- or p- represents a phenylene group, preferably - (CH _{2) t'} - a. t 'is an integer of 1-20, Preferably it is an integer of 2-6, More preferably, it is an integer of 2-3. R ³² (typically a hydrogen atom of R ³² ) 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.

Preferably, X ¹ is

C _1-20 alkylene group,

-R ³¹ -X ^c -R ^32- , or

-X ^d -R ^32-

[Wherein, R ³¹ and R ³² have the same ^{meaning as} described above.]

Can be. Further, the alkylene group refers _{to, - (C δ H 2δ)} - a group having the structure, may be a substituted or unsubstituted, straight-chain or may be branched.

More preferably, X ¹ is

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 '} -

[In formula, s 'and t' are synonymous with the above.]

to be.

In the 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-

[In formula, R <^33> , R <^34> and m 'are synonymous with the above,

u 'is an integer of 1-20, Preferably it is an integer of 2-6, More preferably, it is an integer of 2-3.]. X ^c is preferably -O-.

In the 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 synonymous with the above.]

Indicates.

More preferably, X ¹ is

C _1-20 alkylene group,

-(CH ₂ ) _{s '} -X ^c- (CH ₂ ) _t'- , or

-X ^d- (CH ₂ ) _{t '} -

[Wherein, each symbol is synonymous with the above.]

Can be.

Even more preferably, X ¹ is

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 )-

[In formula, R <^33> , m ', s', t ', and u' are synonymous with the above, v is an integer of 1-20, Preferably it is an integer of 2-6, More preferably, it is 2-3. Is an integer of.]

to be.

In the _{formula, - (C v H 2v)} - is straight and even, and even branched, for example _{-CH 2 -, -CH 2 CH 2} -, -CH 2 CH 2 CH 2 -, -CH ( CH ₃ )-, -CH (CH ₃ ) CH _2- .

The X ₁ group 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 (preferably a C _1-3 perfluoroalkyl group). .

In one embodiment, the X ¹ group may be other than an —OC _1-6 alkylene group.

In another embodiment, as the X ¹ group, for example, the following groups may be mentioned:

[Wherein, R ⁴¹ is each 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;

D is

(In formula, R <^42> respectively independently represents a hydrogen atom, a _C1-6 alkyl group, or a _C1-6 alkoxy group, Preferably a methyl group or a methoxy group, More preferably, a methyl group.)

Is a group selected from

E _is- (CH ₂ ) _ne- (ne is an integer of 2 to 6),

D binds to PFPE of the molecular backbone, and E binds to the group opposite to PFPE.]

As a specific example of X ¹ , for example:

Etc. can be mentioned.

In another preferred embodiment, X ¹ represents X ^{e '} . X ^{e '} is a single bond, an alkylene group having 1 to 6 carbon atoms, -R ⁵¹ -C ₆ H ₄ -R ^52- , -R ⁵¹ -CONR ⁴ -R ^52- , -R ⁵¹ -CONR ⁴ -C ₆ H ₄ -R ^52- , -R ⁵¹ -CO-R ^52- , -R ⁵¹ -CO-C ₆ H ₄ -R ^52- , -R ⁵¹ -SO ₂ NR ⁴ -R ^52- , -R ⁵¹ -SO ₂ NR ⁴ -C ₆ H ₄ -R ^52- , -R ⁵¹ -SO ₂ -R ^52- , or -R ⁵¹ -SO ₂ -C ₆ H ₄ -R ^52- . R ⁵¹ and R ⁵² each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms, and preferably a single bond or an alkylene group having 1 to 3 carbon atoms. R ⁴ is synonymous with the above. The alkylene group is substituted or unsubstituted, preferably unsubstituted. As a substituent of the said alkylene group, a halogen atom, Preferably a fluorine atom is mentioned, for example. It is preferable that the said alkylene group is linear or branched, and is linear.

In a more preferred embodiment, X ^{e '} is

Single Bond,

An alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms,

(In formula, R ^{51 '} and R ^52' are each independently a C1-C6, preferably C1-C3 linear alkylene group,

R ^{4 '} is a hydrogen atom or a methyl group.)

Can be.

In this embodiment, as an example of X ^{e ', it} is, for example.

Single Bond,

An alkylene group having 1 to 6 carbon atoms,

Etc. can be mentioned.

In one embodiment, X ^{e '} is a single bond. In this embodiment, the group having the binding ability between the PFPE and the base layer (that is, in (A1) and (A2), a group with? And enclosed in parentheses) is directly bonded.

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

In said formula, R <^16> is an oxygen atom, phenylene, carbazolylene, -NR <^18> -(in formula, R <^18> represents a hydrogen atom or an organic group) or bivalent oil each independently in each appearance. It is a device. Preferably, R ¹⁶ is an oxygen atom or a divalent polar group.

Examples of the "bivalent polar group" is not particularly limited, -C (O) -, -C (= NR 19) - , and -C (O) NR ¹⁹ - (in these formulas, R ¹⁹ is a hydrogen atom or a lower Alkyl group). The "lower alkyl group" is, for example, an alkyl group having 1 to 6 carbon atoms, for example, a methyl group, an ethyl group, or an n-propyl group, and these may be substituted with one or more fluorine atoms.

In said formula, R <^17> is a hydrogen atom, a fluorine atom, or a lower fluoroalkyl group each independently in each appearance, Preferably it is a fluorine atom. 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, and more preferably a trifluoromethyl group. And pentafluoroethyl group, More preferably, it is a trifluoromethyl group.

In this embodiment, X ¹ is preferably a formula:-(O) _x- (CF ₂ ) _y- (CH ₂ ) _z- (wherein x, y and z are synonymous with above and are in parentheses) The order of existence of each repeating unit enclosed by is arbitrary in formula.

Formulas represented by the formula:-(O) _x- (CF ₂ ) _y- (CH ₂ ) _z -are, 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-] represented by 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). In addition, these groups are bonded to the PFPE side of the left end.

In another preferred embodiment, X ¹ is -O-CFR ^20- (CF ₂ ) _{e '} -.

R ^{20 's} each independently represent a fluorine atom or a lower fluoroalkyl group. The lower fluoroalkyl group here 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 and a pentafluoroethyl group, still more preferably Trifluoromethyl group.

E 'is each independently 0 or 1.

In one embodiment, R ²⁰ is a fluorine atom and e 'is 1.

In another embodiment, examples of the X ¹ group include the following groups:

[In the meal,

Each 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 of T may be bonded to the PFPE of the molecular backbone by

[Wherein, R ⁴² are, each independently, an alkoxy group, preferably a methyl group or a methoxy group in the alkyl group or C _1-6 a hydrogen atom, C _1-6, more preferably represents a methyl group.]

And some of the other T's are-(CH ₂ ) _{n "} -(n" is an integer of 2 to 6) which bind to a group opposite to the PFPE of the molecular backbone, and when present, the remaining Ts are each Independently, it may be a methyl group, a phenyl group, a C _1-6 alkoxy group or a radical capture group or an ultraviolet absorber.

The radical scavenger is not particularly limited as long as the radical scavenger is capable of capturing radicals generated by light irradiation. And residues of acrylates, hindered amines, hindered phenols or triazines.

The ultraviolet absorber is not particularly limited as long as it can absorb ultraviolet rays. Examples thereof include benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, and oxa. And residues of mids, oxanilides, benzoxazinones, and benzoxazoles.

In a preferred embodiment, as a preferable radical trap or ultraviolet absorber,

Can be mentioned.

In this embodiment, X ¹ , X ³ and X ⁴ may be a 3 to 10 valent organic group.

In said formula, X <^2> represents a single bond or a bivalent organic group each independently in each appearance. 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).

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

In one embodiment, the compound represented by the formulas (A1) and (A2) has α of 2 or more.

In one embodiment, t is 2 or more in the compound represented by Formula (A1) and (A2).

In one embodiment, the compound represented by the formulas (A1) and (A2) has α of 1, α 'of 1, and t of 2 or more.

Preferred compounds represented by the formulas (A1) and (A2) include the following formulas (A1 ') and (A2'):

[In meals:

PFPE, each independently, is represented by the formula:

_{- (OC 6 F 12) a} - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -

(In formula, a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1. a, b, The order of existence of each repeating unit with c, d, e or f and enclosed in parentheses is arbitrary in the formula.)

A group represented by;

Each occurrence of Rf independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;

R ¹³ each independently represent a hydroxyl group or a hydrolyzable group;

R ¹⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms;

R ¹¹ each independently represent a hydrogen atom or a halogen atom;

R < ¹² > represents a hydrogen atom or a lower alkyl group each independently in each appearance,

n is an integer of 1-3, Preferably it is 3;

Provided that at least two Si bonded to a hydroxyl group or a hydrolyzable group are present in formulas (A1 ') and (A2');

X ¹ , at each occurrence, is independently —O—CFR ²⁰ — (CF ₂ ) _{e ′} —;

R ²⁰ in each occurrence is independently a fluorine atom or a lower fluoroalkyl group;

e 'is each independently 0 or 1 in each occurrence;

X ² is-(CH ₂ ) _u- ;

u is an integer of 0 to 2 each independently at each occurrence;

t is an integer of 1-10 each independently in each occurrence.]

It is a compound represented by.

