JP6060698B2 - Curable resin composition and coated article - Google Patents

Description

  In the present invention, an organosilicon compound containing (A) a bissilane compound, (B) an epoxy group-containing silane compound and / or (C) an unsaturated group-containing silane compound is optionally added in the presence of (D) inorganic oxide fine particles. Composite resin obtained by hydrolysis / condensation, fluorinated alcohol compound, curing catalyst, water- and oil-repellency containing solvent, storage stability, chemical resistance, and low-temperature curability suitable as a coating agent The present invention relates to a resin composition and an article coated with the curable resin composition.

Various protective displays such as computers, televisions, plasma displays, liquid crystal displays, transparent plastic lenses, covers for various instruments, optical articles such as automobiles, train window glass, etc. are generally subjected to hard protective coatings with excellent scratch resistance. It has become.
Examples of the hard protective coating agent having excellent scratch resistance include those obtained by hydrolyzing silica or tetrafunctional alkoxysilane by a sol-gel method.

For the purpose of improving scratch resistance, it has also been proposed to use a material mainly composed of a bissilane compound containing a perfluoroalkylene group as a spacer (Japanese Patent Laid-Open No. 2004-315712: Patent Document 1). Scratch resistance and adhesion have reached good levels.
However, these hydrolysates have the problem of poor storage stability.
Moreover, although it contained fluorine, effects such as water repellency and oil repellency were not obtained.

JP 2004-315712 A

  The present invention has been made in view of the above circumstances, gives a cured product having excellent water and oil repellency, scratch resistance and chemical resistance, has a low temperature curability of 120 ° C. or less, and has a storage stability. An object is to provide an excellent curable resin composition and an article coated with the same.

  As a result of intensive studies to achieve the above object, the present inventors have hydrolyzed an organosilicon compound containing a bissilane compound having a specific structure and an epoxy group-containing silane compound and / or an unsaturated group-containing silane compound. The curable resin composition comprising a composite resin, a fluorinated alcohol compound, a curing catalyst, and a solvent obtained by condensation forms a low refractive index cured film excellent in scratch resistance at a low temperature. The present inventors have found that it is excellent in water / oil repellency, storage stability, and chemical resistance, and has made the present invention.

（式中、Ｒｆはフルオロアルキル構造又はフルオロポリエーテル構造を含む分子量１００〜４０，０００の１価又は２価の基である。Ｑ¹は少なくとも（ａ＋ｂ）個のＳｉ原子を有する、シロキサン構造、非置換又はハロゲン置換のシルアルキレン構造、シルアリーレン構造又はこれらの２種以上の組み合せからなる（ａ＋ｂ）価の連結基であり、環状構造をなしていてもよい。Ｑ²は炭素数１〜２０の２価の炭化水素基であり、環状構造をなしていてもよく、途中エーテル結合又はエステル結合を含んでいてもよい。Ｒｆが１価のときにはａ’は１であり、かつａは１〜６の整数であり、Ｒｆが２価のときにはａは１であり、かつａ’は２である。ｂは１〜２０の整数である。）
（iii）硬化触媒：０．１〜１０質量部、
（iv）溶剤：固形分の量を０．５〜５０質量％であるように調節する量
を含有してなる硬化性樹脂組成物。
〔２〕
有機ケイ素化合物中、（Ａ）成分の含有量が２０〜８０質量部であり、（Ｂ）成分と（Ｃ）成分の合計量が２０〜８０質量部である〔１〕記載の硬化性樹脂組成物。
〔３〕
（ｉ'）無機酸化物微粒子（Ｄ）、及び
下記一般式（１）で示されるビスシラン化合物（Ａ）と、
Ｘ_nＲ_3-nＳｉ−Ｃ₂Ｈ₄−Ｃ_mＦ_2m−Ｃ₂Ｈ₄−ＳｉＲ_3-nＸ_n （１）
（式中、Ｒは１価の炭化水素基であり、ＸはＯＨ基又は加水分解性基であり、ｎ＝１、２又は３である。ｍ＝２〜２０の整数である。）
エポキシ基含有シラン化合物（Ｂ）及び／又は不飽和基含有シラン化合物（Ｃ）と
を含む有機ケイ素化合物の加水分解・縮合物を含み、（Ｄ）成分と（Ａ）〜（Ｃ）成分の加水分解・縮合物が一体化した複合樹脂：１００質量部、
（ii）下記一般式（２）で示される含フッ素アルコール化合物：０．００５〜２０質量部、

（式中、Ｒｆはフルオロアルキル構造又はフルオロポリエーテル構造を含む分子量１００〜４０，０００の１価又は２価の基である。Ｑ¹は少なくとも（ａ＋ｂ）個のＳｉ原子を有する、シロキサン構造、非置換又はハロゲン置換のシルアルキレン構造、シルアリーレン構造又はこれらの２種以上の組み合せからなる（ａ＋ｂ）価の連結基であり、環状構造をなしていてもよい。Ｑ²は炭素数１〜２０の２価の炭化水素基であり、環状構造をなしていてもよく、途中エーテル結合又はエステル結合を含んでいてもよい。Ｒｆが１価のときにはａ’は１であり、かつａは１〜６の整数であり、Ｒｆが２価のときにはａは１であり、かつａ’は２である。ｂは１〜２０の整数である。）
（iii）硬化触媒：０．１〜１０質量部、
（iv）溶剤：固形分の量を０．５〜５０質量％であるように調節する量
を含有してなる硬化性樹脂組成物。
〔４〕
有機ケイ素化合物中、（Ａ）成分の含有量が２０〜８０質量部であり、（Ｂ）成分と（Ｃ）成分の合計量が２０〜８０質量部であり、無機酸化物微粒子と有機ケイ素化合物の質量比率が１０／９０〜６０／４０である〔３〕記載の硬化性樹脂組成物。
〔５〕
無機酸化物微粒子（Ｄ）が、ＳｉＯ₂、ＴｉＯ₂、ＺｒＯ₂、ＺｎＯ、ＣｅＯ₂から選ばれる１種以上を主成分とするものであることを特徴とする〔３〕又は〔４〕記載の硬化性樹脂組成物。
〔６〕
無機酸化物微粒子（Ｄ）の平均粒子径が、１〜８０ｎｍであることを特徴とする〔３〕〜〔５〕のいずれかに記載の硬化性樹脂組成物。
〔７〕
ビスシラン化合物（Ａ）が、下記式で表されるものであることを特徴とする〔１〕〜〔６〕のいずれかに記載の硬化性樹脂組成物。
（ＣＨ₃Ｏ）₃Ｓｉ−Ｃ₂Ｈ₄−Ｃ_mＦ_2m−Ｃ₂Ｈ₄−Ｓｉ（ＯＣＨ₃）₃
（式中、ｍ＝２〜２０の整数である。）
〔８〕
一般式（２）の含フッ素アルコール化合物において、Ｑ¹が、下記式（３）

［但し、破線は結合手を示し、ａ、ｂは式（２）におけるａ、ｂと同一であり、ａの繰り返し単位を有するユニットはＲｆと結合し、ｂの繰り返し単位を有するユニットは下記式

（但し、Ｑ²は式（２）で定義した通りである。）
で示される基と結合する。また、２種類の繰り返し単位の並びはランダムである。Ｒｆは式（２）で定義した通りである。］
で表される〔１〕〜〔７〕のいずれかに記載の硬化性樹脂組成物。
〔９〕
一般式（２）において、Ｑ²が
−ＣＨ₂ＣＨ₂ＣＨ₂−、
−ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂−、
−ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂−、
−ＣＨ₂ＣＨ₂ＣＨ₂ＯＣＨ₂ＣＨ₂−、
−ＣＨ₂ＣＨ₂ＣＨ₂ＯＣＨ₂ＣＨ₂ＯＣＨ₂ＣＨ₂−、
−ＣＨ₂ＣＨ₂ＣＨ₂ＯＣＨ₂ＣＨ₂ＯＣＨ₂ＣＨ₂ＯＣＨ₂ＣＨ₂−、

で示される群の中より選ばれる〔１〕〜〔８〕のいずれかに記載の硬化性樹脂組成物。
〔１０〕
基材に、〔１〕〜〔９〕のいずれかに記載の硬化性樹脂組成物の硬化被膜が形成、被覆されてなる被覆物品。

