JP2000169481A - Fluorine-containing compound and antifouling article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new fluorine-containing compound capable of synthesizing by a simple technique, scarcely attaching stain when applied onto a transparent substrate, capable of readily removing pollutant, providing an antifouling article excellent in adhesiveness, strength and abrasion resistance of film. SOLUTION: This fluorine-containing compound is obtained by reacting one or more kinds of compounds represented by the formula R1-Af-R1[Af is a divalent fluorine-containing organic group; R1 is (CH2)a-OR2 [R2 is H or the like; (a) is 1-4] e.g. a perfluroalkylene of the formula HO-(CH2)k-Bf-(CH2)k-OH [(k) is 1-4; Bf is (CF2)n (n is 2-12)]} with one or more kinds of silane compounds represented by the formula Si(R3)i (R4)j(OR5)4-(i+j) [R3 and R4 are each an organic group containing at least one of H, carbon, oxygen or fluorine; R5 is an organic group containing at least one selected from aliphatic, alicyclic and aromatic residues; (i) and (j) are each 0 or 1] [e.g. preferably a fluorine- containing silane represented by the formula CF3CH2Si(OCH3)3].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a highly durable fluorine-containing compound which imparts a property that dirt does not easily adhere to the surface of a substrate and easily removes contaminants, and a surface of a transparent substrate coated with the antifouling composition. The present invention relates to an antifouling article.

[0002]

2. Description of the Related Art A transparent substrate such as an antireflection-treated surface used for a display device or the like easily adheres to a stain such as a fingerprint and impairs transparency and reflectivity. Attempts have been made to improve antifouling properties by a method of forming a film. As a method for obtaining such an antifouling layer, an attempt to obtain a water- and oil-repellent film using a fluorine-containing compound has been known. In recent years, for example, a silane compound having a perfluoroalkyl group as disclosed in JP-A-2-22372 has been used. A method of forming a water- and oil-repellent layer by coating a substrate after dissolving in a solvent has become known. However, although these fluorine-containing coatings are excellent in water and oil repellency, they have problems in the ease with which fingerprints are attached and the ability to remove fingerprints. Therefore, it is not satisfactory for use on the display screen surface.

[0003]

A transparent substrate used for a display device or the like easily adheres to stains such as fingerprints, felt-tip pens, makeup, and sweat when used by humans, and once adhered, it is difficult to remove the stains. Therefore, in the present invention, a fluorine-containing compound that can be synthesized by a very simple method that has solved the above-mentioned disadvantages of the conventional technology, and the dirt coated on a transparent substrate is less likely to adhere, and the removal of contaminants is reduced. An object of the present invention is to provide an antifouling article which is easy and excellent in coating adhesion, film strength and abrasion resistance.

[0004]

Means for Solving the Problems To achieve the above object, the antifouling composition of the present invention has the following constitution.

"One or more fluorine-containing alcohol compounds represented by the following general formula and R ¹ -A ^f -R ¹ (A ^f : a divalent fluorine-containing organic group having a linear or branched structure, R ¹ :-(CH ₂ ) _a -OR ² (R ² is a hydrogen atom or-(CH ₂ CH (O
H) CH ₂ O) _b H, or - (wherein _{CH 2 CH 2 O) c -H} , a is an integer from 1 to 4, b is an integer of 1 to 3, c is an integer of 1 to 15. ), A fluorine-containing compound characterized by reacting at least one silane compound represented by the following general formula.

Si (R3) _i (R4) _j (OR5) _{4- (i + j)} (wherein R3 and R4 are organic groups containing a carbon, hydrogen, oxygen or fluorine atom, and R5 is an aliphatic or alicyclic And i represents an integer of 0 or 1, and j represents an integer of 0 or 1.)

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, one or more of the following fluorine-containing alcohol compounds are used. R ¹ -A ^f -R ¹ (A ^f : a linear or branched divalent fluorinated organic group, R ¹ :-(CH ₂ ) _a -OR ² (R ² is a hydrogen atom or-(CH ₂ CH (O
H) CH ₂ O) _b H, or - (wherein _{CH 2 CH 2 O) c -H} , a is an integer from 1 to 4, b is an integer of 1 to 3, c is an integer of 1 to 15. Specific examples include the following.