Compounds represented by the formulas (A1) and (A2) are, for example, a perfluoropolyether derivative corresponding to the Rf-PFPE- moiety as a raw material, and after introduction of iodine at the terminal, -CH ₂ CR ^{12 _{(X 2 -SiR 13 n R 14}} 3-n) - can be obtained by reacting a vinyl monomer corresponding to the.

Formulas (B1) and (B2):

In said formula (B1) and (B2), Rf and PFPE are synonymous with the description regarding said formula (A1) and (A2).

In said formula, X <^3> represents a single bond or 2-10 valent organic group each independently in each appearance. In the compounds represented by the formulas (B1) and (B2), X ³ is a perfluoropolyether moiety (that is, an Rf-PFPE moiety or a -PFPE moiety) that provides mainly water repellency and surface slipperiness. It is interpreted as a linker that connects a silane moiety (ie, a group with β and parentheses) to provide a binding ability with the substrate. Therefore, as long as the compound represented by Formula (B1) and (B2) can exist stably, said X <^3> may be any organic group.

In another embodiment, X ³ represents X ^e . X ^e is synonymous with the above.

In said formula, (beta) is an integer of 1-9, (beta) is an integer of 1-9. These β and β 'may vary depending on the valence of X ³ . In Formula (B1), the sum of (beta) and (beta) 'is the same as the valence of X3. For example, when X3 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 Β 'may be 9 as well. In addition, β and β 'are 1 when X ³ is a divalent organic group. In Formula (B2), β is the value obtained by subtracting 1 from the valence of X ³ .

X ³ is preferably 2 to 7 valent, more preferably 2 to 4 valent, still more preferably a divalent organic group.

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

In another embodiment, X ³ is a divalent organic group, β is 1, and β 'is 1. In this case, formulas (B1) and (B2) are represented by the following formulas (B1 ') and (B2').

Although it does not specifically limit as an example of said X <^3> , For example, the same thing as what was described about X <^1> is mentioned.

Especially, preferable specific X <^3> is

Etc. can be mentioned.

In another preferred form, X ³ represents X ^{e '} . X ^{e '} is synonymous with the above.

In one embodiment, X ^{e '} is a single bond. In this embodiment, the group having the binding ability between the PFPE and the base layer (that is, in (B1) and (B2), groups attached with β and enclosed in parentheses) are directly bonded.

In the formula (B1) and the equation (B2), R ^a is, independently at each _{^{occurrence, -Z 1 -SiR 1 p R 2}} q R 3 r denotes a.

In formula, Z <^1> represents an oxygen atom or a divalent organic group each independently in each appearance.

Z ¹ is preferably a divalent organic group, and forms a siloxane bond with ^a Si atom (Si atom to which R ^a is bonded) at the terminal of the molecular main chain in formula (B1) or (B2). do not include.

Z ¹ is preferably an alkylene group,-(CH ₂ ) _g -O- (CH ₂ ) _h- (wherein g is an integer of 1 to 6, h is an integer of 1 to 6), or- Phenylene- (CH ₂ ) _i -wherein i is an integer from 0 to 6. These groups may be substituted by 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, for example. From the viewpoint of particularly good UV resistance (ultraviolet ray durability), Z ¹ is more preferably a linear or branched alkylene group, still more preferably a linear alkylene group. Carbon number which comprises the said alkylene group of Z <^1> becomes like this. Preferably it is in the range of 1-6, More preferably, it is in the range of 1-3. In addition, it is as having mentioned above about an alkylene group.

In formula, R <^1> represents R ^<a>' each independently in each appearance. R ^{a '} is synonymous with R ^a .

Among R ^a , ^a maximum of 5 Si is linearly connected through the Z ¹ group. That is, in R ^a , when at least one R ¹ is present, at least two Si atoms that are linearly connected through Z ¹ are present in R ^a , but the Si atoms that are linearly connected through such a Z ¹ group The maximum is five. Further, "the number of Si atoms via a group Z ¹ in connection with R ^a straight-chain" refers, it is equal to the repetition number of -Z ¹ -Si- that lead to linear in the R ^a.

For example, an example in which Si atoms are connected through a Z ¹ group in R ^a is shown below.

In the above formula, * means a site bonded to Si of the main chain, Is a predetermined group other than Z ¹ Si is bonded, that is, all three bonds of Si atoms are. In the case of, the end point of repetition of Z ¹ Si is meant. In addition, the number on the upper right side of Si means the appearance number of Si connected linearly through the Z <^1> group counted from *. That is, numbered, the chain Z ¹ Si repetition is ended at the Si ² is 2 is "number of Si atoms are connected to the straight through a Z ¹ of the R ^a", as in, Si ^3, Si ⁴ and Z ¹ Si to Si ⁵ The chain in which the repetition is completed has 3, 4 and 5 "the number of Si atoms connected linearly through the Z ¹ group in R ^a ", respectively. Further, As is apparent from the above formula, R ^a while, Z ¹ Si chains are present a plurality, but they need not all have the same length, or may be any length, respectively.

In a preferred embodiment, as shown below, "the number of Si atoms via a group Z ¹ in connection with R ^a straight-chain" is, in all chains, and one (sedentary) or two (dental caries).

In one embodiment, the number of Si atoms which are linearly connected via the Z ¹ group in R ^a is one or two, preferably one.

In formula, R <^2> represents a hydroxyl group or a hydrolyzable group each independently in each appearance.

As said "hydrolyzable group", the thing similar to Formula (A1) and (A2) is mentioned.

Preferably, R ² is -OR (wherein R represents a substituted or unsubstituted C _1-3 alkyl group, more preferably a methyl group).

In formula, R < ³ > represents a hydrogen atom or a lower alkyl group each independently in each appearance. 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, still more preferably a methyl group.

In formula, p is an integer of 0-3 each independently in each occurrence; q is an integer of 0 to 3 each independently at each occurrence; r is an integer of 0-3 each independently in each occurrence. However, for every -Z ¹ -SiR ¹ _p R ² _q R ³ _r , the sum of p, q and r is three.

In a preferred embodiment, in the R ^{a '(unless} the R ^a' present, R ^a) terminal of the R ^a of the q is preferably 2, and more, for example 2 or 3, more preferably Is 3.

In a preferred embodiment, R ^a is at least one terminal of -Si (-Z ¹ -SiR ² _q R ³ _r ) ₂ or -Si (-Z ¹ -SiR ² _q R ³ _r ) ₃ , preferably May have -Si (-Z ¹ -SiR ² _q R ³ _r ) ₃ . In the formula, the unit of (-Z ¹ -SiR ² _q R ³ _r ) is preferably (-Z ¹ -SiR ² ₃ ). In a more preferred embodiment, the terminal portions of R ^a may all be -Si (-Z ¹ -SiR ² _q R ³ _r ) ₃ , preferably -Si (-Z ¹ -SiR ² ₃ ) ₃ .

In said Formula (B1) and (B2), at least 2 Si couple | bonded with the hydroxyl group or the hydrolyzable group exists. That is, at least two groups represented by SiR ² and / or SiR ^b are present. By having such a structure, the PFPE containing silane compound of this invention can form the surface treatment layer which can be bonded favorably to the surface of a base material.

In said formula, R <^b> represents a hydroxyl group or a hydrolyzable group each independently in each appearance.

R ^b is preferably a hydroxyl group, —OR, —OCOR, —ON═C (R) ₂ , —N (R) ₂ , —NHR, or halogen (wherein R is a substituted or unsubstituted carbon number 1). To an alkyl group of 4 to 4), more preferably -OR. R is an unsubstituted alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group; Substituted alkyl groups, such as a chloromethyl group, are contained. Among them, an alkyl group, particularly an unsubstituted alkyl group, is preferable, and a methyl group or an ethyl group is more preferable. Although a hydroxyl group is not specifically limited, The group which can be hydrolyzed may hydrolyze and generate | occur | produce. More preferably, R ^b is -OR (wherein R represents a substituted or unsubstituted C _1-3 alkyl group, more preferably a methyl group).

In said formula, R < ^c > represents a hydrogen atom or a lower alkyl group each independently in each appearance. 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, still more preferably a methyl group.

In formula, k1 is an integer of 0-3 each independently in each occurrence; l1 is an integer of 0 to 3 each independently at each occurrence; m1 is an integer of 0-3 each independently in each occurrence. However, in every -SiR ^a _k1 R ^b _l1 R ^c _m1 , k1, The sum of l1 and m1 is three. It is preferable that it is 1-3, and, as for k1, it is more preferable that it is three.

The compounds represented by the formulas (B1) and (B2) are, for example, a perfluoropolyether derivative corresponding to the Rf-PFPE- moiety as a raw material, and after introducing a hydroxyl group at the terminal, an unsaturated bond is formed at the terminal. It can obtain by introducing the group which has, the group which has this unsaturated bond, and the silyl derivative which has a halogen atom, and introduce | transduces a hydroxyl group at the terminal in this silyl group, and makes the group which has the unsaturated bond introduce | transduce and react the silyl derivative. For example, it can synthesize as described in international publication 2014/069592.

Formula (C1) and VII (C2):

In said Formula (C1) and (C2), Rf and PFPE are synonymous with the description regarding said Formula (A1) and (A2).

In said formula, X <^4> represents a single bond or 2-10 valent organic group each independently. In the compounds represented by the formulas (C1) and (C2), X ⁴ is a perfluoropolyether moiety (that is, an Rf-PFPE moiety or a -PFPE- moiety) that mainly provides water repellency and surface slipperiness. It is interpreted as a linker which connects the part which provides the binding ability with respect to a base material (that is, the group which attached (gamma) and enclosed in parentheses). Therefore, as long as the said X <^4> can exist stably the compound represented by Formula (C1) and (C2), any organic group may be sufficient.

