JP2001081445A - Surface treatment composition and surface-treated substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a surface treatment composition excellent in water repellency, stainproofness and capability for rolling down water droplets by incorporating, into the same, (A) a silicone compound, (B) a silicon compound, and/or (C) a partial cohydrolyzate of a fluorine-containing silicone compound and a silicon compound. SOLUTION: This composition contains (A) a silicone compound, (B) a silicon compound, and/or (C) a partial cohydrolyzate of a fluorine-containing silicone compound and a silicon compound represented by formula III. Ingredient A is a compound selected from among fluorine-containing silicone compounds each consisting essentially of organosiloxane units each containing a monovalent fluorine-containing organic group represented by formula I and organosiloxane units each having a monovalent silicon- containing organic group represented by formula II and their partial hydrolyzates. Ingredient B is a compound selected from among silicon compounds represented by formula III and their partial hydrolyzates. In the formulas, Rf is a monovalent polyfluorohydrocarbon group or the like; X is a divalent hydrocarbon group or the like; R1 and R20 are each a monovalent organic group; Y1 and Y2 are each a monovalent hydrolyzable group or the like; a>=1; b is 1-3; and j is 1-4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a surface treating agent composition capable of imparting excellent water repellency and water-drop resistance to a substrate surface, and a substrate surface-treated with the composition.

[0002]

2. Description of the Related Art Glass, plastics, ceramics, metal substrates, and substrates whose surfaces have been treated are widely used. Dirt and water adhering to the substrate surface promote damage, contamination, coloring, corrosion, and the like of the substrate surface, and cause changes in the electrical characteristics, mechanical characteristics, optical characteristics, and the like of the substrate.

As a method for solving the above problems, the following composition is directly applied to the surface of a substrate in order to prevent adhesion of dirt (hereinafter referred to as antifouling property) and to prevent adhesion of water (hereinafter referred to as water repellency). Proposals have been made.

A glass surface treatment composition comprising a fluorine-containing silicone compound having a hydrolyzable group and methanol (JP-A-8-302020), a fluorosilicone,
Coating composition comprising a silicon compound having a hydrolyzable group and a non-fluorinated silicone compound having a hydrolyzable group (JP-A-2-283776), a fluorine-containing silicone having a hydrolyzable group and a trifluoromethyl group A fiber treating composition comprising a compound or a concrete surface treating composition (JP-A-5-43698); and a surface treating composition comprising a fluorine-containing silicone compound having a hydrolyzable group (JP-A-8-31403).

[0005]

However, the conventional water repellent composition has a problem that unevenness is apt to occur during application and a problem that water repellency is not maintained for a long time. Further, even if the treated substrate surface is given water repellency, there is a problem that water droplets remain on the substrate surface. In addition, when imparting water repellency to an already used article, it is necessary to apply the water repellent composition directly at normal temperature to impart water repellency. However, there was a problem that sufficient water repellency could not be obtained only by directly applying the conventional water repellent composition at normal temperature.

[0006]

SUMMARY OF THE INVENTION The present invention has been made for the purpose of solving the above-mentioned problems, and when the surface of a substrate is treated with a surface treating agent composition containing a specific compound, the surface of the substrate is improved. It has been found that water repellency, antifouling property, water drop falling property, and water drop removal property can be imparted to water. In addition, they have found that these properties imparted are excellent in durability.

That is, the present invention provides the following silicone compound (A) and the following silicone compound (B), and / or
Provided is a surface treating agent composition characterized by essentially containing a partial cohydrolysis product of the following fluorinated silicone compound (A ¹ ) and a silicon compound (B ¹ ) represented by the following formula 3:

Silicone compound (A): an organosiloxane unit (a ¹ ) in which a monovalent fluorine-containing organic group represented by the following formula 1 is bonded to a silicon atom and a monovalent silicon-containing organic group represented by the following formula 2 A fluorine-containing silicone compound (A ¹ ) composed essentially of an organosiloxane unit (a ² ) bonded to a silicon atom, and a partial hydrolysis product (A ² ) of the fluorine-containing silicone compound (A ¹ ); At least one compound selected from the group consisting of: Silicon compound (B): at ^{least one} compound selected from a silicon compound (B ¹ ) represented by the following formula 3 and a partial hydrolysis product (B ² ) of the silicon compound (B ¹ ). -X-R ^f ··· formula _{1 - (CH 2) a Si} (R 1) 3-b (Y 1) b ··· formula _{^{2 (R 20) 4-j}} Si (Y 2) j ··· Formula 3 However, the symbols in Formulas 1 to 3 have the following meanings. R ^f : a monovalent polyfluorohydrocarbon group or a group in which an etheric oxygen atom is inserted between carbon-carbon bonds of a monovalent polyfluorohydrocarbon group. X: divalent hydrocarbon group or carbon of divalent hydrocarbon group
A group in which an etheric oxygen atom is inserted between carbon bonds. R ¹ and R ²⁰ are each independently a monovalent organic group. Y ¹ and Y ² each independently represent a monovalent hydrolyzable group or an isocyanate group. a: an integer of 1 or more. b: 1, 2, or 3. j: 1, 2, 3, or 4.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The term "organic group" used herein means a group containing a carbon atom. In addition, the term “hydrocarbon group” in this specification refers to a group consisting of only a carbon atom and a hydrogen atom unless there is a description such as “including an etheric oxygen atom”. The hydrocarbon group may be either an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group.

[0010] The silicone compound is a compound in which two or more organosiloxane units formed by bonding an organic group to a silicon atom forming a siloxane bond are linked. The fluorine-containing silicone compound (A ¹ ) in the present invention is defined as an organosiloxane unit (a ¹ ) having a monovalent fluorine-containing organic group (formula 1) bonded to a silicon atom and a monovalent silicon-containing organic group (formula 2). A compound composed essentially of an organosiloxane unit (a ² ) bonded to a silicon atom.

The monovalent fluorine-containing organic group (formula 1) is represented by -XR
a group represented by ^f, and R ^f in the group, monovalent polyfluorohydrocarbon group, or a monovalent polyfluorohydrocarbon group having a carbon - a group having an etheric oxygen atom inserted between carbon bond Show. The monovalent polyfluorohydrocarbon group refers to a group in which two or more hydrogen atoms of the monovalent hydrocarbon group have been substituted with fluorine atoms, and a polyfluoroalkyl group is preferable. The proportion of fluorine atoms in the monovalent polyfluorohydrocarbon group is (1
The number of fluorine atoms in the polyvalent polyfluorohydrocarbon group) / (the number of hydrogen atoms in the hydrocarbon group having the same number of carbon atoms corresponding to the monovalent polyfluorohydrocarbon group) × 100 (%), 60% It is preferably at least 80%, more preferably at least 100%, that is, "monovalent in which substantially all of the hydrogen atoms of the monovalent hydrocarbon group are substituted with fluorine atoms." Perfluorohydrocarbon groups "are preferred.

The monovalent polyfluorohydrocarbon group may have a linear structure or a branched structure, and preferably has a linear structure. When it has a branched structure, it is preferably a short chain having about 1 to 3 carbon atoms in the branched portion. Further, the branched portion is preferably present at a terminal portion of the monovalent polyfluorohydrocarbon group. The carbon number of the monovalent polyfluorohydrocarbon group is preferably from 1 to 18, and particularly preferably from 4 to 12.

Further, the monovalent polyfluorohydrocarbon group is
A polyfluoroalkyl group in which two or more hydrogen atoms of an alkyl group are substituted with fluorine atoms is preferable, and a perfluoroalkyl group in which substantially all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms is particularly preferable. The polyfluoroalkyl group and the perfluoroalkyl group have 1 to 1 carbon atoms.
8 is preferable, and especially 4 to 12 is preferable.