HO- (CH ₂ ) k-Bf- (CH ₂ ) k-OH HO- (CH ₂ CH ₂ O) l- (CH ₂ ) k-Bf- (CH ₂ ) k- (OCH ₂ CH ₂ ) m-OH HOCH ₂ CH (OH) CH ₂ -O- (CH ₂ ) k-Bf- (CH ₂ ) kO-CH ₂ CH (OH) CH ₂ OH k is an integer of 1 to 4, l and m are 1 Bf is a perfluoroalkylene represented by (CF ₂ ) n (n is an integer of 2 or more and 12 or less) or (CF ₂ CF (CF ₃ ) O), (CF ₂ C
(F ₂ O), (CF ₂ O), a divalent organic group containing as a main component a fluorinated polyether group selected from (CF (CF ₃ ) O), to obtain a higher antifouling property Preferably, Bf has a structure in which the main chain has flexibility, has a large molecular weight, and contains the latter perfluoropolyether having a high fluorine content. Among them, those having an arrangement in which the above-mentioned fluorinated polyether groups are randomly distributed provide high antifouling properties due to the flexibility of the main chain. The molecular weight is preferably from 500 to 20,000, more preferably from 1,000 to 10,000. If the molecular weight is less than 500, the antifouling property is reduced, and
If it exceeds 000, the reactivity at the time of synthesis tends to decrease.

The silane compound used for synthesizing the fluorine-containing compound in the present invention has the following structure.

Si (R 3) _i (R 4) _j (OR 5) _{4- (i + j)} (wherein R 3 and R 4 represent an organic group containing at least one selected from carbon, hydrogen, oxygen and a fluorine atom; Represents at least one selected from aliphatic, alicyclic and aromatic residues, i represents 0 or 1, j represents 0 or 1, and k represents an integer of 0 or 1.) Specifically, methyl silicate G, ethyl silicate, n-
Propyl silicate, i-propyl silicate, n-butyl silicate, sec-butyl silicate and t-butyl silicate
Tetraalkoxysilanes such as butyl silicate, furthermore, methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane Silane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, vinyldimethylethoxysilane, vinylmethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloro Propyltriethoxysilane,
γ-chloropropyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N
-Β- (aminoethyl) -γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, methyltriphenoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycid Xymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane,
β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, diethoxy-3-glycidoxypropylmethylsilane, dimethoxy-3-glycidoxypropylmethyl Silane, 3
-Glycidoxypropyldimethoxysilane, γ- (meth) acryloyloxypropyldimethylethoxysilane, γ- (meth) acryloyloxypropylmethyldiethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltri Butoxysilane, γ-glycidoxypropyltrimethoxyethoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-
Glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ- Glycidoxybutyltrimethoxysilane, δ
-Glycidoxybutyltriethoxysilane, (3,4-
Epoxycyclohexyl) methyltrimethoxysilane,
(3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4
-Epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxyethoxysilane, β- (3
4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) propyltriethoxysilane, δ- (3,4
Trialkoxysilanes such as -epoxycyclohexyl) butyltrimethoxysilane, δ- (3,4-epoxycyclohexyl) butyltriethoxysilane, triacyloxysilanes or triphenoxysilanes and dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane Silane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane,
Dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ -Aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane,
α-glycidoxyethylmethyldiethoxysilane, β-
Glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyl Dibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane γ-glycidoxypropylethyldipropoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldi Dialkoxysilane or diacyloxysilanes such as ethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane,
Tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-t
ert-butoxysilane, tetrapentaethoxysilane, tetrapenta-iso-propoxysilane, tetrapenta-n-propoxysilane, tetrapenta-n-butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-butoxysilane, methyltripropoxysilane, Examples thereof include silane compounds such as dimethylethoxysilane, dimethylmethoxysilane, dimethylpropoxysilane, dimethylbutoxysilane, methyldimethoxysilane, hexyltrimethoxysilane, and γ- (meth) acryloyloxypropyltrimethoxysilane.

Among the silane compounds, fluorine-containing silane compounds are particularly preferably used, and the following are exemplified.