In another embodiment, X ⁴ represents X ^e . X ^e is synonymous with the above.

In said formula, (gamma) is an integer of 1-9, (gamma) 'is an integer of 1-9. These γ and γ 'may vary depending on the valence of X ⁴ . In Formula (C1), the sum of (gamma) and (gamma) 'is the same as the valence of X <^4> . For example, when X ⁴ 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 'may be 9. In addition, when X ⁴ is a divalent organic group, γ and γ 'is 1. In Formula (C2), γ is a value obtained by subtracting 1 from the valence of X ⁴ .

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

In one embodiment, X ⁴ is a divalent to tetravalent organic group, γ is 1 to 3, and γ 'is 1.

In another embodiment, X ⁴ is a divalent organic group, γ is 1, and γ 'is 1. In this case, formulas (C1) and (C2) are represented by the following formulas (C1 ') and (C2').

Although it does not specifically limit as an example of said X <^4> , For example, the same thing as what was described about X <^1> is mentioned.

Especially, preferable specific X <^4> is

Etc. can be mentioned.

In another preferred form, X ³ represents X ^{e '} . X ^{e '} is synonymous with the above.

In one embodiment, X ^{e '} is a single bond. In this embodiment, the group having the binding ability between the PFPE and the base layer (that is, in (C1) and (C2), a group having γ attached and enclosed in parentheses) is directly bonded. By having such a structure, it is thought that the bonding force of the group which PFPE and (gamma) add and enclose in parentheses becomes stronger. In addition, carbon atoms directly bonded to PFPE (that is, carbon atoms bonded to R ^d , R ^e and R ^{f in} groups enclosed in γ and parentheses) have less electric charge bias, and as a result, nucleophiles in the carbon atoms It is thought that a reaction or the like hardly occurs, and is stably bonded to the base layer. Such a structure is advantageous in further improving the friction durability of the formed surface treatment layer.

In the formula, R ^d is, independently at each occurrence, -Z ² -CR ⁸¹ _p2 R ⁸² represents an R ⁸³ _{r2 q2.}

In formula, Z <^2> represents an oxygen atom or a divalent organic group each independently in each appearance.

Z ² is preferably a C _1-6 alkylene group,-(CH ₂ ) _g -O- (CH ₂ ) _h- (wherein g is an integer of 0 to 6, for example, 1 to 6 an integer, h is from 0 to 6 integer, for example an integer of 1 to 6), or - phenylene - (CH _{2) i} -, and (wherein, i is an integer of from 0 to 6), more preferably Is a C _1-3 alkylene group. These groups may be substituted by 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, for example.

In the formula, R ⁸¹ each independently represents R ^{d ′} in each occurrence. R ^{d '} is synonymous with R ^d .

Among R ^{d 's} , up to five C's are linearly linked through the Z ² groups. That is, in R ^d , when at least one R ⁸¹ is present, at least ^two C atoms that are linearly linked through the Z ² groups are present in R ^d , but the C atoms that are linearly connected through the Z ² groups are present. The maximum is five. Further, "the number of C atoms that are connected by a straight-chain via a Z ² of R ^d" means, it is equal to the number of iterations of the -Z ² -C- is connected to a straight-chain in the R ^d.

In a preferable embodiment, as shown below, "the number of C atoms connected linearly through the Z ² group in R ^d " is one (left) or two (caries) in all the chains.

In one embodiment, the number of C atoms connected linearly through the Z ₂ groups of R ^d is one or two, preferably one.

In the formula, R ⁸² each independently represents -Y-SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 in each occurrence.

Y represents a bivalent organic group each independently in each appearance.

In a preferred embodiment, Y is a C _1-6 alkylene group,-(CH ₂ ) _{g '} -O- (CH ₂ ) _h' -(wherein g 'is an integer of 0 to 6, for example 1 an integer from 1-6, h 'is from 0 to 6 integer, for example an integer of 1 to 6), or - phenylene _{- (CH 2) i' -} ( wherein, i 'is from 0 to 6 Integer). These groups may be substituted by 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, for example.

In one embodiment, Y may be a C _1-6 alkylene group or -phenylene- (CH ₂ ) _{i '} -. If Y is the aforementioned group, light resistance, in particular ultraviolet resistance, may be higher.

R ⁸⁵ in each occurrence independently represents a hydroxyl group or a hydrolyzable group.

As said "hydrolyzable group", the thing similar to Formula (A1) and (A2) is mentioned.

Preferably, R ⁸⁵ is -OR (wherein R represents a substituted or unsubstituted C _1-3 alkyl group, more preferably an ethyl group or a methyl group, especially a methyl group).

R ⁸⁶ in each occurrence 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, still more preferably a methyl group.

n2 represents an integer of 0 to 3 independently for each (-Y-SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 ) unit, preferably an integer of 1 to 3, more preferably 2 or 3, particularly preferably 3

R ⁸³ in each occurrence 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, still more preferably a methyl group.

In formula, p2 is an integer of 0-3 each independently in each occurrence; q2 is an integer of 0-3 each independently in each occurrence; r2 is an integer of 0-3 each independently in each occurrence. However, according to a per (-Z ² -CR ⁸¹ R ⁸² _{p2 q2} R ⁸³ _r2), p2, q2 and r2 is the sum of the three.

In a preferred embodiment, in the ^'(, R ^d, if the R ^d' does not exist) of the terminal of R ^d R ^d, wherein q2 is preferably 2 and above, for example 2 or 3, more preferably Is 3.

In a preferred embodiment, at least one of the terminal portions of R ^d is -C (-Y-SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 ) ₂ or -C (-Y-SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 ) ₃ , preferably May be -C (-Y-SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 ) ₃ . In the formula, the unit of (-Y-SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 ) is preferably (-Y-SiR ⁸⁵ ₃ ). In a more preferred embodiment, the terminal portions of R ^d may be all —C (—Y—SiR ⁸⁵ _{n 2} R ⁸⁶ _3-n2 ) ₃ , preferably —C (—Y—SiR ⁸⁵ ₃ ) ₃ .

In said formula, R <^e> represents -Y-SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 each independently in each appearance. Here, Y, R ⁸⁵ , R ⁸⁶ and n2 are synonymous with the description in R ⁸² described above.

In said formula, R < ^f > represents a hydrogen atom or a lower alkyl group each independently in each appearance. 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, still more preferably a methyl group.

In formula, k2 is an integer of 0-3 each independently in each occurrence; l2 is an integer of 0-3 each independently at each occurrence; m2 is an integer of 0-3 each independently in each occurrence. However, in every (CR ^d _k2 R ^e _l2 R ^f _m2 ), the sum of k2, l2, and m2 is three.

In one embodiment, at least one k2 is 2 or 3, preferably 3.

In one embodiment, k2 is 2 or 3, preferably 3.

In one embodiment, l 2 is 2 or 3, preferably 3.

In Formulas (C1) and (C2), two or more groups represented by -Y-SiR ⁸⁵ are present. Preferably, in formulas (C1) and (C2), at least one carbon atom bonded to a group represented by two or more -Y-SiR ⁸⁵ is present. That is, it is preferable that 1 or more groups represented by -C- (Y-SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 ) ₂ are present (wherein n 2 is an integer of 1 to 3).

Preferably, in the formulas (C1) and (C2), n2 is an integer of 1 to 3, and at least one q2 is 2 or 3, or at least one l2 is 2 or 3. That is, at least two -Y-SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 groups are present in the _formula .

In one embodiment, the formulas (C1) and (C2) are represented by the following formulas (C1 ") and (C2").

[In meals:

Rf and PFPE are respectively synonymous with the above;

X ^{4 '} is synonymous with X ^4, and preferably represents X ^e ;

X ^e is synonymous with the above;

γ and γ ′ are synonymous with the above, respectively;

Each occurrence of R ^{d '} independently represents -Z ^2' -CR ⁸¹ _{p2 '} R ^82' _{q2 '} R ⁸³ _r2' ;

R ⁸¹ and R ⁸³ are the same as defined above, respectively;

Z ^{2 '} each independently represent -R ^g -Z'- in each occurrence;

Each occurrence of R ^g independently represents a lower alkylene group;

Z 'each independently represents a single bond, an oxygen atom, or a divalent organic group in each occurrence;

R ^{82 '} each independently represent -R ^h -Y'-SiR ⁸⁵ _n2' R ⁸⁶ _{3-n2 '} at each occurrence;

R ^h each independently represent a lower alkylene group;

Y 'each independently represents a single bond, an oxygen atom, or a divalent organic group in each occurrence;

n2 'represents an integer of 1-3 independently from unit (-R ^h -Y'-SiR ⁸⁵ _n2' R ⁸⁶ _{3-n2 '} ), Preferably it is 2 or 3, More preferably, it is 3;

R ⁸⁵ and R ⁸⁶ are the same as defined above, respectively;

p2 'is an integer of 0-3 each independently in each occurrence;

q2 'is an integer of 0-3 each independently at each occurrence;

r2 'is an integer of 0-3 each independently at each occurrence;

_{^{(-Z 2 '-CR 81 p2'}} R 82 'q2' R 83 r2 ') in each unit, p2', q2 'and r2' of the sum is 3;

R ^{e '} each independently represent -R ^h -Y'-SiR ⁸⁵ _n2' R ⁸⁶ _{3-n2 '} at each occurrence;

R ^f is synonymous with the above;

k2 'is an integer of 0-3 each independently at each occurrence;

l2 'is an integer of 0-3 each independently at each occurrence;

m2 'is an integer of 0-3 each independently at each occurrence;

However, in every (CR ^{d '} _k2' R ^{e '} _l2' R ^f _{m2 '} ), the sum of k2', l2 ', and m2' is 3, and at least 1 q2 'is 3, or at least One l2 'is 3.]