Accordingly, the present invention provides the following curable resin composition and coated article.
[1]
(I) a bissilane compound (A) represented by the following general formula (1);
_{X n R 3-n Si-} C 2 H 4 -C m F 2m -C 2 H 4 -SiR 3-n X n (1)
(In the formula, R is a monovalent hydrocarbon group, X is an OH group or a hydrolyzable group, and n = 1, 2, or 3. m = 2 to 20 is an integer.)
Composite resin consisting of hydrolysis / condensation product of organosilicon compound containing epoxy group-containing silane compound (B) and / or unsaturated group-containing silane compound (C): 100 parts by mass
(Ii) Fluorine-containing alcohol compound represented by the following general formula (2): 0.005 to 20 parts by mass

(Wherein, Rf is .Q ¹ is a monovalent or divalent group having a molecular weight 100～40,000 containing a fluoroalkyl structure or fluoropolyether structure having at least (a + b) number of Si atoms, a siloxane structure, An unsubstituted or halogen-substituted silalkylene structure, a silarylene structure, or an (a + b) -valent linking group comprising a combination of two or more thereof, and may have a cyclic structure, Q ² has 1 to 20 carbon atoms A divalent hydrocarbon group, which may have a cyclic structure and may include an ether bond or an ester bond, and when Rf is monovalent, a ′ is 1 and a is 1 to 1. (When Rf is divalent, a is 1 and a ′ is 2. b is an integer of 1 to 20.)
(Iii) Curing catalyst: 0.1 to 10 parts by mass,
(Iv) Solvent: A curable resin composition containing an amount for adjusting the amount of solids to 0.5 to 50% by mass.
[2]
In the organosilicon compound, the content of the component (A) is 20 to 80 parts by mass, and the total amount of the component (B) and the component (C) is 20 to 80 parts by mass. object.
[3]
(I ′) inorganic oxide fine particles (D) , and a bissilane compound (A) represented by the following general formula (1):
_{X n R 3-n Si-} C 2 H 4 -C m F 2m -C 2 H 4 -SiR 3-n X n (1)
(In the formula, R is a monovalent hydrocarbon group, X is an OH group or a hydrolyzable group, and n = 1, 2, or 3. m = 2 to 20 is an integer.)
Comprising an epoxy group-containing silane compound (B) and / or unsaturated group-containing silane compound (C) and hydrolysis-condensation product of an organic silicon compound containing, (D) component and (A) ~ (C) component of hydrolysis Composite resin with integrated decomposition / condensate: 100 parts by mass,
(Ii) Fluorine-containing alcohol compound represented by the following general formula (2): 0.005 to 20 parts by mass

(Wherein, Rf is .Q ¹ is a monovalent or divalent group having a molecular weight 100～40,000 containing a fluoroalkyl structure or fluoropolyether structure having at least (a + b) number of Si atoms, a siloxane structure, An unsubstituted or halogen-substituted silalkylene structure, a silarylene structure, or an (a + b) -valent linking group comprising a combination of two or more thereof, and may have a cyclic structure, Q ² has 1 to 20 carbon atoms A divalent hydrocarbon group, which may have a cyclic structure and may include an ether bond or an ester bond, and when Rf is monovalent, a ′ is 1 and a is 1 to 1. (When Rf is divalent, a is 1 and a ′ is 2. b is an integer of 1 to 20.)
(Iii) Curing catalyst: 0.1 to 10 parts by mass,
(Iv) Solvent: A curable resin composition containing an amount for adjusting the amount of solids to 0.5 to 50% by mass.
[4]
In the organosilicon compound, the content of the component (A) is 20 to 80 parts by mass, the total amount of the component (B) and the component (C) is 20 to 80 parts by mass, and the inorganic oxide fine particles and the organosilicon compound The curable resin composition according to [3], wherein the mass ratio is 10/90 to 60/40.
[5]
[3] or [4], wherein the inorganic oxide fine particles (D) are mainly composed of one or more selected from SiO ₂ , TiO ₂ , ZrO ₂ , ZnO, and CeO ₂ . Curable resin composition.
[6]
The average particle diameter of inorganic oxide microparticles | fine-particles (D) is 1-80 nm, The curable resin composition in any one of [3]-[5] characterized by the above-mentioned.
[7]
The curable resin composition according to any one of [1] to [6], wherein the bissilane compound (A) is represented by the following formula.
_{(CH 3 O) 3 Si-} C 2 H 4 -C m F 2m -C 2 H 4 -Si (OCH 3) 3
(In the formula, m is an integer of 2 to 20.)
[8]
In the fluorine-containing alcohol compound of the general formula (2), Q ¹ represents the following formula (3)

[However, a broken line indicates a bond, a and b are the same as a and b in Formula (2), a unit having a repeating unit of a is bonded to Rf, and a unit having a repeating unit of b is represented by the following formula:

(However, Q ² is as defined in Formula (2).)
It bonds with the group shown by. Also, the arrangement of the two types of repeating units is random. Rf is as defined in Formula (2). ]
The curable resin composition in any one of [1]-[7] represented by these.
[9]
In the general formula (2), Q ² is —CH ₂ CH ₂ CH ₂ —,
_{-CH 2 CH 2 CH 2 CH 2} -,
_{-CH 2 CH 2 CH 2 CH 2} CH 2 -,
_{-CH 2 CH 2 CH 2 OCH 2} CH 2 -,
_{-CH 2 CH 2 CH 2 OCH 2} CH 2 OCH 2 CH 2 -,
_{-CH 2 CH 2 CH 2 OCH 2} CH 2 OCH 2 CH 2 OCH 2 CH 2 -,

The curable resin composition according to any one of [1] to [8], selected from the group represented by:
[10]
A coated article obtained by forming and coating a cured film of the curable resin composition according to any one of [1] to [9] on a base material.

  The curable resin composition of the present invention can be cured at a low temperature of 120 ° C. or less, has excellent storage stability, and provides a cured product having excellent water and oil repellency, scratch resistance, and chemical resistance. Can do.

  The composite resin as component (i) or (i ′) of the present invention comprises (A) a bissilane compound and (B) an epoxy group-containing silane compound and / or (C) an unsaturated group-containing silane compound as an organosilicon compound. If necessary, (D) it is integrated by hydrolysis and condensation in the presence of inorganic oxide fine particles.

The essential component bissilane compound (A) can be represented by the following general formula (1).
_{X n R 3-n Si-} C 2 H 4 -C m F 2m -C 2 H 4 -SiR 3-n X n (1)
(In the formula, R is a monovalent hydrocarbon group, X is an OH group or a hydrolyzable group, and n = 1, 2, or 3. m = 2 to 20 is an integer.)

  If m is 1, sufficient curability may not be obtained. Moreover, when m exceeds 20, as a result of insufficient crosslinking density, the cured film becomes flexible, and good scratch resistance may not be obtained. As a result of the remarkable increase in the boiling point of the silane compound, purification becomes difficult and may be economically disadvantageous, so m preferably satisfies the range of 4 to 12. Particularly preferably, the range of 4 to 8 should be satisfied.

  R represents a monovalent hydrocarbon group such as a linear, branched or cyclic alkyl group such as a methyl, ethyl, butyl, hexyl, or cyclohexyl group, or an aryl group such as a phenyl group, and has 1 to 10 carbon atoms. Those are preferred.

  X represents a halogen atom, an alkoxy group having 1 to 4 carbon atoms, an acyloxy group, an alkenoxy group, a ketoxime group, an alkoxyalkoxy group, or an —NCO group as an OH group or a hydrolyzable group. Specifically, halogen atoms such as OH group, Cl, alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, alkenoxy groups such as isopropenoxy group, acyloxy groups such as acetoxy group, methyl ethyl ketoxime Examples thereof include a ketoxime group such as a group, an alkoxyalkoxy group such as a methoxyethoxy group, and a —NCO group. A methoxy group and an alkoxy group of ethoxy group are preferable because they are easy to handle and can easily control the reaction during hydrolysis.

  N representing the number of siloxane-crosslinkable groups X can be any of 1, 2, and 3, but 2 and 3 are preferred from the viewpoint of curability. In order to increase the crosslink density and bring the scratch resistance to a good level, it is preferable to set n = 3.