As specific examples of the monovalent polyfluorohydrocarbon group,
And the following groups. In the following specific examples
Includes the groups corresponding to the groups of each structural isomerism
You. C_FourF₉− ｛However, F (CF_Two)_Four−, (CF_Three)_TwoC
FCF_Two−, (CF_Three)_ThreeC-, CF_ThreeCF_TwoCF (CF_Three)
Or any of structurally isomeric groups such as —, C_FiveF
₁₁− ｛However, F (CF_Two)_Five−, (CF_Three)_TwoCF (CF
_Two)_Two−, (CF_Three) _ThreeCCF_Two−, F (CF_Two)_ThreeCF (C
F_Three)-And the like.
C₆F₁₃− ｛However, F (CF_Two)_ThreeC (CF_Three)_Two-Etc.
Any of structurally isomeric groups may be used.₈F₁₇−,
C_TenF_{twenty one}-, C₁₂F_{twenty five}-, C₁₄F₂₉-, C₁₆F₃₃-, C
₁₈F₃₇-, C₂₀F₄₁−, (CF_Three)_TwoCF (CF_Two)_s−
(S is an integer of 1 or more), HC_tF_2t− (T is one or more integers
number).

Further, the group in which an etheric oxygen atom is inserted between the carbon-carbon bonds of the monovalent polyfluorohydrocarbon group is defined as the carbon-carbon bond in the monovalent polyfluorohydrocarbon group, or It means a group having an etheric oxygen atom inserted between the above monovalent polyfluorohydrocarbon group and X.

The group having an etheric oxygen atom inserted between carbon-carbon bonds of a monovalent polyfluorohydrocarbon group includes:
A group containing a polyfluorooxyalkylene moiety is preferred, a group containing a perfluorooxyalkylene moiety is particularly preferred, and a group containing a perfluorooxyalkylene moiety and having a terminal perfluoroalkyl group is particularly preferred. Examples of the perfluorooxyalkylene include perfluorooxymethylene, perfluorooxyethylene, perfluorooxypropylene, and perfluorooxybutylene.

Specific examples of the group in which an etheric oxygen atom is inserted between carbon-carbon bonds of a monovalent polyfluorohydrocarbon group include the following groups. F (CF ₂ ) ₅ OC
_{F (CF 3) -, F} [CF (CF 3) CF 2 O] u CF (C
F ₃ ) CF ₂ CF _2- (u is an integer of 1 or more), F [CF
(CF ₃ ) CF ₂ O] _y CF (CF ₃ )-(y is an integer of 1 or more), F (CF ₂ CF ₂ CF ₂ O) _v CF ₂ CF _2- (v is 1
Or an _{integer), (CF 2 CF 2 O} ) w CF 2 CF 2 - (w is an integer of 1 or more).

In the monovalent fluorine-containing organic group represented by the formula 1, X represents a divalent hydrocarbon group or an etheric oxygen atom inserted between carbon-carbon bonds of the divalent hydrocarbon group. Represents a group. Examples of the divalent hydrocarbon group, preferably an alkylene group, the alkylene group may be a branched structure may be straight chain structure, in the present invention - (CH _{2) i} - (where, i is An integer of 1 to 20, preferably an integer of 2 to 8) is preferable. In the case of a branched structure, a branched structure having a short chain having about 1 to 3 carbon atoms is preferable. The group in which an etheric oxygen atom is inserted between the carbon-carbon bonds of the divalent hydrocarbon group is preferably a group in which an etheric oxygen atom is inserted at one position between the carbon-carbon bonds of the above-described alkylene group.

The monovalent fluorine-containing organic group (formula 1) is represented by the following formula 1
a, a monovalent fluorine-containing organic group represented by the following formula 1b or 1c is preferable. However, Equation 1a, Equation 1b,
And the symbols in Formula 1c have the following meanings. R ^f1 and R ^f3 each independently represent a monovalent polyfluorohydrocarbon group. R ^f2 : a monovalent polyfluorohydrocarbon group containing an etheric oxygen atom. X ¹ , X ² , X ³ , X ⁴ , and X ⁵ : each independently represents 2
Valent hydrocarbon group. R ^f1 -X ¹ - ··· formula ^{1a, R f2 -X 2 -O-} X 3 - ··· formula ^{1b, R f3 -X 4 -O-} X 5 - ··· formula 1c.

Examples of R ^f1 and R ^f3 include the same examples as those of the above-mentioned monovalent polyfluorohydrocarbon group, and examples of R ^f2 include those of the above-mentioned monovalent polyfluoro hydrocarbon group. The same example as the group in which an etheric oxygen atom is inserted between carbon-carbon bonds can be mentioned. X ¹ , X ² , X ³ , X ⁴ ,
And X ⁵ are each independently a linear alkylene group represented by — (CH ₂ ) _h — (where h is an integer of 1 to 10, and preferably an integer of 2 to 4). preferable.

Further, the monovalent fluorine-containing organic group (formula 1) is
It is preferably a monovalent fluorinated organic group represented by the following formula 1a ', 1b' or 1c '. Where Equation 1
The symbols in a ′, Formula 1b ′, and Formula 1c ′ have the following meanings. d: an integer of 1 to 18, preferably 6 to 12. e: an integer of 1 to 10, preferably an integer of 1 to 5. g: an integer of 1 to 18, preferably 4 to 12. X ¹ , X ² , X ³ , X ⁴ , X ⁵ : each independently represents a divalent hydrocarbon group, preferably a linear alkylene group. ^{_{C d F 2d + 1 -X 1}} - ··· formula 1a ', F [CF (CF 3) CF 2 O] e CF (CF 3) -X 2 -O-X 3 - ··· formula 1b', ^{_{C g F 2g + 1 -X 4}} -O-X 5 - ··· formula 1c '.

A specific example of the formula 1a 'will be described. However, the perfluoroalkyl group in the following formula preferably has a linear structure. _{C 4 F 9 - (CH 2} ) 2 -, C 4 F 9 - (CH 2)
_{3 -, C 4 F 9 -} (CH 2) 4 -, C 5 F 11 - (CH 2) 2 -,
_{C 5 F 11 - (CH 2} ) 3 -, C 6 F 13 - (CH 2) 2 -, C 8
F _17- (CH ₂ ) _2- , C ₈ F _17- (CH ₂ ) _3- , C ₈ F <sub>17
- (CH 2) 4 -,</sub> C 9 F 19 - (CH 2) 2 -, C 9 F 19 -
_{(CH 2) 3 -, C} 10 F 21 - (CH 2) 2 -.

Specific examples of Formula 1b or Formula 1b 'will be given.
_{F [CF (CF 3) CF} 2 O] 2 CF (CF 3) CH 2 O
_{(CH 2) 3 -, F} [CF (CF 3) CF 2 O] 4 CF (C
_{F 3) CH 2 O (CH} 2) 3 -, F (CF 2 CF 2 CF 2 O) 2
_{CF 2 CF 2 CH 2 O (} CH 2) 3 -.

A specific example of the formula 1c 'will be given. However, the perfluoroalkyl group in the following formula preferably has a linear structure. _{C 4 F 9 - (CH 2} ) 2 -O- (CH 2) 3 -, C 6 F
_{13 - (CH 2) 2 -O-} (CH 2) 3 -, C 8 F 17 - (C
_{H 2) 2 -O- (CH 2} ) 3 -, C 8 F 17 - (CH 2) 3 -O
— (CH ₂ ) ₃ —.

R ¹ in a monovalent silicon-containing organic group (formula 2)
Is preferably a monovalent hydrocarbon group, particularly preferably an alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 10, particularly preferably 1 to 4, and particularly preferably 1 (that is, R ¹ is a methyl group). The alkyl group preferably has a linear structure.

In the monovalent silicon-containing organic group (formula 2), Y ¹ represents a monovalent hydrolyzable group or an isocyanate group (—NCO). Examples of the monovalent hydrolyzable group include a chlorine atom, a bromine atom, a methoxy group, an ethoxy group, and a propoxy group, and among them, a methoxy group and an ethoxy group are preferable. a is preferably an integer of 1 to 4, particularly preferably 2 or 3. b is preferably 2 or 3, and particularly preferably 3.

Specific examples of the monovalent silicon-containing organic group (formula 2) are shown below. _{- (CH 2) 2 Si (} OCH 3) 3, - (CH 2) 2 Si (CH 3) (OCH 3) 2, - (CH 2) 2 SiCl 3, - (CH 2) 3 SiCl 3, - ( _{CH 2) 3 Si (CH 3} ) Cl 2, - (CH 2) 3 Si (OCH 2 CH 3) 3, - (CH 2) 3 Si (CH 3) (OCH 2 CH 3) 2, - (CH 2 ) ₃ Si (OCH ₃ ) ₃ ,-(CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂ ,-(CH ₂ ) ₂ Si (NCO) ₃ ,-(CH ₂ ) ₃ Si (NCO) ₃ , _{- (CH 2) 2 Si (} CH 3) (NCO) 2, - (CH 2) 3 Si (CH 3) (NCO) 2.