R ^g in each occurrence independently represents a lower alkylene group. The lower alkylene group is preferably a C _1-20 alkylene group, more preferably a C _1-6 alkylene group, still more preferably a C _1-3 alkylene group, particularly preferably methylene.

Z 'is preferably an oxygen atom or a divalent organic group, more preferably a divalent organic group, still more preferably a C _1-6 alkylene group,-(CH ₂ ) _{j 1} -O- (CH ₂ ) _h1- (wherein j1 is an integer of 0 to 6, for example, an integer of 1 to 6, h1 is an integer of 0 to 6, for example, an integer of 1 to 6), or -phenylene -(CH ₂ ) _i1- (wherein i1 is an integer of 0 to 6), particularly preferably C _1-6 alkylene group or -phenylene- (CH ₂ ) _i1- , more preferably C _1-6 alkylene group (preferably, C _1-3 alkylene group). These groups may be substituted by 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, for example. In a preferred embodiment, Z 'is unsubstituted.

Z ^{2 ′} is preferably a C _1-3 alkylene group, specifically, —CH ₂ —, —CH ₂ CH ₂ —, or —CH ₂ CH ₂ CH ₂ —.

R ^h each independently represents a lower alkylene group. The lower alkylene group is preferably a C _1-20 alkylene group, more preferably a C _1-6 alkylene group, still more preferably a C _1-3 alkylene group, particularly preferably methylene.

Y 'is a preferable oxygen bond or a divalent organic group. Y 'is more preferably a divalent organic group, and particularly preferably a C _1-6 alkylene group,-(CH ₂ ) _g1' -O- (CH ₂ ) _{h1 '} -(wherein g1' is An integer of 0 to 6, for example, an integer of 1 to 6, and h1 'is an integer of 0 to 6, for example, an integer of 1 to 6, or -phenylene- (CH ₂ ) _i1' -(formula of, i1 'is an integer of from 0 to 6), and more preferably is a C _1-6 alkylene group or - phenylene - (CH _{2) i1'} -, and particularly preferably a C _1-6 alkylene group (preferably Preferably a C _1-3 alkylene group). These groups may be substituted by 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, for example.

In one embodiment, Y 'may be a C _1-6 alkylene group, -O- (CH ₂ ) _h1' -or -phenylene- (CH ₂ ) _{i1 '} -. If Y 'is the aforementioned group, light resistance, in particular ultraviolet resistance, may be higher.

In a preferred embodiment, the -Rh-Y'- may be a C _1-3 alkylene group, specifically -CH _2- , -CH ₂ CH _2- , or -CH ₂ CH ₂ CH _2- .

In one embodiment, at least one k2 'is 2 or 3, preferably 3.

In one embodiment, k2 'is 2 or 3, preferably 3.

In one embodiment, l2 'is 2 or 3, preferably 3.

In a preferred embodiment, l2 'is 3 and n2' is 3.

In the formulas (C1 ″) and (C2 ″), at least one q2 'is 3, or at least one l2' is 3. That is, in formula, at least one -X ^{4 '} -C (-R _h -Y'-SiR ⁸⁵ _n2' R ⁸⁶ _{3-n2 '} ) ₃ group or -Z ^2' -C (-Rh-Y'-SiR ⁸⁵ _n2'R ⁸⁶ _{3-n2 '} ) ₃ groups are present. By having such a structure, the PFPE-containing silane compound of the present form is hardly deteriorated even in a chemically durable environment (for example, in an acid and / or alkali environment, more specifically in an environment where sweat may adhere). ) May contribute to the formation of the surface treatment layer. In addition, the PFPE-containing silane compound of the present embodiment can contribute to the formation of a surface treatment layer having a good friction durability by having the structure as described above, and in particular, even in an environment where it is easy to be exposed to an acid and / or an alkaline environment. It can contribute to the formation of this improved surface treatment layer.

In the formula (C1 ″) or (C2 ″), more preferably, γ is 1, γ 'is 1, and X ^4' represents X ^{e '} . X ^{e '} is synonymous with the above.

The PFPE containing silane compound represented by Formula (C1) or Formula (C2) can be manufactured by combining a well-known method. For example, although the compound represented by Formula (C1 ') whose X <^4> is bivalent is not limited, it can manufacture as follows.

A group containing a double bond (preferably allyl) in a polyhydric alcohol represented by HO-X ⁴ -C (YOH) ₃ (wherein X ⁴ and Y are each independently a divalent organic group), And halogen (preferably bromo) and Hal-X ⁴ -C (YOR-CH = CH ₂ ) ₃ , wherein Hal is halogen, eg Br, R is a divalent organic group, eg For example, an alkylene group) to obtain a double bond-containing halide. Subsequently, the terminal halogen is reacted with a perfluoropolyether group-containing alcohol represented by R ^PFPE- OH (wherein, R ^PFPE is a perfluoropolyether group-containing group) to react with R ^PFPE- OX ⁴ -C. (YOR-CH = CH ₂ ) ₃ is obtained. Subsequently, the terminal -CH = CH _{2 can be} reacted with HSiCl ₃ and alcohol or HSiR ⁸⁵ ₃ to obtain R ^PFPE -OX ⁴ -C (YOR-CH ₂ -CH ₂ -SiR ⁸⁵ ₃ ) ₃ .

In another embodiment, the PFPE-containing compound having -R ⁵¹ -CONH-R ⁵² -as X ^{4 '} , represented by the formula (C1 ") or formula (C2"), is not limited as follows. It can manufacture.

By reacting a compound containing a double bond (preferably allyl) and a compound having an amino group (for example, H ₂ NR ⁵² C (CH ₂ -CH = CH ₂ ) ₃ with R ^PFPE -R ⁵¹ -COOCH ₃ R ^PFPE -R ⁵¹ -CONH-R ⁵² C (-CH ₂ -CH = CH ₂ ) ₃ is synthesized The PFPE-containing compound R ^PFPE is reacted with the obtained compound by HSiCl ₃ and alcohol or HC (OCH ₃ ) ₃ . -R ⁵¹ -CONH-R ⁵² C (CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ) ₃ , wherein R ^PFPE is a PFPE-containing group, and R ⁵¹ and R ⁵² are ^identical to the above. It's right.

(Compound containing an atom having unshared electron pair in molecular structure)

The surface treating agent of the present invention can contribute to the formation of the surface treatment layer having improved friction resistance. In addition, the surface treatment agent of the present invention can contribute to the formation of a surface treatment layer having improved durability, particularly a surface treatment layer which is chemically stable and is hard to deteriorate even in the presence of an acid and / or alkali, for example. This is considered to be because the compound containing the atom having a non-covalent electron pair in the molecular structure exhibits a catalytic effect, thereby making the bond between the substrate and the Si atom more robust.

It is preferable that the compound containing the atom which has a lone pair in the said molecular structure contains at least 1 atom selected from the group which consists of a nitrogen atom, an oxygen atom, a phosphorus atom, and a sulfur atom, and contains a sulfur atom or a nitrogen atom It is more preferable.

The compound containing an atom having a non-covalent electron pair in the molecular structure, at least one functional group selected from the group consisting of amino group, amide group, sulfinyl group, P═O group, S═O group and sulfonyl group in the molecular structure It is preferable to include, and it is more preferable to include at least 1 functional group chosen from the group which consists of P = O group and S = O group.

In a preferred embodiment, the compound containing an atom having a non-covalent electron pair in the molecular structure includes an S═O group in the functional group.

In the said aspect, it is preferable that the compound containing the atom which has a lone pair in the said molecular structure is a compound represented by a formula: R <^91> -S (= O) -R <^92> .

In said formula, R <^91> is a C1-C12 hydrocarbon group and R <^92> is a C1-C12 hydrocarbon group. Preferably, R ⁹¹ is a hydrocarbon group having 1 to 6 carbon atoms, and R ⁹² is a hydrocarbon group having 1 to 6 carbon atoms.

Examples of the hydrocarbon group include a saturated hydrocarbon group, an unsaturated hydrocarbon group having at least one carbon-carbon unsaturated bond, or an aromatic hydrocarbon group. Preferably, as said hydrocarbon group, an alkyl group or a phenyl group is mentioned.

In a preferred embodiment, R ⁹¹ and R ⁹² are each independently an alkyl group having 1 to 6 carbon atoms (specifically a methyl group) at each occurrence.

In the above formula, R ⁹¹ and R ⁹² may be bonded to each other and may form a ring structure together with the S atom bonded to R ⁹¹ and R ⁹² . The ring structure preferably comprises at least one S atom (preferably one S atom) and 3 to 12 carbon atoms, and at least one S atom (preferably one S atom) and 4 to 4 carbon atoms. It is more preferable that it consists of 6.