As a specific example of the bissilane compound satisfying the above,
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 2 -C 2 H 4 -Si (OCH 3) 3,
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 4 -C 2 H 4 -Si (OCH 3) 3,
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 6 -C 2 H 4 -Si (OCH 3) 3,
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 8 -C 2 H 4 -Si (OCH 3) 3,
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 10 -C 2 H 4 -Si (OCH 3) 3,
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 12 -C 2 H 4 -Si (OCH 3) 3,
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 16 -C 2 H 4 -Si (OCH 3) 3,
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 20 -C 2 H 4 -Si (OCH 3) 3,
_{(C 2 H 5 O) 3} Si-C 2 H 4 - (CF 2) 4 -C 2 H 4 -Si (OC 2 H 5) 3,
_{(C 2 H 5 O) 3} Si-C 2 H 4 - (CF 2) 6 -C 2 H 4 -Si (OC 2 H 5) 3,
_{(C 3 H 7 O) 3} Si-C 2 H 4 - (CF 2) 4 -C 2 H 4 -Si (OC 3 H 7) 3,
_{(C 3 H 7 O) 3} Si-C 2 H 4 - (CF 2) 6 -C 2 H 4 -Si (OC 3 H 7) 3,
_{(CH 3 O) 2 (CH} 3) Si-C 2 H 4 - (CF 2) 4 -C 2 H 4 -Si (CH 3) (OCH 3) 2,
_{(CH 3 O) 2 (CH} 3) Si-C 2 H 4 - (CF 2) 6 -C 2 H 4 -Si (CH 3) (OCH 3) 2,
_{(CH 3 O) 2 (C} 6 H 5) Si-C 2 H 4 - (CF 2) 4 -C 2 H 4 -Si (C 6 H 5) (OCH 3) 2,
_{(CH 3 O) 2 (C} 6 H 5) Si-C 2 H 4 - (CF 2) 6 -C 2 H 4 -Si (C 6 H 5) (OCH 3) 2

Among these, preferably,
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 4 -C 2 H 4 -Si (OCH 3) 3,
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 6 -C 2 H 4 -Si (OCH 3) 3,
_{(CH 3 O) 3 Si-} C 2 H 4 - (CF 2) 8 -C 2 H 4 -Si (OCH 3) 3
These bissilane compounds are preferably used.

  It is preferable that 20-80 mass parts of (A) component is mix | blended in 100 mass parts of organosilicon compounds. If it is less than 20 parts by mass, the curability may be deteriorated, and if it is more than 80 parts by mass, the stability may be deteriorated.

In the present invention, in addition to the bissilane compound (A), the epoxy group-containing silane compound (B) and / or the unsaturated group-containing silane compound (C) are cohydrolyzed and condensed.
By cohydrolyzing these, stability is improved.

  Examples of the epoxy group-containing silane compound (B) include alkoxysilanes having a glycidoxyalkyl group and alkoxysilanes having an epoxycycloalkyl group. Examples of the alkoxysilane having a glycidoxyalkyl group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane. Examples of the alkoxysilane having an epoxycycloalkyl group include 3,4-epoxycyclohexyltrimethoxysilane and 3,4-epoxycyclohexyltriethoxysilane.

  Examples of the unsaturated group-containing silane compound (C) include an alkoxysilane having a (meth) acryloxyalkyl group, an alkoxysilane having a styryl group, and the like. Examples of the alkoxysilane having a (meth) acryloxyalkyl group include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, (meth) acryloxymethyltrimethoxysilane, 6- (Meth) acryloxyhexyltrimethoxysilane, 8- (meth) acryloxyoctyltrimethoxysilane, and the like. Examples of the alkoxysilane having a styryl group include styryltrimethoxysilane and styryltriethoxysilane.

The total amount of the component (B) and the component (C) is preferably 20 to 80 parts by mass in 100 parts by mass of the organosilicon compound. If the amount is less than 20 parts by mass, the stability may be deteriorated. If the amount is more than 80 parts by mass, the curability may be deteriorated.
Either (B) component or (C) component may be blended, or both may be blended.

  The silane compound that can be used in combination with the bissilane compound, the epoxy group-containing silane compound, and the unsaturated group-containing silane compound will be described. In addition to these silane compounds, the following compounds are used in a range that does not affect the required properties. be able to. However, the silane compound to be blended is within 20 parts by mass in 100 parts by mass of the organosilicon compound. Preferably, it is within 10 parts by mass.

Specifically, silicates such as tetraethoxysilane, aminofunctional alkoxysilanes such as 3-aminopropyltriethoxysilane, mercaptofunctional alkoxysilanes such as 3-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, Hexyltrimethoxysilane, alkylalkoxysilanes such as decyltrimethoxysilane, phenylalkoxysilanes such as phenyltrimethoxysilane, chloropropyltrimethoxysilane, trifluoropropyltrimethoxysilane, perfluorobutylethyltrimethoxysilane, perfluoro Halogen-substituted alkylalkoxysilanes such as octylethyltrimethoxysilane,
_{CF 3 (CF 2) 7 SO} 2 NH-C 3 H 6 -Si (OCH 3) 3,
_{CF 3 (CF 2) 7 CONH} -C 3 H 6 -Si (OCH 3) 3,
Alkoxysilanes having fluorine-containing substituents such as perfluoropolyether group-containing methoxysilane,
_{(CH 3 O) 3 Si-} C 2 H 4 -Si (OCH 3) 3,
_{(CH 3 O) 3 Si-} C 6 H 12 -Si (OCH 3) 3,
_{(CH 3 O) 2 (CH} 3) Si-C 2 H 4 -Si (CH 3) (OCH 3) 2,
_{(CH 3 O) (CH 3} ) 2 Si-C 2 H 4 -Si (CH 3) 2 (OCH 3),
_{(C 2 H 5 O) 3} Si-C 2 H 4 -Si (OC 2 H 5) 3,
Cl ₃ Si—C ₂ H ₄ —SiCl ₃ ,
_{(CH 3 COO) 3 Si-} C 2 H 4 -Si (OCOCH 3) 3,
_{(CH 3 O) 3 Si-} C 6 H 4 -Si (OCH 3) 3,
_{(CH 3 O) 2 (CH} 3) Si-C 6 H 4 -Si (CH 3) (OCH 3) 2,
_{(CH 3 O) (CH 3} ) 2 Si-C 6 H 4 -Si (CH 3) 2 (OCH 3),
_{(CH 3 O) 3 Si-} C 2 H 4 -C 6 H 4 -C 2 H 4 -Si (OCH 3) 3,
_{(CH 3 O) 2 (CH} 3) Si-C 2 H 4 -C 6 H 4 -C 2 H 4 -Si (CH 3) (OCH 3) 2,
_{(CH 3 O) (CH 3} ) 2 Si-C 2 H 4 -C 6 H 4 -C 2 H 4 -Si (CH 3) 2 (OCH 3)
Examples thereof include bisalkoxysilane compounds not containing a fluorine substituent such as these and derivatives thereof.

A conventionally well-known thing can be used for the inorganic oxide fine particle which is (D) component. As the inorganic material, various metal oxides such as Si, Ti, Zn, Sb, Y, La, Zr, Al, In, Sn, Ce, and Fe can be used. In particular, SiO ₂ , TiO ₂ , ZrO ₂ , ZnO It is preferable that the main component is CeO ₂ . More preferably, the main component is SiO ₂ . In addition, a main component here means containing 50 mass% or more in inorganic oxide microparticles | fine-particles, especially 80 mass% or more and 100 mass% or less.

  The average particle diameter of the inorganic oxide fine particles is preferably 1 to 80 nm, more preferably 3 to 60 nm, and still more preferably 5 to 50 nm. If the average particle size is less than this lower limit, the particles tend to aggregate and become unstable. If the upper limit is exceeded, the transparency of the cured coating may be reduced. In addition, this average particle diameter is based on the volume average particle diameter D50 by a dynamic light scattering method.