As the organosiloxane unit (a ¹ ) in the fluorine-containing silicone compound (A ¹ ), (R ¹⁴ )
(A ¹⁰ ) SiO _2/2 , (A ¹⁰ ) ₂ SiO _2/2 , (A ¹⁰ ) S
iO _3/2 , (A ¹⁰ ) ₃ SiO _1/2 , (R ¹⁴ ) ₂ (A ¹⁰ ) Si
O _{1/2 wherein} A ¹⁰ represents a monovalent fluorine-containing organic group (formula 1), R ¹⁴ represents a monovalent organic group, and a monovalent fluorine-containing organic group (formula 1) and a monovalent silicon-containing organic group. Organic groups other than the group (Formula 2) (hereinafter referred to as “other monovalent organic groups”) are preferred. ].

As the other monovalent organic group, a monovalent hydrocarbon group is preferable, and an alkyl group is particularly preferable. The alkyl group preferably has 1 to 10 carbon atoms, particularly preferably 1 to 4, and particularly preferably 1 (that is, a methyl group).
The alkyl group preferably has a linear structure.

As the organosiloxane unit (a ² ) in the fluorine-containing silicone compound (A ¹ ), (R ¹⁵ )
(B ¹⁰ ) SiO _2/2 , (B ¹⁰ ) ₂ SiO _2/2 , (B ¹⁰ ) S
iO _3/2 , (B ¹⁰ ) ₃ SiO _1/2 , (R ¹⁵ ) (R ¹⁶ ) (B
¹⁰ ) SiO _1/2 , (R ¹⁵ ) ₂ (B ¹⁰ ) SiO _1/2 [where B ¹⁰ represents a monovalent silicon-containing organic group (formula 2), and R ¹⁵ and R ¹⁶ each independently represent It represents a monovalent organic group, and other monovalent organic groups are preferred. ].

Further, the fluorine-containing silicone compound (A ¹ )
Is an organosiloxane unit other than the organosiloxane unit (a ¹ ) or the organosiloxane unit (a ² ) [hereinafter referred to as an organosiloxane unit (a ³ )]. ] Is preferable.

The organosiloxane unit (a ³ ) is an organosiloxane unit in which only other monovalent organic groups are bonded to a silicon atom, and includes (R ¹⁷ ) ₂ SiO _2/2 and (R ¹⁷ ) SiO
_3/2 , (R ¹⁷ ) ₃ SiO _1/2 [where R ¹⁷ is another monovalent organic group. ].

The fluorine-containing silicone compound (A ¹ ) is a compound in which two or more organosiloxane units are linked. The organosiloxane units are preferably connected linearly or branched, and particularly preferably connected linearly. When the fluorinated silicone compound (A ¹ ) has a linear structure, the bonding positions of the monovalent fluorinated organic group (formula 1) and the monovalent silicon-containing organic group (formula 2) are SiO _1/2
Unit or a SiO _2/2 unit.
It is particularly preferred to bind to iO _2/2 units. When the fluorinated silicone compound (A ¹ ) has a branched structure, it may contain a siloxane unit (SiO _4/2 unit) in which a monovalent organic group is not directly bonded to a silicon atom.

The following compounds are preferred as the fluorine-containing silicone compound (A ¹ ) in the present invention. However,
The chain of the organosiloxane units in the following compounds may be block-shaped or random. The symbols in the following formula have the following meanings. R ⁵ : a monovalent fluorine-containing organic group represented by the formula 1, R ⁷ : a monovalent silicon-containing organic group represented by the formula 2, R ² , R ³ , R ⁴ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ each independently represent a monovalent organic group and are a monovalent fluorine-containing organic group represented by Formula 1 or a monovalent silicon-containing organic group represented by Formula 2. You may. n: an integer of 1 or more, m: an integer of 1 or more, k: an integer of 0 or more.

(R ² ) (R ³ ) (R ⁴ ) SiO · [Si (R ⁵ ) (R ⁶ ) O] _n · [Si (R ⁷ )
(R ⁸ ) O] _m · [Si (R ⁹ ) (R ¹⁰ ) O] _k · Si (R ¹¹ ) (R ¹² ) (R ¹³ ) Equation 4, (R ² ) (R ³ ) ( R ⁵ ) SiO · [Si (R ⁷ ) (R ⁸ ) O] _m · [Si (R ⁹ ) (R ¹⁰ ) O] _k · Si
(R ¹¹ ) (R ¹² ) (R ¹³ ), (R ² ) (R ³ ) (R ⁷ ) SiO · [Si (R ⁵ ) (R ⁶ ) O] _n · [Si (R ⁹ ) (R ¹⁰ ) O] _k・ Si
(R ¹¹ ) (R ¹² ) (R ¹³ ), (R ² ) (R ³ ) (R ⁵ ) SiO ・ [Si (R ⁹ ) (R ¹⁰ ) O] _k・ Si (R ⁷ ) (R ¹² ) (R ^13).

Fluorine-containing silicone compound (A¹As)
Is particularly preferably a compound represented by Formula 4. Furthermore, the expression
R in 4^Two, R^Three, R^Four, R⁶, R⁸, R⁹, R^Ten,
R¹¹, R ¹², And R¹³Are preferably other monovalent organic groups.
Particularly, a methyl group is particularly preferable. Also, n is 1 to 30
Is preferable, and 2-20 are especially preferable. m is 1 to 10
Preferably, 1 to 5 are particularly preferred. k is preferably 0 to 100
Particularly preferably, 0 to 80 is particularly preferable. Note that k is 0
If (R⁹) (R^Ten) SiO_2/2There is no unit
Means The ratio of n, m, and k (n / m / k)
Change appropriately to obtain a fluorine content according to the target performance.
(50-0.1) / 1 / (100-1) is preferred.
In particular, (30-0.1) / 1 / (50-1) is preferable.
Good.

Further, since the fluorine-containing silicone compound (A ¹ ) is preferably a compound which is in a fluid state at normal temperature, its molecular weight is preferably about 4 × 10 ² to 1 × 10 ⁶ , and
× 10 ³ to 1 × 10 ⁴ is particularly preferred.

The fluorine content in the fluorinated silicone compound (A ¹ ) is preferably from 5 to 80% by weight, particularly preferably from 10 to 50% by weight. The monovalent silicon-containing organic group (formula 2) in the fluorine-containing silicone compound (A ¹ ) is 1 to 20.
Are preferred, and 1 to 10 are particularly preferred.

Specific examples of the fluorine-containing silicone compound (A ¹ ) represented by Formula 4 include the following compounds.
However, in the following formula, A ¹¹ is-(CH ₂ ) ₃ OCH ₂ CF
(CF ₃ ) [OCF ₂ CF (CF ₃ )] ₃ F is shown.

(CH_Three)_ThreeSiO ・ {Si [(CH_Two)_Two(CF_Two)₇CF_Three] (CH_Three) O}_Five
・ [Si (CH_Three)_TwoO]₄₅・ {Si [(CH_Two)_TwoSi (OCH_Three)_Three] (CH_Three) O} ・ Si (CH_Three)
_Three, [(CH_ThreeO)_ThreeSi (CH_Two)_Two] (CH_Three)_TwoSiO ・ {Si [(CH_Two)_Three(CF_Two)₇CF_Three] (CH
_Three) O]_Five・ [Si (CH_Three)_TwoO]₄₅・ Si (CH_Three)_Two[(CH_Two)_TwoSi (OCH_Three)_Three], (CH_Three)_ThreeSiO ・ [SiA¹¹(CH_Three) O]_Five・ [Si (CH_Three)_TwoO]₄₅・ {Si [(CH_Two)_TwoS
i (OCH_Three)_Three] (CH_Three) O} ・ Si (CH_Three)_Three, [(CH_ThreeO)_ThreeSi (CH_Two)_Two] (CH_Three)_TwoSiO ・ {SiA¹¹(CH_Three) O}_Five・ [Si (CH_Three)
_TwoO]₄₅・ Si (CH_Three)_Two[(CH_Two) _TwoSi (OCH_Three)_Three], (CH_Three)_ThreeSiO ・ {Si [(CH_Two)_ThreeO (CF_Two)₇CF_Three] (CH_Three) O}_Five・ [Si (CH_Three)
_TwoO]₄₅・ {Si [(CH_Two)_TwoSi (OCH _Three)_Three] (CH_Three) O} ・ Si (CH_Three)_Three.