Examples of the ring structure include a saturated four-membered ring structure composed of one S atom and three carbon atoms, a saturated five-membered ring structure composed of one S atom and four carbon atoms, one S atom and five carbon atoms Saturated 6-membered ring structure, Unsaturated 5-membered ring structure consisting of one S atom and four carbon atoms, Unsaturated six-membered ring structure consisting of one S atom and five carbon atoms, and the like, and specifically one S atom And a saturated five-membered ring structure composed of four carbon atoms, an unsaturated five-membered ring structure composed of one S atom and four carbon atoms, and the like. As for the carbon atom which comprises the said ring structure, the at least 1 hydrogen atom couple | bonded with the said carbon atom may be substituted by substituents, such as an alkyl group (for example, C1-C6), a phenyl group, and the said substituent You do not have to have it.

It is preferable that the compound containing the atom which has a non-covalent electron pair in the said molecular structure is at least 1 compound chosen from the group which consists of an aliphatic amine compound, an aromatic amine compound, a phosphate amide compound, an amide compound, a urea compound, and a sulfoxide compound, More preferably at least one compound selected from the group consisting of aliphatic amine compounds, aromatic amines, phosphate amides, urea compounds and sulfoxide compounds, and selected from the group consisting of sulfoxide compounds, aliphatic amine compounds and aromatic amine compounds. It is especially preferable that it is at least one compound, and it is more preferable that it is a sulfoxide compound.

As said aliphatic amine compound, diethylamine, triethylamine, etc. are mentioned, for example. As said aromatic amine compound, aniline, pyridine, etc. are mentioned, for example. As said phosphate amide compound, hexamethylphosphoramide etc. are mentioned, for example. Examples of the amide compound include N, N-diethylacetamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methylformamide, N, N-dimethylformamide and N- Methyl pyrrolidone etc. are mentioned. Tetramethyl urea etc. are mentioned as said urea compound. Dimethyl sulfoxide (DMSO), tetramethylene sulfoxide, methylphenyl sulfoxide, diphenyl sulfoxide, etc. are mentioned as said sulfoxide compound. Among these compounds, dimethyl sulfoxide or tetramethylene sulfoxide is preferably used.

The molecular weight of the compound containing the atom which has a lone pair in the said molecular structure may be in the range of 50-500, for example, and may especially exist in the range of 50-200.

The compound containing the atom which has a lone pair in a molecular structure can be contained 0.0002 mass% or more with respect to the whole surface treating agent, for example. It is preferable that 0.02 mass% or more is contained with respect to the whole surface treating agent, and, as for the said compound, it is more preferable that 0.04 mass% or more is contained. The said compound may be contained 10 mass% or less with respect to the whole surface treating agent, for example, 1 mass% or less is contained especially. The surface treating agent of this invention can contribute to formation of the surface treatment layer which is more durable by containing the said compound in the above concentration.

The compound containing an atom having a non-covalent electron pair in its molecular structure is preferably contained in a surface treatment agent with respect to 1 mol of Si atoms bonded to the hydroxyl group or hydrolyzable group of the PFPE-containing silane compound, preferably 0.03 mol or more. It is more preferable, It is still more preferable to contain 0.15 mol or more, It is especially preferable to contain 0.33 mol or more. By including the compound containing the atom which has a non-covalent electron pair in a molecular structure at the above concentration, the surface treating agent of this invention can contribute especially to formation of the surface treatment layer with favorable durability.

It is preferable that the compound containing the atom which has a lone pair of electrons in a molecular structure is contained 10 mol or less with respect to 1 mol of Si atoms couple | bonded with the hydroxyl group or the hydrolysis group of a PFPE containing silane compound, and 6 mol or less is included in a surface treating agent. It is more preferable, and it is especially preferable that 2 mol or less is included. By including a compound containing an atom having a non-covalent electron pair in a molecular structure at such concentrations, the handleability of the surface treating agent of the present invention can be improved, and in particular, the clouding of the surface treating agent can be prevented.

In one aspect, 3 mol or less of compounds containing the atom which has a non-covalent electron pair in a molecular structure may be contained with respect to 1 mol of Si atoms couple | bonded with the hydroxyl group or the hydrolysis group of a PFPE containing silane compound in a surface treating agent.

It is preferable that the compound containing the atom which has a non-covalent electron pair in a molecular structure contains 0.01-10 mol with respect to 1 mol of Si atoms couple | bonded with the hydroxyl group or the hydrolysis group of a PFPE containing silane compound in a surface treating agent, and 0.01-3 mol It is more preferable that it is contained, and it is especially preferable that 0.33-2 mol is contained.

In one embodiment, it is preferable that the compound containing the atom which has a lone pair of electrons in a molecular structure contains 0.03-3 mol with respect to 1 mol of Si atoms couple | bonded with the hydroxyl group or hydrolyzation group of a PFPE containing silane compound in a surface treating agent. And it is more preferable that 0.3-3 mol is contained.

It is preferable that the compound containing the atom which has a non-covalent electron pair in a molecular structure is contained 0.01 mol or more with respect to 1 mol of PFPE containing silane compounds in a surface treating agent, It is more preferable that 0.1 mol or more is included, 0.15 mol or more is contained It is still more preferable, It is more preferable to contain 0.2 mol or more, It is especially preferable to contain 0.3 mol or more. By including the compound containing the atom which has a non-covalent electron pair in a molecular structure at the above concentration, the surface treating agent of this invention can contribute especially to formation of the surface treatment layer with favorable durability.

It is preferable that 15 mol or less is contained with respect to 1 mol of PFPE containing silane compounds in a surface treating agent, and, as for the compound containing the atom which has a non-covalent electron pair in a molecular structure, it is more preferable that 10 mol or less is included, and 7 mol or less is contained Is particularly preferred.

It is preferable that 6 mol or less is contained with respect to 1 mol of PFPE containing silane compounds in a surface treating agent, and, as for the compound containing the atom which has a non-covalent electron pair in a molecular structure, it is more preferable that 3 mol or less is included, and 1 mol or less is contained Is particularly preferred. By including a compound containing an atom having a non-covalent electron pair in a molecular structure at such concentrations, the handleability of the surface treating agent of the present invention can be improved, and in particular, the clouding of the surface treating agent can be prevented.

In one embodiment, it is preferable that 0.01-15 mol is contained with respect to 1 mol of PFPE containing silane compounds in a surface treating agent, and, as for the compound containing the atom which has a non-covalent electron pair in a molecular structure, 0.01-10 mol is more contained. It is more preferable that 0.1-10 mol is contained, It is especially preferable that 0.3-7 mol is contained, It is more preferable that 0.5-7 mol is contained.

It is preferable that 0.01-6 mol is contained with respect to 1 mol of PFPE containing silane compounds in a surface treating agent, and, as for the compound containing the atom which has a non-covalent electron pair in a molecular structure, 0.1-3 mol are more preferable, 0.3-2 It is particularly preferable that molar is included.

The density | concentration of the compound containing the atom which has a lone pair in a molecular structure contained in a surface treating agent can be measured using glass chromatography, 1H-NMR, etc., for example.

The surface treatment agent of the present invention can impart water repellency, oil repellency, antifouling property, friction durability, and UV resistance to the substrate, and is not particularly limited, but may be suitably used as an antifouling coating agent.

The surface treating agent of the present invention may be diluted with a solvent. As such a solvent, there is no particular limitation, but for example:

Perfluorohexane, CF ₃ CF ₂ CHCl ₂ , CF ₃ CH ₂ CF ₂ CH ₃ , CF ₃ CHFCHFC ₂ F ₅ , 1,1,1,2,2,3,3,4,4,5,5, 6,6-tridecafluorooctane, 1,1,2,2,3,3,4-heptafluorocyclopentane ((Zeroora H (trade name)), C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ , CF ₃ CH ₂ OCF ₂ CHF ₂ , C ₆ F ₁₃ CH = CH ₂ , xylenehexafluoride, perfluorobenzene, methylpentadecafluoroheptylketone, trifluoroethanol, pentafluoro propanol, hexafluoro-isopropanol, HCF ₂ CF ₂ CH ₂ OH, with methane sulfonate, trifluoromethyl trifluoroacetic acid and _{CF 3 O (CF 2 CF 2} O) m1 (CF 2 O) n1 CF 2 CF 3 [ In the formula, m1 and n1 are each independently an integer of 0 or more and 1000 or less, and the existence order of each repeating unit enclosed in parentheses with m1 or n1 is arbitrary in the formula, provided that the sum of m ₁ and n1 is 1 or more. ], 1,1-dichloro-2,3,3,3-tetrafluoro-1-propene, 1,2-dichloro-1,3,3,3-tetrafluoro-1- Lofen, 1,2-dichloro-3,3,3-trifluoro-1-propene, 1,1-dichloro-3,3,3-trifluoro-1-propene, 1,1,2- A fluorine atom-containing solvent selected from the group consisting of trichloro-3,3,3-trifluoro-1-propene, 1,1,1,4,4,4-hexafluoro-2-butene, and the like Can be.

As the solvent, C ₆ F ₁₃ OCH ₃ may be used.

It is preferable that the moisture content contained in the said solvent is 20 ppm or less in mass conversion. The said moisture content can be measured using the Karl Fischer method. By such a water content, the storage stability of a surface treating agent can be improved.

The surface treating agent of this invention may contain the another component. As such other components, although not particularly limited, for example, other surface treatment compounds, (non-reactive) fluoropolyether compounds which can be understood as fluorine-containing oils, preferably perfluoro (poly) ether compounds ( Hereinafter, a "fluorine-containing oil", a silicone compound (hereinafter referred to as "silicone oil") which can be understood as a silicone oil (hereinafter referred to as "silicone oil"), a catalyst, and the like can be given.