The inorganic oxide fine particles are preferably dispersed in water or an organic solvent. Examples of the organic solvent include methanol, ethanol, propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, diacetone alcohol and the like, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, glycol ethers such as propylene glycol monomethyl ether acetate, ethers such as dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and acetyl acetone, ethyl acetate , Esters such as butyl acetate and ethyl acetoacetate, xylene, Etc. can be mentioned as specific examples.
The particles may be porous and / or inorganic oxide fine particles having voids inside.

  The mass ratio with the organosilicon compound satisfies the range of inorganic oxide fine particles / organosilicon compound = 0/100 to 60/40, particularly 10/90 to 60/40 when inorganic oxide fine particles are contained. Good. If it is out of this range, sufficient wear resistance and hardness may not be obtained. More preferably, it should satisfy the range of 20/80 to 50/50, particularly preferably 30/70 to 45/55.

  In the present invention, the composite resin obtained by hydrolyzing and condensing the organosilicon compound containing the bissilane compound (A) in the presence of the inorganic oxide fine particles (D) as necessary is used. A conventionally known method can be applied as the hydrolysis / condensation method.

  When performing the hydrolysis / condensation, the following can be used as a catalyst. Acids such as hydrochloric acid, nitric acid, acetic acid and maleic acid, alkali metal hydroxides such as NaOH and KOH, amine compounds such as ammonia, triethylamine, dibutylamine, hexylamine and octylamine, and salts of amine compounds, benzyltriethylammonium chloride , Bases such as quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide, fluorides such as potassium fluoride and sodium fluoride, solid acidic catalysts or solid basic catalysts (eg ion exchange) Resin catalysts, etc.), metal salts of organic carboxylic acids such as iron-2-ethylhexoate, titanium naphthate, zinc stearate, dibutyltin diacetate, tetrabutoxytitanium, tetra-i-propoxytitanium, dibutoxy- (bis -2,4-penta Diate) organic titanium esters such as titanium, di-i-propoxy (bis-2,4-pentanedionate) titanium, tetrabutoxyzirconium, tetra-i-propoxyzirconium, dibutoxy- (bis-2,4-pentanedionate) ) Organic compounds such as organic zirconium esters such as zirconium, di-i-propoxy (bis-2,4-pentanedionate) zirconium, alkoxyaluminum compounds such as aluminum triisopropoxide, and aluminum chelate compounds such as aluminum acetylacetonate complex Metal compounds, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (β-aminoethyl) -3-aminopropyltrimethoxysilane, N- (β-aminoethyl) -3-aminopropyl Aminoalkyl-substituted alkoxysilanes such as triethoxysilane and the like, may be used singly or in combination.

  The addition amount of this catalyst is 0.01-10 mass parts with respect to 100 mass parts of organosilicon compounds, Preferably it is 0.1-5 mass parts. If this amount is less than 0.01 parts by mass, it may take too long to complete the reaction, and the reaction may not proceed. Moreover, when it exceeds 10 mass parts, it is disadvantageous in cost, and there exists a possibility that the obtained reaction material may color, side reaction may increase, or may become unstable.

  The hydrolysis / condensation reaction is preferably carried out in a system diluted with a solvent. As this solvent, alcohols such as methanol, ethanol, propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, glycol ethers such as propylene glycol monomethyl ether acetate, ethers such as dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and acetyl acetone, ethyl acetate , Esters such as butyl acetate and ethyl acetoacetate, xylene, Etc. The. Although the addition amount of the solvent is arbitrary, it is preferable to adjust so that the amount of the active ingredient in the solution is 0.5 to 50% by mass. Preferably it is 1-30 mass%.

  In the hydrolysis / condensation reaction, inorganic oxide fine particles and an organic silicon compound containing a bissilane compound are dispersed and mixed in the organic solvent, and the hydrolysis / condensation catalyst is added to the organic solvent as necessary. Hydrolysis water is added to perform hydrolysis and condensation. The amount of water used for hydrolysis is preferably 0.3 to 10 moles of water relative to the total number of moles of hydrolyzable groups (SiX) of all organosilicon compounds. If the amount is less than this amount, hydrolysis does not proceed sufficiently, and crosslinking between the inorganic oxide fine particles and the binder derived from the organosilicon compound may not proceed sufficiently. On the other hand, when the coating solution is exceeded, the remaining water may not be sufficiently volatilized and the film may be whitened. More preferably, 0.5 to 5 times mol of water is used. The organosilicon compound may be hydrolyzed all at once in the presence of the inorganic oxide fine particles, or may be added in multiple stages and hydrolyzed.

（式中、Ｒｆはフルオロアルキル構造又はフルオロポリエーテル構造を含む分子量１００〜４０，０００の１価又は２価の基である。Ｑ¹は少なくとも（ａ＋ｂ）個のＳｉ原子を有する、シロキサン構造、非置換又はハロゲン置換のシルアルキレン構造、シルアリーレン構造又はこれらの２種以上の組み合せからなる（ａ＋ｂ）価の連結基であり、環状構造をなしていてもよい。Ｑ²は炭素数１〜２０の２価の炭化水素基であり、環状構造をなしていてもよく、途中エーテル結合又はエステル結合を含んでいてもよい。Ｒｆが１価のときにはａ’は１であり、かつａは１〜６の整数であり、Ｒｆが２価のときにはａは１であり、かつａ’は２である。ｂは１〜２０の整数である。） The component (ii) fluorine-containing alcohol component is represented by the following general formula (2) and can impart water and oil repellency and dissolves in the system and does not separate.

(Wherein, Rf is .Q ¹ is a monovalent or divalent group having a molecular weight 100～40,000 containing a fluoroalkyl structure or fluoropolyether structure having at least (a + b) number of Si atoms, a siloxane structure, An unsubstituted or halogen-substituted silalkylene structure, a silarylene structure, or an (a + b) -valent linking group comprising a combination of two or more thereof, and may have a cyclic structure, Q ² has 1 to 20 carbon atoms A divalent hydrocarbon group, which may have a cyclic structure and may include an ether bond or an ester bond, and when Rf is monovalent, a ′ is 1 and a is 1 to 1. (When Rf is divalent, a is 1 and a ′ is 2. b is an integer of 1 to 20.)

In the formula (2), Rf is a monovalent or divalent group containing a fluoroalkyl structure or a fluoropolyether structure, the molecular weight as Rf is 100 to 40,000, preferably 500 to 20,000, and Formula -C _i F _2i O-
(I is an integer of 1 to 6 independently for each unit.)
Those containing 1 to 500, preferably 2 to 400, more preferably 4 to 200 repeating units represented by formula (1) are suitable. In the present invention, the molecular weight is a number average molecular weight calculated from the ratio between the terminal structure and the main chain structure based on ¹ H-NMR and ¹⁹ F-NMR.

A particularly preferable structure as Rf can be represented by the following general formula (4) or (4 ′).
− [Q ³ −Rf′−Q ³ −T] _v −Qf−Rf′−Q ³ − (4)
F-Rf′-Q ³ − (4 ′)

  Rf ′ is a perfluoropolyether group having a divalent molecular weight of 300 to 30,000, particularly 500 to 20,000, and may contain a branch, and is particularly represented by the following formulas (5) to (7). Divalent perfluoropolyether groups are preferred.

（式（５）中、Ｙはそれぞれ独立にＦ又はＣＦ₃基、ｒは２〜６の整数、ｍ１、ｎ１はそれぞれ０〜２００、好ましくは０〜１００の整数、但し、ｍ１＋ｎ１は２〜２００、好ましくは３〜１５０の整数である。ｓは０〜６の整数であり、各繰り返し単位はランダムに結合されていてよい。）

（式中、ｊは１〜３の整数、ｋは１〜２００、好ましくは１〜６０の整数である。）

（式中、ＹはＦ又はＣＦ₃基、ｊは１〜３の整数、ｔ、ｕはそれぞれ０〜２００、好ましくは２〜１００の整数、但し、ｔ＋ｕは２〜３００、好ましくは４〜２００の整数である。各繰り返し単位はランダムに結合されていてもよい。）

(In Formula (5), Y is each independently F or CF ₃ group, r is an integer of 2 to 6, m1 and n1 are each 0 to 200, preferably 0 to 100, provided that m1 + n1 is 2 to 200. And preferably an integer of 3 to 150. s is an integer of 0 to 6, and each repeating unit may be bonded at random.)