CF ₃ CH ₂ Si (OCH ₃ ) ₃ , CF ₃ CH ₂ Si (OC ₂ H ₅ ) ₃ , C ₄ F
₉ CH ₂ Si (OCH ₃ ) ₃ , C ₄ F ₉ CH ₂ Si (OC ₂ H ₅ ) ₃ , C ₆ F ₁₃ CH ₂ Si (OCH ₃ )
_{3, C 6 F 13 CH 2} Si (OC 2 H 5) 3, C 8 F 17 CH 2 Si (OCH 3) 3, C 8 F 17 CH 2
_{Si (OC 2 H 5) 3} , CF 3 C 2 H 4 Si (OCH 3) 3, CF 3 C 2 H 4 Si (OC 2 H 5) 3, C
₄ F ₉ C ₂ H ₄ Si (OCH ₃ ) ₃ , C ₄ F ₉ C ₂ H ₄ Si (OC ₂ H ₅ ) ₃ , C ₆ F ₁₃ C ₂ H ₄ Si
_{(OCH 3) 3, C 6} F 13 C 2 H 4 Si (OC 2 H 5) 3, C 8 F 17 C 2 H 4 Si (OCH 3) 3,
C ₈ F ₁₇ C ₂ H ₄ Si (OC ₂ H ₅ ) ₃ , C ₆ F ₁₃ C ₂ H ₄ SiCH ₃ (OCH ₃ ) ₂ , C ₆ F ₁₃ C
₃ H ₆ Si (OC ₂ H ₅ ) ₃ , C ₈ F ₁₇ C ₂ H ₄ SiCH ₃ (OCH ₃ ) ₂ , C ₁₆ F ₃₃ C ₂ H ₄ Si
_{(OCH 3) 3, C 18} F 37 C 2 H 4 Si (OCH 3) 3, C 20 F 41 C 2 H 4 Si (OC
H ₃ ) ₃ .

In general, the functional group-containing fluorine-containing compound can be produced by various methods. In the present invention, one or more of the above-mentioned fluorine-containing polyhydric alcohol and one or more of the silane compounds are subjected to the following alcohol removal. By performing the condensation, a fluorine-containing compound can be easily obtained. In addition, this compound is generally a polycondensate, and has a feature of having high adhesion to a substrate when containing an unreacted alkoxysilane group in the molecule.

The dealcoholation reaction -Rx-OH + RyO-Si- → -Rx-O-
The Si- + RyOH reaction can be carried out without solvent or in a solvent. As the solvent, a polar solvent such as DMF or DMSO or a fluorine-based solvent such as perfluorohexane, perfluorooctane or trifluoroxylene is used. it can. The reaction temperature is preferably from room temperature to about 200 ° C., but it is preferable to carry out the reaction at a temperature at which the produced alcohol evaporates. Further, in order to completely remove the formed alcohol, 5 to 20
The reaction may be completed by reducing the pressure to 0 torr.

In the condensation by the dealcoholation reaction, sodium or a basic catalyst such as sodium hydroxide or lithium hydroxide, or a metal such as sodium methoxide or sodium ethoxide for the purpose of increasing the reaction rate. Alkoxides can also be used as catalysts.

It is preferable to add 50 to 400 moles of a silane compound to 100 moles of the fluorinated alcohol and to conduct condensation polymerization by a dealcoholization reaction. If it exceeds 300, the antifouling property tends to decrease.

For the purpose of adjusting the molecular weight, a molecular weight modifier may be used. The molecular weight regulator is not particularly limited, but a compound represented by the following formula 5 or 6 is desirable.

X1X2X3Si (OR6) Formula 5 (X1, X2, X3 represent an organic group containing a carbon, hydrogen, oxygen, nitrogen, sulfur or fluorine atom, and R6 represents an aliphatic, alicyclic or aromatic residue. indicating each.) R7-OH ··· equation 6 (R7 are specific examples of compounds represented by a monovalent organic group) formula _{5 (CH 3) 3 Si (} OC
H ₃ ), (CH ₃ ) ₃ Si (OC ₂ H ₅ ) and the like. Specific examples of the compound represented by the formula 6 include F (CF ₂ ) pCH ₂ OH and F (CF ₂ )
pCH ₂ CH ₂ OH, H (CF ₂ ) pCH ₂ OH, F (CF ₂ ) p (CH ₂ ) ₆ OH, CF ₃ (CF ₃ )
_{CF (CF 2) rCH 2 CH} 2 OH, CF 3 (CF 3) CF (CF 2) r (CH 2) 6 OH (p is 1
An integer of 10 to 10, and r is an integer of 1 to 8).

The number average molecular weight of the fluorine-containing compound thus synthesized is preferably from 1 × 10 ³ to 1 × 10 ⁶ .