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 (1) is mentioned.

In the formula, Rf ⁵ represents a C1-C16 alkyl group (preferably a C _1-16 perfluoroalkyl group) which may be substituted by one or more fluorine atoms, and Rf ⁶ represents one or further substituted by a fluorine atom having 1 to 16 alkyl group (preferably, C _1-16 perfluoroalkyl group), it represents a fluorine atom or a hydrogen atom, Rf ⁵ and Rf ⁶ is, more preferably, Each independently is a C _1-3 perfluoroalkyl group.

a ', b', c 'and d' each represent the number of four types of repeating units of the perfluoro (poly) ether constituting the main skeleton of the polymer, and are each independently an integer of 0 or more and 300 or less, a The sum of ', b', c 'and d' is at least 1, preferably 1 to 300, more preferably 20 to 300. The order of existence of each repeating unit enclosed in parentheses with the subscript a ', b', c 'or d' is arbitrary in the formula. Of these repeating units,-(OC ₄ F ₈ )-is-(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 )-. -(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 ))-, Preferably-(OCF ₂ CF ₂ CF ₂ )-. -(OC ₂ F ₄ )-may be either-(OCF ₂ CF ₂ )-or-(OCF (CF ₃ ))-, but is preferably-(OCF ₂ CF ₂ )-.

As an example of the perfluoro (poly) ether compound represented by the said General formula (1), the compound (one type or mixture of 2 or more types) represented by any of the following general formulas (1a) and (1b) is mentioned. Can be.

In these formulae, Rf ⁵ and Rf ⁶ are as described above; In formula (1a), b "is an integer of 1 or more and 100 or less; In formula (1b), a" and b "are each independently an integer of 1 or more and 30 or less, and c" and d "are respectively Independently, it is an integer of 1 or more and 300 or less. The order of existence of each repeating unit attached with the subscript a ", b", c ", d", and enclosed in parentheses is arbitrary in a formula.

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

In the surface treating agent of the present invention, the fluorine-containing oil is a total of 100 parts by mass of the perfluoro (poly) ether group-containing silane compound and the carboxylic acid ester compound (in the case of two or more kinds, respectively, the sum of these and the following degrees) Similarly), for example, it may be included in 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 General formula (1a) and the compound represented by General formula (1b) may be used independently, respectively, and may be used in combination. It is preferable to use the compound represented by the general formula (1b) than the compound represented by the general formula (1a) because higher surface slipperiness is obtained. When using these in combination, the mass ratio of the compound represented by general formula (1a) and the compound represented by general formula (1b) is preferably 1: 1 to 1:30, and 1: 1 to 1:10 is used. More preferred. According to such a mass ratio, the surface treatment layer excellent in the balance of surface slipperiness and friction durability can be obtained.

In one embodiment, the fluorine-containing oil contains one or more compounds represented by general formula (1b). In such an aspect, the mass ratio of the perfluoro (poly) ether group-containing silane compound and the compound represented by formula (1b) in the surface treatment agent is preferably 10: 1 to 1:10, and 4: 1 to 1 It is more preferable that it is: 4.

In one embodiment, it is preferable that the average molecular weight of the compound represented by Formula (1a) is 2,000-8,000.

In one embodiment, it is preferable that the average molecular weight of the compound represented by Formula (1b) is 8,000-30,000.

In another embodiment, the average molecular weight of the compound represented by formula (1b) is preferably 3,000 to 8,000.

In a preferable embodiment, when forming a surface treatment layer by a vacuum vapor deposition method, you may make a number average molecular weight of a fluorine-containing oil larger than the number average molecular weight of a perfluoro (poly) ether group containing silane compound. For example, the number average molecular weight of the fluorine-containing oil may be 2,000 or more, preferably 3,000 or more, and more preferably 5,000 or more than the number average molecular weight of the perfluoro (poly) ether group-containing silane compound. By setting it as such a number average molecular weight, more excellent friction durability and surface slipperiness | lubricacy can be obtained.

In addition, from another viewpoint, the fluorine-containing oil may be a compound represented by the general formula Rf'-F (wherein Rf 'is a C _5-16 perfluoroalkyl group). Moreover, the chlorotrifluoroethylene oligomer may be sufficient. The compound represented by Rf'-F and the chlorotrifluoroethylene oligomer are preferable in terms of obtaining high affinity with the perfluoro (poly) ether group-containing silane compound wherein Rf ¹ is a C _1-16 perfluoroalkyl group. Do.

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 dimethylsilicone oil, methylphenylsilicone oil and methylhydrogensilicone oil. Examples of the modified silicone oils include straight silicone oils modified with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol and the like. As cyclic silicone oil, cyclic dimethylsiloxane oil etc. are mentioned, for example.

In the surface treating agent of the present invention, such silicone oil is, for example, 0 to 300 parts by mass, preferably 0 to 100 parts by mass of the PFPE-containing silane compound (when these are two or more, the sum thereof and the following also). To 200 parts by mass.

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

Examples of the catalyst include an acid (for example, acetic acid, trifluoroacetic acid, etc.), a base (for example, ammonia, triethylamine, diethylamine, etc.), a transition metal (for example, Ti, Ni, Sn, etc.). ), And the like.

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

As other components, in addition to the above, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyl trimethoxysilane, 3-glycidoxy propyl trimethoxysilane, methyl triacetoxysilane, etc. are mentioned, for example. .

As another component, a C1-C6 alcohol compound is mentioned besides the above, for example.

[Pellets]

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

The surface treatment agent of the present invention is suitably used as a surface treatment agent in that water repellency, oil repellency, antifouling property, waterproofness, high friction durability and UV resistance can be imparted to the substrate. Specifically, the surface treating agent of the present invention is not particularly limited, but may be suitably used as an antifouling coating or a waterproof coating.

[article]

Next, the article of this invention is demonstrated.

The article of this invention contains a base material and the layer (surface treatment layer) formed in the surface treatment agent of this invention on the surface of this base material. This article can be manufactured as follows, for example.

First, a base material is prepared. The base material which can be used for the present invention may be, for example, glass, resin (natural or synthetic resin, for example, may be a general plastic material, plate, film, or other forms), metal (metal such as aluminum, copper, iron, etc.). May be composed of any suitable material such as a single body or a composite such as an alloy), ceramics, semiconductors (silicon, germanium, etc.), fibers (fabrics, nonwovens, etc.), fur, leather, wood, ceramics, stone, etc. Can be.

As the glass, sapphire glass, soda lime glass, alkali aluminosilicate glass, borosilicate glass, alkali free glass, crystal glass, quartz glass are preferable, chemically strengthened soda lime glass, chemically strengthened alkali aluminosilicate glass, and chemically bonded Borosilicate glass is particularly preferred.

As resin, acrylic resin and polycarbonate are preferable.

For example, when the article to be manufactured is an optical member, the material which comprises the surface of a base material may be an optical member material, for example, glass or transparent plastics. In addition, when the article to be manufactured is an optical member, some layer (or film | membrane), for example, a hard-coat layer, an antireflection layer, etc. may be formed in the surface (outermost layer) of a base material. As the antireflection layer, any of a single layer antireflection layer and a multilayer antireflection layer may be used. Examples of the inorganic material 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 multi-layer anti-reflection layer, the outermost layer, it is preferable to use SiO ₂ and / or SiO. When the article to be manufactured is an optical glass component for touch panels, you may have a thin film using a transparent electrode, for example, indium tin oxide (ITO), indium zinc oxide, etc., on a part of the surface of the substrate (glass). . In addition, the base material has an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coat film layer, a polarizing film, a high-order film, a liquid crystal display module, etc. according to the specific specification etc. You may be.

The shape of the base material is not particularly limited. In addition, the surface area | region of the base material which should form a surface treatment layer should just be at least a part of the surface of a base material, and can be suitably determined according to the use, specific specification, etc. of the article to be manufactured.

As such a base material, the surface part may consist of a material which originally has a hydroxyl group at least. Examples of such a material include glass, and metals (particularly nonmetals), ceramics, semiconductors, etc., in which a natural oxide film or a thermal oxide film is formed on the surface thereof. Or, when it is not enough even if it has a hydroxyl group like resin etc., or when it does not have a hydroxyl group originally, it can introduce or increase a hydroxyl group on the surface of a base material by giving some pretreatment to a base material. Examples of such pretreatment include plasma treatment (for example, corona discharge) and ion beam irradiation. Plasma treatment can be suitably used to clean up the substrate surface (removing foreign matters, etc.) while allowing hydroxyl groups to be introduced or increased on the substrate surface. In addition, as another example of such pretreatment, an interfacial adsorbent having a carbon-carbon unsaturated bond group is previously formed in the form of a monomolecular film on the surface of the substrate by the LB method (Rangmue-Blodgett method), chemical adsorption method, or the like, and thereafter, The method of cleaving an unsaturated bond in the atmosphere containing these etc. is mentioned.

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

Subsequently, the film of the surface treating agent of this invention mentioned above is formed in the surface of such a base material, this film is post-processed as needed, and a surface treating layer is formed by the surface treating agent of this invention by this.

The film formation of the surface treating agent of this invention can be implemented by applying the surface treating agent of this invention so that the said surface may be coat | covered with respect to the surface of a base material. The coating method is not particularly limited. For example, wet coating and dry coating can be used.