(In the formula, j is an integer of 1 to 3, and k is an integer of 1 to 200, preferably 1 to 60.)

Wherein Y is an F or CF ₃ group, j is an integer of 1 to 3, t and u are each 0 to 200, preferably 2 to 100, provided that t + u is 2 to 300, preferably 4 to 200. (Each repeating unit may be bonded at random.)

Q ³ is a divalent organic group, preferably a divalent hydrocarbon group having 2 to 20 carbon atoms, which may contain an oxygen atom, a nitrogen atom, a fluorine atom or a silicon atom, and a cyclic structure or It may be a group having an unsaturated bond. Examples of such Q ³ include the following. In the formula, Ph represents a phenyl group.

が好ましい。 Especially among these

Is preferred.

（式中、Ｑ²、ａ、ｂは前述の通りであり、Ｑ⁴は少なくとも（ａ＋ｂ）個のＳｉ原子を有する、シロキサン構造、非置換又はハロゲン置換のシルアルキレン構造、シルアリーレン構造又はこれらの２種以上の組み合せからなる（ａ＋ｂ）価の連結基であり、前述のＱ¹の（ａ＋ｂ）価のうち、２価分がＱ³との結合に使用されたシロキサン構造、非置換又はハロゲン置換のシルアルキレン構造、シルアリーレン構造又はこれらの２種以上の組み合せからなる構造である。）
で表される２価の連結基である。 T is the following formula (8)

(Wherein Q ² , a, and b are as defined above, and Q ⁴ has at least (a + b) Si atoms, a siloxane structure, an unsubstituted or halogen-substituted silalkylene structure, a silarylene structure, or a combination thereof. A (a + b) -valent linking group composed of a combination of two or more of the above-mentioned Q ¹ (a + b) valence, wherein the divalent siloxane structure is used for bonding to Q ³ , unsubstituted or halogen-substituted These are silalkylene structures, silarylene structures, or a combination of two or more of these.)
It is a bivalent coupling group represented by these.

Examples of Q ⁴ include the following. However, in the following formula, the divalent bond indicated by the solid line is bonded to Q ^3, and the (a + b−2) bond indicated by the broken line is −Q ² —OH. (Wherein Q ² is as described above). In addition, in the case of the following formula (a), -Q ² -OH is connected to the broken lines of the units at both ends, and (a + b-2) units are formed by these units at both ends and the unit (a + b-4). min bond to bind a group represented by -Q ² -OH. In addition, the arrangement of the above-described units for two valences indicated by the solid line, (a + b−2) units, and p units are random. a and b are each preferably an integer of 1 to 4 and a + b is an integer of 3 to 6, particularly 3 to 5. p is 0 or an integer of 1 or more, and the upper limit of p is preferably 12 or less.

Here, Q ⁵ is an (a + b) -valent linking group, and examples thereof include the following.

Qf is Q ³ , or a fluorine atom when v = 0.
Further, v is an integer of 0 to 5, but when Qf is a fluorine atom, v is 0 and Rf has the following structure (4 ′).
F-Rf′-Q ³ − (4 ′)

Specific examples of Rf include the following.

（上記式中、ｊ、ｋ、ｍ１、ｎ１、ｒ、ｓ、ｔ、ｕは上述した通りである。）

(In the above formula, j, k, m1, n1, r, s, t, and u are as described above.)

  In the formula (2), a is an integer of 1 to 6, b is an integer of 1 to 20, a 'is 1 or 2, and when Rf is monovalent, a is an integer of 1 to 6, A ′ is 1, and when Rf is divalent, a is 1 and a ′ is 2. b is an integer of 1 to 20, particularly preferably an integer of 1 to 6, and a + b is preferably an integer of 3 to 6, particularly 3 to 5.

In the formula (2), Q ¹ is an (a + b) -valent compound comprising a siloxane structure having at least (a + b) Si atoms, an unsubstituted or halogen-substituted silalkylene structure, a silarylene structure, or a combination of two or more thereof. The linking group may have a cyclic structure, and specifically, the following structures are shown. However, in the following formula, a and b are as defined above, preferably both a and b are integers of 1 to 4, and a + b is an integer of 3 to 6, particularly 3 to 5. p is an integer of 0 or 1 or more, the arrangement of each of a units, b units, and p units is random, and a bond indicated by a broken line of each of the a units and b units is Rf− or -Q (wherein, Rf, Q ² are as defined above.) ² -OH is bonded to any one of the radicals represented by. In addition, it is preferable that the upper limit of p is 12 or less.

The a + b unit can be represented separately as a unit and b unit, Rf is connected to the bond of the unit a, and -Q ² —OH is connected to the bond of the unit b. Are linked (Rf and Q ² are as described above). In the case of formula (b), Rf or -Q ² -OH is connected to the broken lines of the units at both ends, and (a + b) units are constituted by these units at both ends and the unit (a + b-2). To do.

Q ⁵ is as described above, and examples of Q ⁵ are the same as those described above.

［式中、ａ、ｂは上記と同じであり、破線は結合手を示し、ａの繰り返し単位を有するユニットは上記Ｒｆと結合し、ｂの繰り返し単位を有するユニットは下記式
−Ｑ²−ＯＨ
（式中、Ｑ²は上記と同じである。）
で示される基と結合する。また、２種類の繰り返し単位の並びはランダムである。］ Q ¹ is more preferably a structure represented by the following formula (3).

[Wherein, a and b are the same as above, the broken line indicates a bond, a unit having a repeating unit of a is bonded to the above Rf, and a unit having a repeating unit of b is represented by the following formula -Q ² -OH
(Wherein Q ² is the same as above)
It bonds with the group shown by. Also, the arrangement of the two types of repeating units is random. ]

In the formula (2), Q ² is a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 2 to 15 carbon atoms, and may have a cyclic structure, and an ether bond (—O—) or an ester bond on the way (-COO-) may be included. Specifically, the following structures are exemplified.
-CH ₂ CH ₂ CH ₂ -,
_{-CH 2 CH 2 CH 2 CH 2} -,
_{-CH 2 CH 2 CH 2 CH 2} CH 2 -,
_{-CH 2 CH 2 CH 2 OCH 2} CH 2 -,
_{-CH 2 CH 2 CH 2 OCH 2} CH 2 OCH 2 CH 2 -,
_{-CH 2 CH 2 CH 2 OCH 2} CH 2 OCH 2 CH 2 OCH 2 CH 2 -,

The fluorine-containing alcohol compound represented by the general formula (2) as described above can be synthesized, for example, by the following method.
First, with respect to the fluorine-containing compound (a) having an olefin group at the terminal, a polyfunctional Si—H compound (for example, a siloxane having 2 or more, preferably 3 or more Si—H groups in the molecule, (Silalkylene, silarylene, or an organosilicon compound composed of a combination of two or more thereof) (b) is subjected to a hydrosilylation addition reaction under an excessive Si-H group condition to produce a fluorine-containing polyfunctional Si-H compound (c) Is synthesized.

Among such compounds (a), the following formula (9) can be shown as an example of generalizing a particularly desirable structure.
Rf ⁰ − (CH═CH ₂ ) _x (9)

Here, Rf ⁰ is represented by the following formula: − [Q ⁶ −Rf′−Q ³ −T] _v −Qf−Rf′−Q ⁶ −
F-Rf′-Q ⁶ −
It is represented by In the above formula, Rf ′, T, Qf, Q ³ and v are as described above, Q ⁶ is a divalent organic group, preferably a C 1-20 divalent hydrocarbon group, oxygen It may contain an atom, nitrogen atom, fluorine atom or silicon atom, and may be a group having a cyclic structure or an unsaturated bond. x is 2 when Rf ⁰ is monovalent and 1 when Rf ⁰ is monovalent.

Examples of Q ⁶ include the following. In the following examples, Ph represents a phenyl group.

The following can be illustrated as a particularly preferable compound (a).

（上記式中、ｊ、ｋ、ｍ１、ｎ１、ｒ、ｓは上述した通りである。）

(In the above formula, j, k, m1, n1, r, and s are as described above.)

The compound (b) can be expressed as a general formula in the form of the following formula (10).
Q ¹ − (H) _{a + b} (10)
(In the formula, Q ¹ , a and b are as described above, and H shown in parentheses is a hydrogen atom directly bonded to an Si atom in the Q ¹ structure.)