[(CH_ThreeO)_ThreeSi (CH_Two)_Two] (CH_Three)_TwoSiO ・ {Si [(CH_Two)_ThreeO
(CF_Two)₇CF_Three] (CH_Three) O]_Five・ [Si (CH_Three)_TwoO]₄₅・ Si (CH_Three)_Two[(CH_Two)_TwoSi
(OCH_Three)_Three], (CH_Three)_ThreeSiO ・ {Si [(CH_Two)_Two(CF_Two)₇CF_Three] (CH_Three) O}_Five・ [Si (CH_Three)_TwoO]
₄₅・ {Si [(CH_Two)_TwoSi (OC_TwoH _Five)_Three] (CH_Three) O} ・ Si (CH_Three)_Three, [(C_TwoH_FiveO)_ThreeSi (CH_Two)_Two] (CH_Three)_TwoSiO ・ {Si [(CH_Two)_Three(CF_Two)₇CF_Three] (C
H_Three) O]_Five・ [Si (CH_Three)_TwoO]₄₅・ Si (CH_Three)_Two[(CH_Two)_TwoSi (OC_TwoH_Five)_Three], [(C_TwoH_FiveO)_ThreeSi (CH_Two)_Two] (CH_Three)_TwoSiO ・ {Si [(CH_Two)_Two(CF_Two)_ThreeCF_Three] (C
H_Three) O]_Five・ [Si (CH_Three)_TwoO]₄₅・ Si (CH_Three)_Two[(CH_Two)_TwoSi (OC_TwoH_Five)_Three], (CH_Three)_ThreeSiO ・ [SiA¹¹(CH_Three) O]_Five・ [Si (CH_Three)_TwoO]₄₅・ {Si [(CH_Two)_TwoS
i (OC_TwoH_Five)_Three] (CH_Three) O} ・ Si (CH_Three)_Three.

[(C_TwoH_FiveO)_ThreeSi (CH_Two)_Two] (CH_Three)_TwoSiO ・ {SiA¹¹(C
H_Three) O}_Five・ [Si (CH_Three)_TwoO]₄₅・ Si (CH_Three)_Two[(CH_Two)_TwoSi (OC_TwoH_Five)_Three], (CH_Three)_ThreeSiO ・ {Si [(CH_Two)_ThreeO (CF_Two)₇CF_Three] (CH_Three) O}_Five・ [Si (CH_Three)
_TwoO]₄₅・ {Si [(CH_Two)_TwoSi (OC_TwoH_Five)_Three] (CH_Three) O} ・ Si (CH_Three)_Three, [(C_TwoH_FiveO)_ThreeSi (CH_Two)_Two] (CH_Three)_TwoSiO ・ {Si [(CH_Two)_ThreeO (CF_Two)₇CF_Three]
(CH_Three) O]_Five・ [Si (CH_Three)_TwoO]_{Four Five}・ Si (CH_Three)_Two[(CH_Two)_TwoSi (OC
_TwoH_Five)_Three], (CH_Three)_ThreeSiO ・ {Si [(CH_Two)_Two(CF_Two)₇CF_Three] (CH_Three) O}_Five・ [Si (CH_Three)_TwoO]
₄₅・ {Si [(CH_Two)_TwoSi (NCO) _Three] (CH_Three) O} ・ Si (CH_Three)_Three, (CH_Three)_ThreeSiO ・ [SiA¹¹(CH_Three) O]_Five・ [Si (CH_Three)_TwoO]₄₅・ {Si [(CH_Two)_TwoS
i (NCO)_Three] (CH_Three) O} ・ Si (CH_Three)_Three.

(CH_Three)_ThreeSiO ・ {Si [(CH_Two)_ThreeO (CF_Two)₇CF_Three] (CH_Three) O}
_Five・ [Si (CH_Three)_TwoO]₄₅・ {Si [(CH_Two)_TwoSi (NCO)_Three] (CH_Three) O} ・ Si (CH_Three)
_Three, [(OCN)_ThreeSi (CH_Two)_Two] (CH_Three)_TwoSiO ・ {Si [(CH_Two)_ThreeO (CF_Two)₇CF_Three] (CH
_Three) O]_Five・ [Si (CH_Three)_TwoO]₄₅・ Si (CH_Three)_Two[(CH_Two)_TwoSi (NCO)_Three], [(OCN)_ThreeSi (CH_Two)_Two] (CH_Three)_TwoSiO ・ {Si [(CH_Two)_Three(CF_Two)₇CF_Three] (C
H_Three) O}_Five・ [Si (CH_Three)_TwoO]₄₅・ Si (CH_Three)_Two[(CH_Two)_TwoSi (NCO)_Three], [(OCN)_ThreeSi (CH_Two)_Two] (CH_Three)_TwoSiO ・ {SiA¹¹(CH_Three) O}_Five・ [Si (CH_Three)_Two
O]₄₅・ Si (CH_Three)_Two[(CH_Two)_TwoSi (NCO)_Three], (CH_Three)_ThreeSiO ・ {Si [(CH_Two)_Two(CF_Two)₇CF_Three] (CH_Three) O}_Five・ [Si (CH_Three)_TwoO]
₄₅・ {Si [(CH_Two)_TwoSi (NCO) _Three] (CH_Three) O} ・ Si (CH_Three)_Three.

(CH_Three)_ThreeSiO ・ [SiA¹¹(CH_Three) O]_Five・ [Si (CH_Three)_TwoO]₄₅
・ {Si [(CH_Two)_TwoSiCl_Three] (CH_Three) O} ・ Si (CH_Three) _Three, (CH_Three)_ThreeSiO ・ {Si [(CH_Two)_ThreeO (CF_Two)₇CF_Three] (CH_Three) O}_Five・ [Si (CH_Three)
_TwoO]₄₅・ {Si [(CH_Two)_TwoSiCl_Three] (CH_Three) O} ・ Si (CH_Three)_Three, [(OCN)_ThreeSi (CH_Two)_Two] (CH_Three)_TwoSiO ・ {Si [(CH_Two)_ThreeO (CF_Two)₇CF_Three] (CH
_Three) O]_Five・ [Si (CH_Three)_TwoO]₄₅・ Si (CH_Three)_Two[(CH_Two)_TwoSiCl_Three], (CH_Three)_ThreeSiO ・ [SiA¹¹(CH_Three) O]_Five・ [Si (CH_Three)_TwoO]₄₅・ {Si [(CH_Two)_TwoS
iCl_Three] (CH_Three) O} ・ Si (CH_Three) _Three, [Cl_ThreeSi (CH_Two)_Two] (CH_Three)_TwoSiO ・ {SiA¹¹(CH_Three) O}_Five・ [Si (CH_Three)_TwoO]
₄₅・ Si (CH_Three)_Two[(CH_Two)_TwoSiCl_Three].