Examples of the wet coating method 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 deposition), sputtering, CVD, and similar methods. Specific examples of the vapor deposition method (usually, the vacuum vapor deposition method) include resistance heating, high frequency heating using an electron beam, microwaves, and the like, and similar methods. Specific examples of the CVD method include plasma-CVD, optical CVD, thermal CVD, and similar methods.

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

In the case of using the wet coating method, the surface treating agent of the present invention may be applied to the surface of the substrate after being diluted with a solvent. In view 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 perfluoro aliphatic hydrocarbons (for example, perfluorohexane, perfluoromethylcyclohexane And perfluoro-1,3-dimethylcyclohexane); Polyfluoro aromatic hydrocarbons (eg bis (trifluoromethyl) benzene); Polyfluoro aliphatic hydrocarbons (e.g., C ₆ F ₁₃ CH ₂ CH ₃ (e.g. Asahiclean® AC-6000, manufactured by Asahi Glass Co., Ltd.), 1,1,2,2, 3,3,4-heptafluorocyclopentane (e.g., Aurora (registered trademark) H of Nippon Xeon Co., Ltd.); hydrofluorocarbon (HFC) (e.g., 1,1,1, 3,3-pentafluorobutane (HFC-365mfc); hydrochlorofluorocarbons (e.g. HCFC-225 (Asacycline® AK225)); hydrofluoroether (HFE) (e.g. Perfluoropropylmethyl ether (C ₃ F ₇ OCH ₃ ) (e.g. Novec ™ 7000 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutylmethyl ether (C ₄ F ₉ OCH ₃ ) (example For example, Novec (trade name) 7100 manufactured by Sumitomo 3M Co., Ltd., perfluorobutylethyl ether (C ₄ F ₉ OC ₂ H ₅ ) (e.g., Novec (trade name) manufactured by Sumitomo 3M Corporation). Alkyl perfluoroalkyl ethers such as 00) and perfluorohexyl methyl ether (C ₂ F ₅ CF (OCH ₃ ) C ₃ F ₇ ) (e.g. Novec 7300 manufactured by Sumitomo 3M Co., Ltd.). (Perfluoroalkyl group and alkyl group may be linear or branched), or CF ₃ CH ₂ OCF ₂ CHF ₂ (e.g., AsahiClean (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.)), 1,2-dichloro-1,3,3,3-tetrafluoro-1-propene (e.g., Bertrel (registered trademark) cion manufactured by Mitsui DuPont Fluoro Chemical Co., Ltd.) and the like. It can be used individually or in mixture of 2 or more types In addition, in order to adjust the solubility of a perfluoro (poly) ether group containing silane compound and a perfluoro polyether modified compound, for example, It can also be mixed with a solvent.

In the case of using a dry coating method, the surface treatment agent of the present invention may be applied as it is, or after dilution with the solvent described above, the dry coating method may be applied.

It is preferable to perform film formation so that the surface treating agent of this invention may exist with a catalyst for hydrolysis and dehydration condensation in a film | membrane. For the sake of simplicity, in the case of the wet coating method, after diluting the surface treatment agent of the present invention with a solvent, the catalyst may be added to the dilution liquid of the surface treatment agent of the present invention immediately before application to the substrate surface. In the case of the dry coating method, pellets in which the surface treating agent of the present invention to which the catalyst is added are deposited (usually, vacuum deposition) as it is, or the metal porous body such as iron or copper is impregnated with the surface treating agent of the present invention to which the catalyst is added You may perform vapor deposition (usually a vacuum vapor deposition) process using a type | mold substance.

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.

Subsequently, the membrane is post-treated if necessary. Although this post-treatment is not specifically limited, For example, water supply and dry heating may be performed sequentially, and in more detail, you may carry out as follows.

After forming the surface treating agent of this invention on the surface of a base material as mentioned above, water is supplied to this film (henceforth a "precursor film"). The method of supplying water is not particularly limited, and for example, condensation due to the temperature difference between the precursor film (and the substrate) and the ambient atmosphere, or spraying of water vapor (steam) may be used.

The supply of water is, for example, 0 to 250 ° C, preferably 60 ° C or more, more preferably 100 ° C or more, preferably 180 ° C or less, and more preferably 150 ° C or less. Can be. By supplying water in such a temperature range, it is possible to advance hydrolysis. Although the pressure in this case is not specifically limited, It can simply be normal pressure.

Subsequently, the precursor film is heated on the surface of the base material in a dry atmosphere exceeding 60 ° C. The dry heating method is not particularly limited, and the precursor film is a temperature exceeding 60 ° C, preferably exceeding 100 ° C, for example, 250 ° C or less, preferably 180 ° C or less, together with the substrate. What is necessary is just to arrange | position in an atmosphere of unsaturated steam pressure. Although the pressure in this case is not specifically limited, It can simply be normal pressure.

Under such an atmosphere, between the perfluoro (poly) ether group-containing silane compounds of the present invention, groups bonded to Si after hydrolysis rapidly dehydrate and condense. 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 surface of a base material, and dehydration condenses when the reactive group which exists in a base material surface is a hydroxyl group. As a result, a bond is formed between the perfluoro (poly) ether group-containing silane compound and the substrate.

Said moisture supply and dry heating may be performed continuously by using superheated steam.

Post-processing can be performed as mentioned above. It should be noted that such post-treatment may be carried out to further improve the friction durability, but is not essential to making the articles of the present invention. For example, after applying the surface treating agent of this invention to the base material surface, you may just leave it as it is.

As mentioned above, the surface treatment layer derived from the film | membrane of the surface treating agent of this invention is formed in the surface of a base material, and the article of this invention is manufactured. The surface treatment layer obtained by this has favorable UV resistance. In addition to the good UV resistance, the surface treatment layer may be water-repellent, oil-repellent, antifouling (for example, to prevent adhesion of contamination such as fingerprints) and surface slippery (or depending on the composition of the composition to be used). Lubricity, for example, wiping off of dirt such as fingerprints, excellent touch to a finger), high friction durability, and the like, and can be suitably used as a functional thin film.

That is, this invention also relates to the optical material which has the said hardened | cured material in outermost layer.

As the optical material, in addition to the optical materials related to the display and the like as exemplified later, various kinds of optical materials are preferably mentioned: for example, a cathode ray tube (CRT; eg, TV, personal computer monitor), liquid crystal display, plasma Anti-reflective coating on displays such as displays, organic EL displays, inorganic thin film EL dot matrix displays, rear projection displays, fluorescent display tubes (VFDs), field emission displays (FEDs), or protective plates of these displays, or their surfaces To carry out.

The article having the 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: lenses such as glasses; Front protective plates, antireflection plates, polarizing plates, antiglare plates of displays such as PDPs and LCDs; Touch panel sheets for devices such as mobile phones and portable information terminals; The disk surface of an optical disk such as a Blu-ray (registered trademark) disk, a DVD disk, a CD-R, or a MO; Optical fiber etc.

In addition, the article which has a surface treatment layer obtained by this invention may be a medical apparatus or a medical material.

The thickness of the surface treatment layer is not particularly limited. In the case of the optical member, the thickness of the surface treatment layer is in the range of 1 to 50 nm, more preferably 1 to 30 nm, and particularly preferably 1 to 15 nm, and the optical performance, surface slipperiness, friction durability, and antifouling properties It is preferable at the point.

As another aspect, after forming another layer on the surface of a base material, you may form the film of the surface treatment layer obtained by this invention on the surface of the layer.

In the above, the article obtained using the surface treating agent of this invention was demonstrated in detail. In addition, the use of the surface treating agent of this invention, a usage method, the manufacturing method of an article, etc. are not limited to what was illustrated above.

EXAMPLE

Although the surface treating agent of this invention is demonstrated further more concretely through the following example, this invention is not limited to these Examples.

(Examples 1 to 4 and Comparative Example 1)

The mixture or compound shown in following Table 1 was melt | dissolved in hydrofluoroether (Three company make, Novec HFE7200) so that total concentration might be 20 wt%, and the surface treatment agent was prepared.

Compound A used in the Example and the comparative example is as follows.

Perfluoropolyether group-containing silane compound (A)

The surface treating agent prepared above was vacuum-deposited on the chemically strengthened glass (the Corning company make, "gorilla" glass, thickness 0.7mm). The processing conditions of vacuum evaporation were 3.0x10 <^-3> Pa. First, a silicon dioxide film having a thickness of 5 nm was formed on the surface of the chemically strengthened glass, and then, 4 mg of the surface treating agent (ie, Compound A in Examples 1 to 4) per chemically strengthened glass (55 mm x 100 mm). And 0.8 mg of a mixture of DMSO, and 0.8 mg of Compound A in Comparative Example 1). Subsequently, after leaving the obtained chemically strengthened glass with a vapor deposition film in the atmosphere at a temperature of 150 ° C. for 30 minutes, the resultant was cooled to room temperature to form a surface treatment layer.

<Evaluation of friction durability>

About the surface treatment layer formed in said Example 1-4 and Comparative Example 1, the friction durability test shown below was implemented as evaluation of actual use durability.

As an initial evaluation, after forming a surface treatment layer, the static contact angle of water was measured in the state which has not contacted the surface yet (zero friction times). The measurement of the static contact angle of water was performed in 1 microliter of water using the contact angle measuring apparatus (made by Kyowa Kaimen Kagaku Co., Ltd.).