Among these, the following can be illustrated as a preferable compound (b).

（上記式中、ａ、ｂは前述の通りであり、ｐは０又は１以上の整数である。）

(In the above formula, a and b are as described above, and p is 0 or an integer of 1 or more.)

  By performing an addition reaction at a reaction temperature of 60 to 150 ° C., preferably 70 to 120 ° C. in the presence of a platinum group metal-based addition reaction catalyst in any combination of the compound (a) and the compound (b) as described above. A fluorine-containing polyfunctional Si—H compound (c) can be obtained.

For example, when the compound (a) is monofunctional (x = 1 in the formula (9)), the compound (b) is 1 if the number of compounds (a) to be added to one molecule is less than (a + b). For example, the compound (c) obtained by adding a number can be represented by the following general formula (11).
(Rf ⁰ -C ₂ H ₄ ) _a -Q ^1- (H) _b (11)
(In the formula, Rf ⁰ , Q ¹ , a, and b are as described above, and H shown in parentheses is a hydrogen atom directly bonded to an Si atom in the Q ¹ structure.)

（式中、Ｔ²は

で示される基であり、Ｑ¹、Ｑ⁴、Ｒｆ⁰、ａ、ｂ、ｖは前述の通りであり、かっこ内に示されたＨはＱ¹又はＱ⁴構造中のＳｉ原子に直接結合する水素原子である。） On the other hand, when the compound (a) is bifunctional (x = 2 in the formula (9)), it is desirable to add the compound (a): compound (b) = v + 1: v + 2 (molar ratio). (V is as described above), and the resulting compound (c) can be expressed, for example, as in formula (12). When v = 0, the compound (a) has one molecule at both ends. (B) is introduced.

(Where T ² is

Q ¹ , Q ⁴ , Rf ⁰ , a, b, v are as described above, and H shown in parentheses is directly bonded to the Si atom in the Q ¹ or Q ⁴ structure. It is a hydrogen atom. )

  The above addition reaction can be carried out without a solvent, but may be diluted with a solvent as necessary. At this time, a widely used organic solvent such as toluene, xylene, and isooctane can be used as the diluting solvent. However, the boiling point is not lower than the target reaction temperature and does not inhibit the reaction. ) Is preferably soluble at the reaction temperature. For example, a partially fluorine-modified solvent such as a fluorine-modified aromatic hydrocarbon solvent such as m-xylene hexafluoride or benzotrifluoride or a fluorine-modified ether solvent such as methyl perfluorobutyl ether is desirable. Hexafluoride is preferred.

  As the addition reaction catalyst, for example, a compound containing platinum, rhodium or palladium can be used. Among them, a compound containing platinum is preferable, hexachloroplatinic acid (IV) hexahydrate, platinum carbonyl vinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde / octanol complex, Alternatively, platinum supported on activated carbon can be used. The compounding amount of the catalyst is preferably such that the amount of metal contained is 0.1 to 5,000 mass ppm, more preferably 1 to 1,000 mass ppm with respect to the compound (a).

In the addition reaction, the order in which the components are charged is not particularly limited. For example, the method of gradually heating the mixture of the compound (a), the compound (b) and the catalyst from room temperature to the addition reaction temperature, the compound (a), the compound (b ) And a dilute solvent mixture after heating to the target reaction temperature, adding the catalyst, dropping the compound (a) to the mixture of the compound (b) and catalyst heated to the target reaction temperature, The method of dripping the mixture of a compound (a) and a catalyst etc. to the compound (b) heated to reaction temperature to make can be taken. Among them, a method of adding a catalyst after heating a mixture of the compound (a), the compound (b) and the diluting solvent to a target reaction temperature or a compound (b) heated to a target reaction temperature. A method of dropping the mixture of (a) and the catalyst is particularly preferable. These methods can be used by diluting each component or mixture with a solvent as necessary. The above reaction is carried out in a dry atmosphere in air or an inert gas (N ₂ , Ar, etc.) at a reaction temperature of 50 to 150 ° C., preferably 60 to 120 ° C., for 0.5 to 96 hours, preferably 1 to 48. It is desirable to do time.

  The compounding amount of the compound (b) with respect to the compound (a) is such that the number of compounds (a) to be added is less than (a + b) per molecule of the compound (b), and v in the compound (c) is 0. Any amount may be used as long as it is an integer of ˜5, but in order to prevent three-dimensional crosslinking, compound (b) is excessive with respect to the terminal olefin group such as an allyl group of compound (a). It is desirable to remove the unreacted compound (b) by distillation under reduced pressure or the like after the addition reaction using an amount, and the compound (b) with respect to 1 equivalent of a terminal olefin group such as an allyl group of the compound (a). Is preferably reacted in the presence of 1 to 10 equivalents, particularly 2 to 6 equivalents. If necessary, an addition reaction may be carried out stepwise after synthesizing an intermediate having a small v. For example, after synthesizing the compound (c) with v = 0 in the formula (12) using the compound (a) with x = 2 in the formula (9), the formula (c) The compound (c) of v = 3 can be obtained by reacting again 1 mol of the compound (a) of x = 2 in 9). Alternatively, in the compound (c), the component having the target value of v can be separated from a mixture having different v by any separation means. For example, you may take out only the component of v = 1 from a mixture of v = 0-3 in a compound (c) by means, such as a preparative chromatograph.

The fluorine-containing alcohol compound used in the present invention is an addition reaction between the Si—H group of the compound (c) obtained as described above and the compound (d) having a terminal olefin group and an alcoholic hydroxyl group in one molecule. Can be obtained by performing As such a compound (d), the following are particularly preferable. These compounds (d) can be used alone or in combination of any two or more.
CH ₂ = CHCH ₂ OH,
CH ₂ = CHCH ₂ CH ₂ OH,
CH ₂ = CHCH ₂ CH ₂ CH ₂ OH,
CH ₂ = CHCH ₂ OCH ₂ CH ₂ OH,
_{CH 2 = CHCH 2 OCH 2 CH} 2 OCH 2 CH 2 OH,
_{CH 2 = CHCH 2 OCH 2 CH} 2 OCH 2 CH 2 OCH 2 CH 2 OH,

The addition reaction of the compound (c) and the compound (d) can be performed by the same method as the addition reaction of the compound (a) and the compound (b) described above. That is, in the presence of the above-mentioned addition reaction catalyst, in a dry atmosphere, in air or an inert gas (N ₂ , Ar, etc.), a reaction temperature of 50 to 150 ° C., preferably 60 to 120 ° C., for 0.5 to 96 hours, Preferably, the reaction can be carried out in any order of addition by performing dilution as necessary for 1 to 48 hours.

  The compounding amount of the compound (d) with respect to the compound (c) can be set to an arbitrary amount, but the compound (d) is added using an equimolar amount or an excess amount with respect to the Si—H group of the compound (c). After the reaction, it is desirable to remove the unreacted compound (d) by distillation under reduced pressure or the like. In particular, the compound (d) is added in an amount of 1.0 to 1.0 to 1 equivalent of the Si—H group of the compound (c). It is desirable to carry out the reaction in the presence of 2.0, preferably 1.0 to 1.2 equivalents.

In the present invention, the fluorinated alcohol compound may be represented by the following formula (Rf) _a- [Q ^1- (H) _b ] _{c in} addition to the above method.
(Wherein Q ¹ , a, b, c and Rf are as described above.)
It can also be obtained by carrying out an addition reaction between the fluorine-containing organosilicon compounds (e) and (d) represented by In this case, the reaction conditions and the like can be the same as the reaction conditions for the compound (c) and the compound (d) described above.

Examples of the particularly preferable structure of the fluorinated alcohol compound of the component (ii) thus obtained include the following.

（上記式中、ｎ１、ｊ、ｔ、ｕは上記と同じである。）

(In the above formula, n1, j, t and u are the same as above.)