(CH ₃ ) ₃ SiO. {Si [(CH ₂ ) ₃ O (CF ₂ ) ₇ CF ₃ ] (CH ₃ ) O}
₅ • [Si (CH ₃ ) ₂ O] ₄₅ • {Si [(CH ₂ ) ₂ SiCl ₃ ] (CH ₃ ) O} • Si (CH ₃ ) ₃ , [Cl ₃ Si (CH ₂ ) ₂ ] (CH ₃ ) ₂ SiO ・ {Si [(CH ₂ ) ₃ O (CF ₂ ) ₇ CF ₃ ] (CH ₃ )
O} ₅ · [Si (CH ₃ ) ₂ O] ₄₅ · Si (CH ₃ ) ₂ [(CH ₂ ) ₂ SiCl ₃ ], (CH ₃ ) ₃ SiO · {Si [(CH ₂ ) ₂ (CF ₂ ) ₇ CF ₃ ] (CH ₃ ) O} ₅ · [Si (CH ₃ ) ₂ O]
₄₅ • {Si [(CH ₂ ) ₂ SiCl ₃ ] (CH ₃ ) O} • Si (CH ₃ ) ₃ , [Cl ₃ Si (CH ₂ ) ₂ ] (CH ₃ ) ₂ SiO • {Si [(CH ₂ ) ₃ (CF ₂ ) ₇ CF ₃ ] (CH ₃ ) O]
₅ • [Si (CH ₃ ) ₂ O] ₄₅ • Si (CH ₃ ) ₂ [(CH ₂ ) ₂ SiCl ₃ ], [Cl ₃ Si (CH ₂ ) ₂ ] (CH ₃ ) ₂ SiO • {Si [( CH ₂ ) ₂ (CF ₂ ) ₃ CF ₃ ] (CH ₃ ) O]
₅ • [Si (CH ₃ ) ₂ O] ₄₅ • Si (CH ₃ ) ₂ [(CH ₂ ) ₂ SiCl ₃ ].

(CH_Three)_ThreeSiO ・ [SiA¹¹(CH_Three) O]_Five・ [Si (CH_Three)_TwoO]₄₅
・ {Si [(CH_Two)_TwoSiCl_Three] (CH_Three) O} ・ Si (CH_Three) _Three, [Cl_ThreeSi (CH_Two)_Two] (CH_Three)_TwoSiO ・ {SiA¹¹(CH_Three) O}_Five・ [Si (CH_Three)_TwoO]
₄₅・ Si (CH_Three)_Two[(CH_Two)_TwoSiCl_Three], (CH_Three)_ThreeSiO ・ {Si [(CH_Two)_ThreeO (CF_Two)₇CF_Three] (CH_Three) O}_Five・ [Si (CH_Three)
_TwoO]₄₅・ {Si [(CH_Two)_TwoSiCl_Three] (CH_Three) O} ・ Si (CH_Three)_Three, [Cl_ThreeSi (CH_Two)_Two] (CH_Three)_TwoSiO ・ {Si [(CH_Two)_ThreeO (CF_Two)₇CF_Three] (CH_Three)
O]_Five・ [Si (CH_Three)_TwoO]₄₅・ Si (CH_Three)_Two[(CH_Two)_TwoSiCl_Three].

As a method for producing the fluorine-containing silicone compound (A ¹ ), a known method can be employed. For example, a cyclic polysiloxane having a monovalent fluorinated organic group (formula 1) bonded thereto, a cyclic polysiloxane having a monovalent silicon-containing organic group (formula 2) bonded thereto, and optionally a cyclic polysiloxane having another monovalent organic group bonded thereto. A method of co-hydrolyzing polysiloxane with disiloxane (JP-A-8-302020) can be mentioned.

Further, a cyclic polysiloxane to which a monovalent silicon-containing organic group (formula 2) is bonded, a cyclic polysiloxane to which a hydrogen atom is bonded, and a disiloxane are co-hydrolyzed, for example, to directly bond to a silicon atom. Hydrogen atom and 1
It is also possible to adopt a method in which a hydrosilicone compound having a valent silicon-containing organic group (formula 2) is prepared, and a compound represented by the following formula 5 is hydrosilylated with the hydrosilicone compound.

[0049] However, R ^f is of the formula 5 are the same groups as R ^f in formula 1, X ⁶ are each independently a single bond, a divalent hydrocarbon group or a divalent hydrocarbon radical, A group having an etheric oxygen atom inserted between carbon-carbon bonds is shown, and a single bond or an alkylene group is preferable. R ^f -X ⁶ -CH ₂ CH = CH ₂ Formula 5 The silicone compound (A) is a fluorine-containing silicone compound (A ¹ ) and a partial hydrolysis product (A) of the fluorine-containing silicone compound (A ¹ ). ² ) one or more compounds selected from

In the present specification, a partial hydrolysis product or a partial co-hydrolysis product refers to a compound having a monovalent hydrolyzable group or an isocyanate group (hereinafter, referred to as a hydrolyzable compound) and water. Refers to a compound formed by hydrolysis. The partial hydrolysis product refers to a compound generated from one or more hydrolyzable compounds, and the partial co-hydrolysis product refers to a compound generated from two or more hydrolyzable compounds. In the following, the partial hydrolysis products and the partial co-hydrolysis products are collectively referred to as partial hydrolysis products.

As the partial hydrolysis product, a compound having a monovalent hydrolyzable group or an isocyanate group (hereinafter, referred to as a compound having a monovalent hydrolyzable group or an isocyanate group)
It is called a hydrolyzable compound. )), A compound in which a part of the group has reacted with water to be converted to an OH group, a compound formed by forming a Si—O—Si bond by dehydration-condensation between the compounds converted to the OH group, or Mixtures of these compounds are mentioned, usually a mixture. A known method can be employed as a method for producing the partial hydrolysis product. For example, a method of simply mixing a hydrolyzable compound and water,
A method of mixing the hydrolyzable compound and water in the presence of an acid,
There is a method of mixing a hydrolyzable compound and water in the presence of an alkali.

In the present invention, when a partial hydrolysis product is prepared, it is preferable to carry out hydrolysis in the presence of an acid from the viewpoint of the stability of the composition, the physical strength of the formed film, and the like. The amount of water required for partial hydrolysis is not limited,
It is preferably at least equimolar to the total number of moles of the divalent hydrolyzable group and the isocyanate, and particularly preferably at most 500 times the mole. The acid is preferably nitric acid, hydrochloric acid, sulfuric acid, methanesulfonic acid or acetic acid. The amount of acid is 0.
It is preferably from 0.05 to 10% by weight. When the amount of the acid is increased, there is a problem that the operation during the production becomes difficult. The acid used for producing the partial hydrolysis product may remain in the composition as it is, or may be removed by a method such as neutralization and desalting. The amount of the acid remaining in the composition is preferably 0.05 to 0.3% by weight from the viewpoint of the stability of the composition and the like.

The production of the partial hydrolysis product may be carried out using only the hydrolyzable compound, water and acid, and is preferably carried out in the presence of an organic solvent. The amount of the organic solvent is preferably 9 to 2000 times the weight of the hydrolyzable compound.

As the organic solvent, an acetic acid ester type, a fluorinated type, a hydrocarbon type, an alcohol type and a ketone type organic solvent are preferable, and particularly, an acetic acid ester type and an alcohol type are preferable. The preferred embodiment of the organic solvent is the same as the preferred embodiment of the organic solvent contained in the composition described later.

The hydrolyzable compound may be used alone or in combination of two or more. The partial hydrolysis product to be formed may be one kind or two or more kinds.
A partial hydrolysis product consisting of two or more species can be used as it is.

As the partial hydrolysis product (A ² ), a part of the monovalent hydrolyzable group or the isocyanate group (Y ¹ ) in the fluorine-containing silicone compound (A ¹ ) reacts with water to form an OH group. Examples of the compound include a compound formed by dehydration-condensation between a changed compound and a compound converted to the OH group to form a Si—O—Si bond, and usually a mixture of two or more kinds. In addition, the fluorine-containing silicone compound (A ¹ ) that forms the partial hydrolysis product (A ² ) may be one type or two or more types.

The silicone compound (A) is at least one compound selected from the group consisting of a fluorine-containing silicone compound (A ¹ ) and a partial hydrolysis product (A ² ). Only the fluorine-containing silicone compound (A ¹ ) is used. Or only a partial hydrolysis product (A ² ) or a combination of a fluorine-containing silicone compound (A ¹ ) and a partial hydrolysis product (A ² ). When the silicone compound (A) is composed of the fluorinated silicone compound (A ¹ ) and the partial hydrolysis product (A ² ), their ratio is not particularly limited.

The silicon compound (B ¹ ) is a compound represented by Formula 3. The silicon compound (B ¹ ) and the partial hydrolysis product (B ² ) of the silicon compound (B ¹ ) can improve the abrasion resistance, chemical resistance, weather resistance and the like of the composition.