Thereafter, the sample article on which the surface treatment layer is formed is horizontally placed, and the following friction contactor is brought into contact with the surface of the surface treatment layer (the contact surface is a circle having a diameter of 1 cm), and a load of 5 N is applied thereto. The friction was reciprocated at a speed of 40 mm / sec with a load applied. The friction was reciprocated up to 4000 times, and the static contact angle (degrees) of water was measured for every 1000 round trips (the number of frictions). The test was stopped when the measured value of the static contact angle of water became less than 60 degrees. The results are shown in Table 2 (in the table, the symbol "-" is not measured).

Friction

As a rubbing machine, what covered the surface (diameter 1cm) of the silicon rubber processed product shown below using the cotton which dipped artificial sweat of the composition shown below was used.

Composition of artificial sweat

Anhydrous Disodium Phosphate: 2g

Sodium Chloride: 20g

85% Lactic Acid: 2 g

Histidine hydrochloride: 5 g

Distilled Water: 1㎏

Silicon rubber workpiece

The product which processed the silicone rubber stopper SR-51 made from Tigers polymer into the cylinder shape of diameter 1cm and thickness 1cm.

From the result of Table 2, it was confirmed that the surface treatment layers of Examples 1-4 suppressed the fall of contact angle, and showed the outstanding durability. This is considered to be because the chemical resistance and the frictional resistance of the formed surface treatment layer were improved by the catalytic effect of DMSO, and the PFPE-containing silane compound and the substrate (reinforced glass) were bonded more firmly.

The present invention can be suitably used to form a surface treatment layer on the surface of various substrates, especially optical members where transparency is required.

Claims (16)

Formula (A1), Formula (A2), Formula (B1), Formula (B2), Formula (C1) or Formula (C2):

[In meals:
PFPE, independently at each occurrence, is represented by the formula:
_{- (OC 6 F 12) a} - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
(a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, the sum of a, b, c, d, e and f is at least 1, and a, b, c, d The order of the existence of each repeating unit, enclosed in parentheses, with e or f is arbitrary in the formula.)
A group represented by;
Each occurrence of Rf independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;
R ¹³ each independently represent a hydroxyl group or a hydrolyzable group;
R ¹⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms;
R ¹¹ each independently represent a hydrogen atom or a halogen atom;
R < ¹² > represents a hydrogen atom or a lower alkyl group each independently in each appearance,
n is an integer of 0 to 3, independently for each (-SiR ¹³ _n R ¹⁴ _3-n ) unit;
Provided that at least two Si bonded to a hydroxyl group or a hydrolyzable group are present in formulas (A1) and (A2);
Each X ¹ independently represents a single bond or a 2 to 10 valent organic group;
X ² in each occurrence independently represent a single bond or a divalent organic group,
t is an integer of 1-10 each independently in each occurrence;
α is an integer of 1 to 9 each independently at each occurrence;
α 'are each independently an integer of 1 to 9;
X <^3> represents a single bond or a 2-10 valent organic group each independently in each appearance;
β is an integer of 1 to 9 each independently at each occurrence;
β 'are each independently an integer of 1 to 9;
Each occurrence of R ^a independently represents -Z ¹ -SiR ¹ _p R ² _q R ³ _r ;
Z ¹ in each occurrence independently represents an oxygen atom or a divalent organic group;
R ¹ each independently represent R ^{a ′} in each occurrence;
R ^{a '} is synonymous with R ^a ;
Among R ^a , at most 5 Si is linearly connected through the Z ¹ group;
R ² in each occurrence independently represents a hydroxyl group or a hydrolyzable group;
R < ³ > represents a hydrogen atom or a lower alkyl group each independently in each appearance,
p is an integer of 0 to 3 each independently at each occurrence;
q is an integer of 0 to 3 each independently at each occurrence;
r is an integer of 0 to 3 each independently at each occurrence;
However, for each -Z ¹ -SiR ¹ _p R ² _q R ³ _r , the sum of p, q and r is 3, and in formulas (B1) and (B2), Si bonded to a hydroxyl group or a hydrolyzable group is represented by At least two are present;
Each occurrence of R ^b independently represents a hydroxyl group or a hydrolyzable group;
Each occurrence of R ^c independently represents a hydrogen atom or a lower alkyl group,
k1 is an integer of 0-3 each independently at each occurrence;
l1 is an integer of 0 to 3 each independently at each occurrence;
m1 is an integer of 0-3 each independently at each occurrence;
However, in every -SiR ^a _k1 R ^b _l1 R ^c _m1 , the sum of k1, l1 and m1 is 3,
X ⁴ in each occurrence independently represents a single bond or a 2 to 10 valent organic group;
γ is an integer of 1 to 9 each independently at each occurrence;
γ 'are each independently an integer of 1 to 9;
Each occurrence of R ^d independently represents -Z ² -CR ⁸¹ _p2 R ⁸² _q2 R ⁸³ _r2 ;
Z ² each independently represent an oxygen atom or a divalent organic group;
R ⁸¹ in each occurrence independently represents R ^{d ′} ;
R ^{d '} is synonymous with R ^d ;
Among R ^d , up to 5 C may be connected linearly through the Z ² group;
R ⁸² each independently represent —Y—SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 in each occurrence;
Y represents a divalent organic group each independently in each appearance;
R ⁸⁵ each independently represent a hydroxyl group or a hydrolyzable group;
R ⁸⁶ each independently at each occurrence represents a hydrogen atom or a lower alkyl group,
n2 represents an integer of 0 to 3 independently for each (-Y-SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 ) unit;
R ⁸³ at each occurrence independently represent a hydrogen atom or a lower alkyl group,
p2 is an integer of 0-3 each independently at each occurrence;
q2 is an integer of 0-3 each independently in each occurrence;
r2 is an integer of 0 to 3 each independently at each occurrence;
Provided that for each -Z ² -CR ⁸¹ _p2 R ⁸² _q2 R ⁸³ _r2 , the sum of p2, q2 and r2 is 3;
R ^e each independently represent —Y—SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 at each occurrence;
R ^f each independently represents a hydrogen atom or a lower alkyl group,
k2 is an integer of 0-3 each independently at each occurrence;
l2 is an integer of 0-3 each independently at each occurrence;
m2 is an integer of 0-3 each independently at each occurrence;
However, in each of (CR ^d _k2 R ^e _l2 R ^f _m2 ), the sum of k2, l2 and m2 is 3, and in the formulas (C1) and (C2), the group represented by -Y-SiR ⁸⁵ is 2 or more. exist.]
The surface treating agent containing the perfluoro (poly) ether group containing silane compound represented by any of and the compound containing the atom which has a lone pair in a molecular structure. The surface treating agent of Claim 1 in which the compound containing the atom which has a lone pair in a molecular structure contains at least 1 atom chosen from the group which consists of a nitrogen atom, an oxygen atom, a phosphorus atom, and a sulfur atom. The compound according to claim 1 or 2, wherein the compound containing an atom having a non-covalent electron pair in its molecular structure is selected from the group consisting of aliphatic amine compounds, aromatic amine compounds, phosphate amide compounds, amide compounds, urea compounds, and sulfoxide compounds. Surface treatment agent. The compound according to any one of claims 1 to 3, wherein the compound containing an atom having a non-covalent electron pair in its molecular structure is at least one compound selected from the group consisting of sulfoxide compounds, aliphatic amine compounds, and aromatic amine compounds. , Surface treatment agent. The method according to any one of claims 1 to 4, wherein the compound containing an atom having a non-covalent electron pair in its molecular structure is 0.01 to 10 moles with respect to 1 mole of Si atom bonded to a hydroxyl group or hydrolyzable group of the PFPE-containing silane compound. Surface treatment agent containing. The surface treating agent according to any one of claims 1 to 5, wherein R ^f is independently a perfluoroalkyl group having 1 to 16 carbon atoms in each occurrence. The PFPE according to any one of claims 1 to 6, independently in each occurrence, of the following formulas (a), (b) or (c):

[Wherein d is an integer of 1 to 200.]

[Wherein, c and d are each independently an integer of 0 or more and 30 or less;
e and f are each independently an integer of 1 or more and 200 or less;
the sum of c, d, e and f is an integer of 10 or more and 200 or less;
The order of existence of each repeating unit appended with the subscripts c, d, e or f and enclosed in parentheses is arbitrary in the formula.]

[Wherein, R ⁶ is OCF ₂ or OC ₂ F ₄ ;
R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or a combination of two or three groups selected from these groups;
j is an integer from 2 to 100.]
Phosphorus, surface treatment agent. The surface treating agent of any one of Claims 1-7 whose number average molecular weights of an Rf-PFPE part are 500-30,000 each independently. The surface treating agent according to any one of claims 1 to 8, wherein each of X ¹ , X ^3, and X ⁴ is a divalent organic group each independently. The surface treating agent according to any one of claims 1 to 9, further comprising one or more other components selected from fluorine-containing oils, silicone oils, and catalysts. The surface treating agent according to any one of claims 1 to 10, further comprising a solvent. The surface treatment agent according to any one of claims 1 to 11, which is used as an antifouling coating or a waterproof coating. The surface treating agent according to any one of claims 1 to 12, which is for vacuum deposition. A pellet containing the surface treating agent according to any one of claims 1 to 13. An article comprising a substrate and a layer formed of the surface treating agent according to any one of claims 1 to 13 on the surface of the substrate. The article of claim 15, wherein the article is an optical member.