  This invention is a curable resin composition which mix | blended the fluorine-containing alcohol compound obtained as mentioned above. By curing this, it is possible to provide a curable resin composition that imparts antifouling properties, fingerprint resistance, water repellency, and oil repellency to the surface of the cured product. The blending amount of the fluorinated alcohol of the component (ii) is 0.005 to 20 parts by mass, preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the solid content of the component (i) or (i ′). is there. If the value exceeds the above upper limit, the added fluorine-containing alcohol compound component layer may be thick, and the performance as a cured product may be impaired. If the value is less than the lower limit, the surface of the hard coat layer may be sufficiently covered. It may not be possible.

(Iii) The curing catalyst of the component is various metal compounds. Specifically, tetrabutoxy titanium, tetra-i-propoxy titanium, dibutoxy- (bis-2,4-pentanedionate) titanium, di-i-propoxy (bis-2,4-pentanedionate) titanium, and the like. Organics such as organic titanium esters, tetrabutoxyzirconium, tetra-i-propoxyzirconium, dibutoxy- (bis-2,4-pentanedionate) zirconium, di-i-propoxy (bis-2,4-pentanedionate) zirconium Alkoxy aluminum compounds such as zirconium ester and aluminum triisopropoxide, aluminum chelate compounds such as aluminum acetylacetonate complex, Hf, V, Nb, Ta, Mo, W, Fe, Ru, Co, Rh, Ni, Zn, Ga Of In, Ge, Sn, etc. It can be exemplified derivatives, but is not limited thereto.
Among these, an aluminum acetylacetonate complex is preferable in terms of achieving both stability and curability.

  The addition amount of the curing catalyst is 0.1 to 10 parts by mass, preferably 0.5 to 7 parts by mass with respect to 100 parts by mass of the solid content of the component (i) or (i ′). When this amount is less than 0.1 parts by mass, the curability may be lowered or the stability may be deteriorated. On the other hand, if the amount is more than 10 parts by mass, the reaction product obtained may be colored or the scratch resistance may be lowered.

  The solvent of the component (iv) is the same as the reaction solvent described above, and is methanol, ethanol, propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, diacetone alcohol. Alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, glycol ethers such as propylene glycol monomethyl ether acetate, ethers such as dioxane and tetrahydrofuran, acetone, methyl ethyl ketone, Ketones such as methyl isobutyl ketone, cyclohexanone, acetylacetone, ethyl acetate, butyl acetate, ethyl acetoacetate Esters etc., xylene, and toluene. Although the addition amount of the solvent is arbitrary, it is preferable to adjust so that the amount of the solid content (active ingredient) in the solution is 0.5 to 50% by mass. Preferably it is 1-30 mass%.

  The curable resin composition containing the composite resin of the present invention and an organic solvent can be used as a coating agent composition. If necessary, a silicon-containing or fluorine-containing surfactant may be added to this coating agent composition. Specifically, various polyether-modified silicone compounds and various fluorine-containing interfaces sold by Sumitomo 3M (trade name: Fluorard), DuPont (fluoroalkyl polyether), and Asahi Glass (trade name: Surflon) Examples include an activator and a SiOH group-terminated oligomer obtained by hydrolyzing and condensing perfluorosilane alone. The addition amount may be in the range of 0.01 to 10% by mass with respect to the solid content in the coating agent composition, and is effective for ensuring leveling properties during coating.

  The coating agent composition of the present invention obtained by the above method, further includes an organic and inorganic ultraviolet absorber, and a buffer for controlling the pH in the system to pH 2 to 7 where silanol groups are likely to exist stably. For example, optional components such as acetic acid-sodium acetate and disodium hydrogen phosphate-citric acid may be contained.

  The film thickness of the film formed on the substrate surface by the curable resin composition or the coating agent composition according to the present invention is usually controlled to 0.01 to 10 μm. The method for coating the surface of the composition with the composition is not particularly limited, such as a dipping method, a spin coating method, a flow coating method, a roll coating method, a spray coating method, or a screen printing method. Therefore, it is preferable to carry out the film thickness to a predetermined thickness by a dipping method, a spray method and a roll coating method.

  The present curable resin composition is coated on a synthetic resin transparent substrate. Specific examples of the synthetic resin are all applicable as long as they have excellent optical characteristics, but polycarbonate resins, polyalkylene terephthalate resins such as polyethylene terephthalate (PET), diacetyl cellulose, acetate butyrate cellulose, triacetyl Cellulose resins such as cellulose, acrylic resins, polystyrene resins, polyimide resins, polyester resins, polyethersulfone resins, polyarylate and other liquid crystalline resins, polyurethane resins, polysulfone resins, polyetherketone resins, trimethylpentene, polyvinylnorbornene Examples thereof include polyolefin resins such as ring structure-containing polyolefin resins, and composite resins thereof, but are not limited thereto. Particularly preferred are polycarbonate resins, polyalkylene terephthalate resins such as PET, triacetyl cellulose resins, acrylic resins, and polyolefin resins. The transparent substrate may be a molded part, a plate, or a film.

  When the resin composition is applied to a substrate, the resin composition can be cured even at 25 ° C. for 10 hours. When coating in a line is assumed, curing is preferably performed at 120 ° C. or less and within 10 minutes, and more preferably at 80 ° C. or less and within 5 minutes.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, in the following example,% is mass%, a part is mass part, and the average molecular weight in this specification shows the number average molecular weight of polystyrene conversion by gel permeation chromatography (henceforth GPC).

[Synthesis Example 1]
In a flask equipped with a stirrer, a condenser and a thermometer, a bissilane compound (CH ₃ O) ₃ Si—C ₂ H ₄ —C ₄ F ₈ —C ₂ H ₄ —Si (OCH ₃ ) ₃
200 parts, 100 parts of 3-glycidoxypropyltrimethoxysilane, 50 parts of 3-methacryloxypropyltrimethoxysilane, 500 parts of methanol silica sol (Nissan Chemical Industry Co., Ltd., containing 30% silica concentration), isopropyl alcohol 500 parts and 3 parts of a cation exchange resin were added and stirred and mixed at 25 ° C. 80 parts of water was added dropwise over 10 minutes. Further, the mixture was stirred at 40 ° C. for 3 hours to complete hydrolysis and condensation. This solution is diluted with isopropyl alcohol to a non-volatile content of 20%, the cation exchange resin is filtered off, 1.5 parts of polyether-modified silicone and 10 parts of aluminum acetoacetate (aluminum acetylacetonate) are added, and coating is performed. Agent solution (i) was prepared.

[Synthesis Example 2]
In a flask equipped with a stirrer, a condenser and a thermometer, a bissilane compound (CH ₃ O) ₃ Si—C ₂ H ₄ —C ₄ F ₈ —C ₂ H ₄ —Si (OCH ₃ ) ₃
350 parts of methanol, 500 parts of methanol silica sol (manufactured by Nissan Chemical Industries, containing 30% silica concentration), 500 parts of isopropyl alcohol, and 3 parts of cation exchange resin were stirred and mixed at 25 ° C. 80 parts of water was added dropwise over 10 minutes. Further, the mixture was stirred at 40 ° C. for 3 hours to complete hydrolysis and condensation. This solution is diluted with isopropyl alcohol to a non-volatile content of 20%, the cation exchange resin is filtered off, 1.5 parts of polyether-modified silicone and 10 parts of aluminum acetoacetate are added, and coating agent solution (ii) is added. Prepared.

In addition, various physical properties in the examples were measured and evaluated by the following methods.
[Painting method]
It was applied to an acrylic plate having a cleaned surface with a bar coater so as to have a film thickness of 5 μm and cured at 25 ° C. for 6 hours.
〔appearance〕
The transparency of the coating film and the presence or absence of defects were confirmed visually.
〔Pencil hardness〕
Judgment is made by the hardness of the pencil lead when a scratch is generated by scratching with the pencil lead at 45 °.
[Taber abrasion test]
Using a Taber abrasion tester (with wear wheel CS-10F), the abrasion test (500 g load, 100 revolutions) of the cured film is performed, and the haze of the cured film before and after the abrasion test is measured using a turbidimeter (NDH2000, Nippon Denshoku Industries). Haze after the wear test—Haze before the wear test was taken as ΔHaze.
[Water contact angle, oleic acid contact angle]
It measured using the contact angle meter (A3 type | mold by Kyowa Interface Science company).
(Dynamic friction coefficient)
Measured with Shinto Science HEIDON TRIBOGEAR TYPE HSS2000.
[Magic repellency]
Teranishi Chemical Company Magic Ink No. 500 Black [fingerprint wiping property]
After attaching the fingerprint, wipe it off with tissue paper, and visually determine the remaining oil.
[Storage stability]
The coating agent solution is allowed to stand at 25 ° C. for 30 days.