(R ²⁰ ) _4-j Si (Y ² ) _j Equation 3 where the symbols have the following meanings. R ²⁰ : monovalent organic group, Y ² : monovalent hydrolyzable group or isocyanate group, j: 1, 2, 3 or 4.

As R ²⁰ , R ^f1 — (CH ₂ ) _n — (where R ^f1 is a monovalent polyfluoroalkyl group or an etheric oxygen atom inserted between carbon-carbon bonds of the monovalent polyfluoroalkyl group) And the same group as R ^f in Formula 1 is preferable, and n is an integer of 2 to 4.). R ^f1 is preferably a perfluoroalkyl group. Y ² is preferably an alkoxy group, a halogen atom, or an isocyanate group, particularly preferably a methoxy group, an ethoxy group, or a chlorine atom. j is preferably an integer of 1 to 3, particularly preferably 3.

As specific examples of the silicon compound (B ¹ ),
The following compounds are mentioned. However, the perfluoroalkyl group in the following formula is preferably a linear perfluoroalkyl group. Si (OCH ₃ ) ₄ , Si (OCH
₂ CH ₃ ) ₄ , Si (NCO) ₄ , SiCl ₄ , CH ₃ Si
(OCH ₃ ) ₃ , CH ₃ Si (OCH ₂ CH ₃ ) ₃ , CH ₃ S
i (NCO) ₃ , CH ₃ SiCl ₃ , C ₈ F ₁₇ (CH ₂ ) ₂ S
i (OCH ₃ ) ₃ , C ₈ F ₁₇ (CH ₂ ) ₂ Si (OCH ₂ CH
_{3) 3, C 8 F 17} (CH 2) 2 Si (NCO) 3, C 8 F
₁₇ (CH ₂ ) ₂ SiCl ₃ , C ₄ F ₉ (CH ₂ ) ₂ Si (OC
_{H 3) 3, C 4 F} 9 (CH 2) 2 Si (OCH 2 CH 3) 3, C 4
F ₉ (CH ₂ ) ₂ Si (NCO) ₃ , C ₄ F ₉ (CH ₂ ) ₂ Si
Cl _3.

The silicon compound (B ² ) is a partial hydrolysis product of the silicon compound (B ¹ ) represented by the formula (3). Specifically, a compound in which a part of a monovalent hydrolyzable group or an isocyanate group in the silicon compound (B ¹ ) has reacted with water to change to an OH group, And a mixture of these compounds formed by forming a Si—O—Si bond, and a mixture is preferable. The silicon compound (B ¹ ) used for the partial hydrolysis may be one kind or two or more kinds.

[0063] Silicon compound (B), silicon compound (B ^1), and, the silicon compound partial hydrolysis product of ^{(B 1) (B 2)} , is at least one compound selected from. The silicon compound (B) is a silicon compound (B
Even if it consists only of ¹ ), the partial hydrolysis product (B ² )
It may be composed of only a silicon compound (B ¹ ) and a partial hydrolysis product (B ² ). When the silicon compound (B) is composed of the silicon compound (B ¹ ) and the partial hydrolysis product (B ² ), their ratio is not particularly limited.

The surface treatment composition of the present invention includes a partial hydrolyzate of the silicone compound (A) and the silicon compound (B) and / or the fluorine-containing silicone compound (A ¹ ) and the silicon compound (B ¹ ). Degradation products as essential components.

When the composition is a composition comprising the silicone compound (A) and the silicone compound (B) (hereinafter also referred to as composition 1), the fluorine-containing silicone compound (A ¹ )
And the total amount of the partial hydrolyzate (A ² ) in the composition 1 was 0.1%.
It is preferably from 1 to 50% by weight, particularly preferably from 1 to 10% by weight. Also, a silicon compound (B ¹ )
And the total amount of the silicon compound (B ² ) in the composition 1 is preferably 0.1 to 50% by weight, more preferably 1 to 10% by weight.
% By weight.

When the composition of the present invention essentially contains a partial co-hydrolysis product of a fluorine-containing silicone compound (A ¹ ) and a silicon compound (B ¹ ) (hereinafter also referred to as composition 2), As the co-hydrolysis product, a part of the monovalent hydrolyzable group or isocyanate group present in the fluorine-containing silicone compound (A ¹ ) and the silicon compound (B ¹ ) reacts with water to form an OH group. Compounds that have been changed, compounds formed by dehydration-condensation between the compounds that have been converted to the OH groups to form Si—O—Si bonds, or a mixture of these compounds are mentioned, and a mixture is preferable.

As the composition 2, the silicon compound (B ¹ ) was added to the fluorine-containing silicone compound (A ¹ ) in an amount of 0.1 to 0.1%.
Compositions comprising 50% by weight, preferably 1 to 10% by weight, of partially co-hydrolyzed products are preferred. Also,
The amount of the partial co-hydrolysis product in the composition 2 is 0.2 to 10
It is preferably 0% by weight.

The surface treating composition of the present invention includes a fluorine-containing silicone compound (A ¹ ) and a silicon compound (B ¹ ).
Preferred are compositions that require a partial co-hydrolysate with
Further, the composition may contain a fluorine-containing silicone compound (A) or a silicon compound (B).

The surface-treating composition of the present invention may be subjected to surface treatment as it is, or may be surface-treated after adding other compounds, if necessary. Is preferred.

The other compound is preferably an organic solvent.
Examples of the organic solvent include acetic acid organic solvents such as butyl acetate and ethyl acetate, fluorinated solvents such as perfluoro (2-n-butyltetrahydrofuran) and perfluoro (tri-n-butylamine), isopropyl alcohol, ethyl alcohol, and the like. Alcohol solvents such as butyl alcohol are preferred. Furthermore, from the viewpoint of the stability of the composition, the organic solvent when Y ¹ and Y ² are each a monovalent hydrolyzable group is preferably an alcoholic solvent, and Y ¹ and Y ² are isocyanate groups. In this case, the organic solvent is preferably an acetate-based organic solvent. The amount of the organic solvent is preferably 9 to 2000 times the total weight of the fluorine-containing silicone compound (A ¹ ), the silicon compound (B ¹ ) and the partial co-hydrolysis product.

The surface treatment composition of the present invention may contain additives. The additive is a silicone compound (A),
The selection may be made in consideration of the reactivity and compatibility with the silicon compound (B) and the partial co-hydrolysis product, for example, fine particles of metal oxides such as silica, alumina, zirconia, titania, and tin oxide; Resins. If coloring is necessary, a dye, a pigment or the like may be added. In addition, an antioxidant, an ultraviolet absorber, or the like may be added, and when it is desired to impart conductivity, antistatic property, or the like, a material having a resistance value suitable for the purpose [eg, tin oxide, ITO
(In ₂ O ₃ —SnO ₂ ), zinc oxide and the like].
Additives may be present in the composition in an amount of 0.01 to 20 wt%,
It is preferred that Excessive addition is not preferred because the water-dropping property and abrasion resistance of the coating of the present invention are reduced.

The surface treating agent composition of the present invention is applied to the surface of a substrate to form a film on the surface of the substrate. Examples of the treatment method include a treatment method in which the material is attached to the surface of the base material and then dried. In this treatment, no special pretreatment is necessary, but it may be carried out according to the purpose. For example, alkali treatment with an aqueous solution of sodium hydroxide or potassium hydroxide, acid treatment with an aqueous solution of hydrofluoric acid or hydrochloric acid, discharge treatment by plasma irradiation, corona discharge, or the like, polishing treatment with various abrasives such as cerium oxide, alumina, etc. Blast processing can be performed.

Examples of the method of attaching to the surface of the base material include ordinary coating methods, for example, methods such as brush coating, flow coating, spin coating, dip coating, spray coating, squeegee coating and various printing coatings are preferable. . Further, the surface-treated substrate is usually dried. As the drying temperature, a normal drying temperature of about 0 ° C. to 50 ° C. can be adopted, and excellent performance can be exhibited at the normal drying temperature, which is economically advantageous. Further, heat treatment may be performed for the purpose of increasing the drying speed or for increasing the persistence of the effect. Drying can be performed in the atmosphere. The conditions for the heat treatment may be selected in consideration of the heat resistance of the base material.
The temperature is preferably about 0 to 400 ° C, and the time is preferably about 1 to 60 minutes.

The thickness of the film obtained by using the surface treating agent composition of the present invention is not particularly limited.
μm or less, and particularly preferably from 0.1 to 0.1 μm. The thickness of the film can be appropriately controlled by the component concentration of the surface treatment agent composition, application conditions, heating conditions, and the like.

Further, since the coating obtained from the surface treating agent composition of the present invention has a low refractive index, low reflectivity can be imparted by controlling the thickness of the coating to a thickness at which optical interference occurs. Further, a film obtained from the surface treatment agent composition of the present invention,
Since it has excellent surface slipperiness, it has high durability against abrasion.

As the base material, for example, glass, plastics, metal, ceramics, other inorganic materials and organic materials or a combination thereof (composite material, laminated material, etc.)
And the like. Further, the surface of the base material may be a surface of a coating film of a coating metal or the like, or a surface of a surface-treated layer of surface-treated glass (for example, a surface provided with a sol-gel film, a sputter film, a CVD film, a vapor-deposited film, and the like). . Examples of the shape of the base material include a shape having a flat surface, an entire surface, or a partial curvature.

The surface treatment composition of the present invention can be used at room temperature (10
(Approximately 30 ° C. to about 30 ° C.), so that a substrate that cannot be heated can be treated, and a wide range of substrates can be imparted with properties such as water repellency and water droplet persistence. A substrate particularly effective in the present invention is a substrate made of a transparent material such as glass.
The surface-treated substrate is preferably used as an article for transportation equipment or an article for construction / building.

Examples of articles for transport equipment include outer panels, window glasses, mirrors, visibility (CCD) lenses, exterior members such as display device surface materials, and instrument panel surface material. On the surface of the transport equipment article obtained by the present invention,
Since water repellency and water droplet falling properties are imparted, water droplets adhering to the surface can be easily removed. Also, it is difficult to freeze even in an environment where water droplets freeze on the surface. And these performances are more remarkable than the conventional surface treatment composition. Examples of building / building articles include window glass, roof glass, door glass, partition glass, greenhouse glass, mirror, display shelf glass, and the like.

[0079]

EXAMPLES The present invention will be described below in more detail with reference to Examples, but the present invention is not limited thereto. Various evaluation methods in the examples are as follows. In addition, the way in which the siloxane units of the fluorine-containing silicone compound are linked in the examples indicates that they are random.

[Water repellency] The contact angle of water (unit: degree) was measured. [Water drop falling property] After dropping 50 μl of water droplets on a sample substrate held horizontally (at an angle of 0 °), the sample substrate was tilted, and the angle between the substrate and the horizontal plane when the water droplet started rolling was read (unit: degrees). .

[Water Drop Residue] Water was sprayed on the entire surface of the sample from a nozzle 20 cm apart from the vertical sample for 1 hour, and water drops remaining on the sample surface were visually observed and evaluated according to the following criteria. . A: no water droplets remain on the sample surface; B: water droplets remain on less than 20% of the sample surface area; C: water droplets remain on 20% to 70% of the sample surface area; D: water droplets on more than 70% of the sample surface area Spread wet. [Evaluation of water repellency durability] After immersion in boiling water for 6 hours,
The water repellency, falling property of water droplets, and remaining water droplets were evaluated.

[Synthesis Example 1] 20 equipped with a stirrer and a thermometer
A 0 mL four-necked flask is sufficiently purged with nitrogen, and (CH
_Three)_ThreeSiO [SiH (CH_Three) O]_Five[Si (CH_Three)
_TwoO]₄₅Si (CH_Three)_Three100 g. 90 temperature
° C, then F (CF_Two)₈CH_TwoCH_TwoCH = CH_Two
49.9 g, CH_Two= CHSiCl_Three4.3 g of chloride
Mixed with platinic acid (dissolved to 2 ppm in platinum conversion)
The compound was dropped into the four-neck flask from the dropping funnel.
As the reaction proceeded, the internal temperature rose to 100 ° C.
After stirring for 1 hour, disappearance of H-Si peak was confirmed by IR
After one hour, the reaction was stopped. The product obtained is NM
As a result of analysis by R and IR, the structure represented by the following formula (a) was obtained.
I confirmed that it was built. (CH_Three)_ThreeSiO ・ {Si [(CH_Two)_Four(CF_Two)₈F] (CH_Three) O}_Four・ [Si (CH_Three)_TwoO]₄₅
・ {Si [(CH_Two)_TwoSiCl_Three] (CH _Three) O} ・ Si (CH_Three)_Three... Equation (a).

[Synthesis Example 2] 20 equipped with a stirrer and a thermometer
A 0 mL four-necked flask is sufficiently purged with nitrogen, and H (C
H ₃ ) ₂ SiO · ｛Si [(CH ₂ ) ₂ (CF ₂ ) ₄ F] (C
H ₃ ) O｝ _5. [(CH ₃ ) ₂ SiO] ₄₅ .Si (CH ₃ ) ₂
H was added in an amount of 100 g. After raising the temperature to 90 ° C., CH
_A mixture of 3.23 g of ₂ = CHSiCl ₃ and chloroplatinic acid (dissolved to 2 ppm in terms of platinum) was dropped from a dropping funnel into a four-necked flask. It was observed that the internal temperature rose to 100 ° C. as the reaction proceeded.
After stirring for 1 hour, the disappearance of the H-Si peak was confirmed by IR, and the reaction was stopped after 1 hour. The product obtained is NM
As a result of analysis by R and IR, it was confirmed that the structure was represented by the following formula (b). [Cl ₃ Si (CH ₂ ) ₂ ] (CH ₃ ) ₂ SiO ・ {Si [(CH ₂ ) ₂ (CF ₂ ) ₄ F] (CH ₃ ) O} ₅・
[Si (CH ₃ ) ₂ O] ₄₅ · Si (CH ₃ ) ₂ [(CH ₂ ) ₂ SiCl ₃ ] ... Formula (b).

Synthesis Example 3 20 equipped with a stirrer and a thermometer
A 0 mL four-necked flask is sufficiently purged with nitrogen, and (CH
_Three)_ThreeSiO. [SiH (CH_Three) O]_Five・ [(CH_Three)_TwoS
iO]₄₅・ Si (CH_Three)_Three100 g. Temperature 9
After the temperature was raised to 0 ° C., F (CF_Two)₈CH_TwoCH_TwoCH = CH
_Two49.9 g, CH_Two= CHSi (OCH_TwoCH_Three)_Threeof
5 g and chloroplatinic acid (dissolved to 2 ppm in terms of platinum)
Solution) from the dropping funnel into the four-necked flask
It was dropped. As the reaction progresses, the internal temperature rises to 100 ° C
Rose. After stirring for 1 hour, IR peak of H-Si
After confirming disappearance, the reaction was stopped one hour later. Obtained raw
As a result of analyzing the product by NMR and IR, the following formula (c) was obtained.
It was confirmed that the structure was represented. (CH_Three)_ThreeSiO ・ {Si [(CH_Two)_Four(CF_Two)₈F] (CH_Three) O]_Four・ [Si (CH_Three)_TwoO]₄₅
・ {Si [(CH_Two)_TwoSi (OCH_TwoCH _Three)_Three] (CH_Three) O} ・ Si (CH_Three)_Three···formula
(C).

[Synthesis Example 4] 20 equipped with a stirrer and a thermometer
A 0 mL four-necked flask is sufficiently purged with nitrogen, and H (C
H ₃ ) ₂ SiO · ｛Si [(CH ₂ ) ₂ (CF ₂ ) ₈ F] (C
H ₃ ) O｝ _5. [(CH ₃ ) ₂ SiO] ₄₅ .Si (CH ₃ ) ₂
H was added in an amount of 100 g. After raising the temperature to 90 ° C., CH
_A mixture of 6.3 g of ₂ = CHSi (OCH ₂ CH ₃ ) ₃ and chloroplatinic acid (dissolved to 2 ppm in terms of platinum) was dropped from a dropping funnel into a four-necked flask. As the reaction proceeded, the internal temperature rose to 100 ° C. After stirring for 1 hour, after confirming disappearance of the H-Si peak by IR,
After one hour, the reaction was stopped. NMR of the obtained product,
As a result of analysis by IR, it was confirmed that the structure was represented by the following formula (d). [(CH ₃ CH ₂ O) ₃ Si (CH ₂ ) ₂ ] (CH ₃ ) ₂ SiO • {Si [(CH ₂ ) ₂ (CF ₂ ) ₈ F] (C
H ₃ ) O} _5. [Si (CH ₃ ) ₂ O] ₄₅ .Si (CH ₃ ) ₂ [(CH ₂ ) ₂ Si (OCH ₂ CH ₃ ) ₃ ]
... Equation (d).