[Example 1]
The coating agent solution (i) obtained in Synthesis Example 1 was mixed with 1 part by mass of the following F-1.
The obtained compounded liquid was coated on a glass plate with a wire bar having a gap of 24 μm, and allowed to stand at 25 ° C. for 12 hours, and then the characteristics of the cured coated surface were examined. The results are shown in Table 1.

[Examples 2 and 3, Comparative Examples 1 to 3]
The coating agent solution (i) or (ii) obtained in Synthesis Example 1 or 2 is mixed with 1 part by mass of the following F-1 to F-4, and the resulting mixture is used in the same manner as in Example 1. The characteristics of the coated surface were examined. The results are shown in Table 1.

［Ｒｆ’：−ＣＦ₂（ＯＣＦ₂ＣＦ₂）_p（ＯＣＦ₂）_qＯＣＦ₂−
（ｐ／ｑ＝０．９、ｐ＋ｑ≒４５）］

［Ｒｆ’：−ＣＦ₂（ＯＣＦ₂ＣＦ₂）_p（ＯＣＦ₂）_qＯＣＦ₂−
（ｐ／ｑ＝０．９、ｐ＋ｑ≒４５）］
及び、本発明に相当しない化合物（Ｆ−４）
ＨＯＣＨ₂ＲＦＣＨ₂ＯＨ （Ｆ−４）
［ＲＦ：−ＣＦ₂（ＯＣＦ₂ＣＦ₂）_p（ＯＣＦ₂）_qＯＣＦ₂−
（ｐ／ｑ＝０．９、ｐ＋ｑ≒４５）］ The following compounds of the present invention (F-1 to F-3)

[Rf ′: —CF ₂ (OCF ₂ CF ₂ ) _p (OCF ₂ ) _q OCF ₂ −
(P / q = 0.9, p + q≈45)]

[Rf ′: —CF ₂ (OCF ₂ CF ₂ ) _p (OCF ₂ ) _q OCF ₂ −
(P / q = 0.9, p + q≈45)]
And the compound (F-4) not corresponding to the present invention
HOCH ₂ RFCH ₂ OH (F-4)
_{[RF: -CF 2 (OCF 2} CF 2) p (OCF 2) q OCF 2 -
(P / q = 0.9, p + q≈45)]

Claims (10)

(I) a bissilane compound (A) represented by the following general formula (1);
_{X n R 3-n Si-} C 2 H 4 -C m F 2m -C 2 H 4 -SiR 3-n X n (1)
(In the formula, R is a monovalent hydrocarbon group, X is an OH group or a hydrolyzable group, and n = 1, 2, or 3. m = 2 to 20 is an integer.)
Composite resin consisting of hydrolysis / condensation product of organosilicon compound containing epoxy group-containing silane compound (B) and / or unsaturated group-containing silane compound (C): 100 parts by mass
(Ii) Fluorine-containing alcohol compound represented by the following general formula (2): 0.005 to 20 parts by mass

(Wherein, Rf is .Q ¹ is a monovalent or divalent group having a molecular weight 100～40,000 containing a fluoroalkyl structure or fluoropolyether structure having at least (a + b) number of Si atoms, a siloxane structure, An unsubstituted or halogen-substituted silalkylene structure, a silarylene structure, or an (a + b) -valent linking group comprising a combination of two or more thereof, and may have a cyclic structure, Q ² has 1 to 20 carbon atoms A divalent hydrocarbon group, which may have a cyclic structure and may include an ether bond or an ester bond, and when Rf is monovalent, a ′ is 1 and a is 1 to 1. (When Rf is divalent, a is 1 and a ′ is 2. b is an integer of 1 to 20.)
(Iii) Curing catalyst: 0.1 to 10 parts by mass,
(Iv) Solvent: A curable resin composition containing an amount for adjusting the amount of solids to 0.5 to 50% by mass.   The curable resin composition according to claim 1, wherein the content of the component (A) is 20 to 80 parts by mass in the organosilicon compound, and the total amount of the component (B) and the component (C) is 20 to 80 parts by mass. object. (I ′) inorganic oxide fine particles (D) , and a bissilane compound (A) represented by the following general formula (1):
_{X n R 3-n Si-} C 2 H 4 -C m F 2m -C 2 H 4 -SiR 3-n X n (1)
(In the formula, R is a monovalent hydrocarbon group, X is an OH group or a hydrolyzable group, and n = 1, 2, or 3. m = 2 to 20 is an integer.)
Comprising an epoxy group-containing silane compound (B) and / or unsaturated group-containing silane compound (C) and hydrolysis-condensation product of an organic silicon compound containing, (D) component and (A) ~ (C) component of hydrolysis Composite resin with integrated decomposition / condensate: 100 parts by mass,
(Ii) Fluorine-containing alcohol compound represented by the following general formula (2): 0.005 to 20 parts by mass

(Wherein, Rf is .Q ¹ is a monovalent or divalent group having a molecular weight 100～40,000 containing a fluoroalkyl structure or fluoropolyether structure having at least (a + b) number of Si atoms, a siloxane structure, An unsubstituted or halogen-substituted silalkylene structure, a silarylene structure, or an (a + b) -valent linking group comprising a combination of two or more thereof, and may have a cyclic structure, Q ² has 1 to 20 carbon atoms A divalent hydrocarbon group, which may have a cyclic structure and may include an ether bond or an ester bond, and when Rf is monovalent, a ′ is 1 and a is 1 to 1. (When Rf is divalent, a is 1 and a ′ is 2. b is an integer of 1 to 20.)
(Iii) Curing catalyst: 0.1 to 10 parts by mass,
(Iv) Solvent: A curable resin composition containing an amount for adjusting the amount of solids to 0.5 to 50% by mass.   In the organosilicon compound, the content of the component (A) is 20 to 80 parts by mass, the total amount of the component (B) and the component (C) is 20 to 80 parts by mass, and the inorganic oxide fine particles and the organosilicon compound The curable resin composition according to claim 3, wherein the mass ratio is 10/90 to 60/40. Inorganic oxide fine particles (D) _{is, SiO 2, TiO 2, ZrO} 2, ZnO, curable according to claim 3, characterized in that as a main component at least one member selected from CeO ₂ Resin composition.   The curable resin composition according to any one of claims 3 to 5, wherein the inorganic oxide fine particles (D) have an average particle diameter of 1 to 80 nm. The curable resin composition according to any one of claims 1 to 6, wherein the bissilane compound (A) is represented by the following formula.
_{(CH 3 O) 3 Si-} C 2 H 4 -C m F 2m -C 2 H 4 -Si (OCH 3) 3
(In the formula, m is an integer of 2 to 20.) In the fluorine-containing alcohol compound of the general formula (2), Q ¹ represents the following formula (3)

[However, a broken line indicates a bond, a and b are the same as a and b in Formula (2), a unit having a repeating unit of a is bonded to Rf, and a unit having a repeating unit of b is represented by the following formula:

(However, Q ² is as defined in Formula (2).)
It bonds with the group shown by. Also, the arrangement of the two types of repeating units is random. Rf is as defined in Formula (2). ]
The curable resin composition of any one of Claims 1-7 represented by these. In the general formula (2), Q ² is —CH ₂ CH ₂ CH ₂ —,
_{-CH 2 CH 2 CH 2 CH 2} -,
_{-CH 2 CH 2 CH 2 CH 2} CH 2 -,
_{-CH 2 CH 2 CH 2 OCH 2} CH 2 -,
_{-CH 2 CH 2 CH 2 OCH 2} CH 2 OCH 2 CH 2 -,
_{-CH 2 CH 2 CH 2 OCH 2} CH 2 OCH 2 CH 2 OCH 2 CH 2 -,

The curable resin composition of any one of Claims 1-8 chosen from the group shown by these.   A coated article obtained by forming and coating a cured film of the curable resin composition according to any one of claims 1 to 9 on a substrate.