Example 1 In a flask equipped with a stirrer and a thermometer, 97.0 g of butyl acetate, 3.0 g of the compound represented by the formula (a) and F (CF ₂ ) ₈ (CH ₂ ) ₂ SiCl ₃ were added. 1.
5 g was added, and the mixture was stirred at 25 ° C. for 30 minutes, and further stirred at 25 ° C. for 24 hours to obtain a treating agent. 0.5 mL of a treating agent was dropped on a glass substrate (10 cm × 10 cm, 3.5 mm in thickness) which had been polished and washed in advance, and spread using a tissue paper in the manner of car waxing to prepare a sample substrate. Table 1 shows the evaluation results.

Example 2 A sample substrate was prepared by changing the compound represented by the formula (a) in Example 1 to the compound represented by the formula (b). Table 1 shows the evaluation results.

Example 3 A flask equipped with a stirrer and thermometer was charged with 50.0 g of 2-propanol and butyl acetate.
0 g, 3.0 g of the compound represented by the formula (c), F (C
1.5 g of F ₂ ) ₈ (CH ₂ ) ₂ Si (OCH ₂ CH ₃ ) ₃ was added and stirred at 25 ° C. for 30 minutes. Then, 3.0 g of a 0.6% by weight aqueous nitric acid solution was added, and the mixture was stirred at 25 ° C. for 24 hours to obtain a treating agent. 0.5 mL of a treating agent was dropped on a glass substrate (10 cm × 10 cm, 3.5 mm in thickness) which had been polished and washed in advance, and spread using a tissue paper in the manner of car waxing to prepare a sample substrate. Table 1 shows the results obtained by heating the obtained sample substrate at 200 ° C. for 30 minutes.

Example 4 A sample substrate was prepared by changing the compound represented by the formula (c) in Example 3 to the compound represented by the formula (d). Table 1 shows the evaluation results.

[Embodiment 5] F (C
F ₂ ) ₈ (CH ₂ ) ₂ Si (OCH ₂ CH ₃ ) ₃ to CH ₃ Si
(OCH ₃ ) ₃ was changed to a sample substrate. Table 1 shows the evaluation results.

Comparative Example 1 A sample substrate was prepared in Example 1 without using the compound represented by the formula (a). Table 1 shows the evaluation results.

[Comparative Example 2] F (C
A sample substrate was prepared without using F ₂ ) ₈ (CH ₂ ) ₂ SiCl ₃ . Table 1 shows the evaluation results.

[Evaluation of Durability of Sample Substrate]
5. The sample substrates obtained in Comparative Examples 1 and 2 were immersed in the chemicals shown in Table 2 or Table 24 below for 24 hours,
The water-dropping property and the water-drop remaining property were evaluated. The results are shown in Table 2 or Table 3. The samples obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were reciprocated 1500 times with a flannel cloth under a load of 1 kg. Table 4 shows the results of the evaluation of the water repellency, water droplet falling property, and water droplet remaining property after the abrasion test.

[0094]

[Table 1]

[0095]

[Table 2]

[0096]

[Table 3]

[0097]

[Table 4]

[0098]

The surface treating agent composition of the present invention can impart excellent water repellency, water droplet falling properties and water droplet removing properties to the surface of a substrate. In addition, uniform treatment can be performed on the substrate surface without coating unevenness.
Furthermore, the effect imparted by the surface treatment composition of the present invention can last for a long time. In particular, it can provide water droplets with excellent durability, which cannot be exhibited by the fluorine-containing silicone compound (A ¹ ) alone. Therefore, even if the substrate treated with the surface treatment agent composition of the present invention is washed with warm water, even if it is subjected to friction on the surface, or even if a chemical adheres, water droplets adhered to the surface are easily formed. Can be excluded.

Further, the surface treating agent composition of the present invention can exhibit excellent performance both when treated at room temperature and when subjected to heat treatment, and is therefore excellent in versatility. Furthermore, since the substrate can be treated at room temperature, it can be easily treated even for a substrate that has been used once, so that it can be used as a repair agent (repair agent).

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Mami Kodera F-term (reference) 4G059 AA01 AC22 FA22 4H020 BA36 2-59-8 Akuwanishi, Seya-ku, Yokohama-shi, Kanagawa

Claims (7)

[Claims] 1. A partial copolymer of the following silicone compound (A) and the following silicon compound (B), and / or the following fluorine-containing silicone compound (A ¹ ) and a silicon compound (B ¹ ) represented by the following formula 3: A surface treating agent composition comprising a hydrolysis product as an essential component. Silicone compound (A): an organosiloxane unit (a ¹ ) in which a monovalent fluorine-containing organic group represented by the following formula 1 is bonded to a silicon atom and a monovalent silicon-containing organic group represented by the following formula 2 are substituted by a silicon atom It is selected from a fluorine-containing silicone compound (A ¹ ) composed essentially of a bound organosiloxane unit (a ² ) and a partial hydrolysis product (A ² ) of the fluorine-containing silicone compound (A ¹ ). One or more compounds. Silicon compound (B): at ^{least one} compound selected from a silicon compound (B ¹ ) represented by the following formula 3 and a partial hydrolysis product (B ² ) of the silicon compound (B ¹ ). -X-R ^f ··· formula _{1 - (CH 2) a Si} (R 1) 3-b (Y 1) b ··· formula _{^{2 (R 20) 4-j}} Si (Y 2) j ··· Formula 3 However, the symbols in Formulas 1 to 3 have the following meanings. R ^f : a monovalent polyfluorohydrocarbon group or a group in which an etheric oxygen atom is inserted between carbon-carbon bonds of a monovalent polyfluorohydrocarbon group. X: divalent hydrocarbon group or carbon of divalent hydrocarbon group
A group in which an etheric oxygen atom is inserted between carbon bonds. R ¹ and R ²⁰ are each independently a monovalent organic group. Y ¹ and Y ² each independently represent a monovalent hydrolyzable group or an isocyanate group. a: an integer of 1 or more. b: 1, 2, or 3. j: 1, 2, 3, or 4. 2. A fluorine-containing silicone compound (A ¹ ) and a compound of the formula (3)
In represented by silicon compound (B ¹⁾ and partial cohydrolysis product, the surface treatment composition according to claim 1, characterized in that it comprises as essential. 3. The surface treatment composition according to claim 1, wherein the fluorine-containing silicone compound (A ¹ ) is a compound represented by the following formula 4. However, the symbols in Equation 4 have the following meanings. In addition, the manner of connecting the organosiloxane units in Formula 4 may be a block or a random manner. R ⁵ : a monovalent fluorine-containing organic group represented by the above formula 1. R ⁷ : a monovalent silicon-containing organic group represented by the above formula 2. R ² , R ³ , R ⁴ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ each independently represent a monovalent organic group;
Or a monovalent silicon-containing organic group represented by the above formula (2). n: an integer of 1 or more. m: an integer of 1 or more. k: an integer of 0 or more. (R ² ) (R ³ ) (R ⁴ ) SiO · [Si (R ⁵ ) (R ⁶ ) O] _n · [Si (R ⁷ ) (R ⁸ ) O] _m · [Si
(R ⁹ ) (R ¹⁰ ) O] _k · Si (R ¹¹ ) (R ¹² ) (R ¹³ ) ・ ・ ・ Equation 4 4. The surface treatment composition according to claim 1, which comprises an organic solvent. 5. A surface-treated substrate having a film formed from the surface treatment composition according to claim 1 on the surface of the substrate. 6. The surface-treated substrate according to claim 5, wherein the substrate is a glass substrate. 7. The surface treating agent composition according to any one of claims 1 to 4, which is adhered to a substrate surface.
A method for producing a surface-treated substrate, characterized by drying at 0 ° C.