When the thus obtained fluorine-containing compound is coated on a transparent substrate, an antifouling transparent substrate can be obtained. Examples of the coating method include a wet process and a dry process. The wet process is not particularly limited, but a coating containing a fluorine-containing compound is applied by a solution coating method such as spin coating, dip coating, die coating, spray coating, bar coating, roll coating, curtain flow coating, or gravure coating. Then, the solvent is removed, and if necessary, the mixture is cured at room temperature or by heating. As a solvent to be used, a general polar solvent or a fluorine-based solvent such as perfluorohexane, perfluorooctane, trifluoroxylene and the like is preferable. In addition, pure water or an acidic aqueous solution such as hydrochloric acid, acetic acid, phosphoric acid, nitric acid or sulfuric acid, or aluminum acetyl for accelerating hardening is used to hydrolyze unreacted alkoxysilane groups in the molecule and promote condensation by siloxane bonds. A metal alkoxide such as acetonate may be added. In addition, surfactants such as a fluorine-based surfactant or a silicon-based surfactant as modifiers for antifouling performance, optical performance, and surface performance, Si, Al, Sn, Sb, Zn,
Oxidation of Ti, fine particles such as magnesium fluoride and calcium fluoride, fluororesins such as polytetrafluoroethylene, and organic silicon compounds such as ethyl silicate and perfluorooctylethyltrimethoxysilane or a hydrolyzate thereof are also added. good.

On the other hand, the dry process is not particularly limited, but includes a vacuum deposition method, an ion beam assisted deposition method, an ion plating method, a sputtering method,
A method in which a fluorine-containing compound is coated on a transparent substrate by a vapor phase growth method such as a VD method is exemplified.

The preferred film thickness of the fluorine-containing compound film is 1 nm to 100 nm, more preferably 10 nm to 50 nm. If the thickness is less than 1 nm, the antifouling effect is poor, and if it is more than 100 nm, the film strength tends to be weak.

In a preferred embodiment of the present invention, the above-mentioned fluorine-containing compound is provided on a single-layer or multilayer antireflection film of an organic or inorganic component. Normal,
The antireflection film using an organic component as a binder is formed by a wet process, and the antireflection film of an inorganic component is formed by a dry process. Above all, the outermost layer of the antireflection film is composed of a layer mainly composed of silicon dioxide, and an antireflection film capable of chemically bonding to the fluorine-containing compound of the present invention is preferable in view of film strength and adhesion. Although the present invention is not limited thereto, it is preferable that the antireflection film is obtained by coating an inorganic oxide, an inorganic nitride, a fluorine-containing inorganic compound, or the like with a single layer or a multilayer. Examples of the inorganic compound used include oxides such as silicon monoxide, silicon dioxide, zirconium oxide, aluminum oxide, yttrium oxide, ytterbium oxide, cerium oxide, hafnium oxide, tin oxide, ITO, inorganic nitrides such as silicon nitride, and fluorine. And fluorine-containing inorganic compounds such as magnesium fluoride, calcium fluoride, sodium fluoride, cesium fluoride, and lithium fluoride.

The method of forming the inorganic antireflection film is not particularly limited, but is formed by a vacuum deposition method, an ion beam assisted deposition method, an ion plating method, a sputtering method, or the like.

When the transparent substrate is a resin such as polymethyl methacrylate, a hard coat layer is preferably provided between the substrate and the antireflection film for the purpose of increasing the surface hardness.

By coating a fluorine-containing compound having excellent antifouling properties, abrasion resistance and film strength of the present invention on a transparent substrate by the above method, the desired antifouling article can be obtained. You can get it.

[0027]

Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

(Synthesis Example 1) 15 mmol of perfluoropolyethylene glycol compound HO-CH ₂ CF ₂ (CF ₂ CF ₂ O) n-CF ₂ CH ₂ -OH (number average molecular weight 1500), 8 mmol of ethyl silicate and sodium methoxide (Catalyst) 0.005
g, stirred at 100 ° C for 1 hour, reacted at 150 ° C for 4 hours while gradually increasing the temperature, and further reacted at 150 ° C under reduced pressure of 20 torr for 1 hour to obtain a colorless viscous liquid. Was.

(Synthesis Example 2) HO-CH ₂ -CF ₂ (OC ₂ F ₄ ) p (OCF ₂ ) qO
CF ₂ -CH ₂ -OH (Ausimont FOMBLIN Z DOL number average molecular weight 2000; p / q = 1) 15 mmol, ethyl silicate 8 mmol and sodium methoxide (catalyst) 0.00
5 g were mixed and stirred at 100 ° C. for 1 hour, and reacted at 150 ° C. for 4 hours while gradually increasing the temperature, and then further at 20 torr.
When the reaction was carried out at 150 ° C. for 1 hour under reduced pressure, a yellow viscous liquid was obtained.

(Synthesis Example 3) HO-CH ₂ -CF ₂ (OC ₂ F ₄ ) p (OCF ₂ ) qO
15 mmol of CF ₂ -CH ₂ -OH (FOMBLIN Z DOL number-average molecular weight 2000; p / q = 1) of Asimont and CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂
11 mmol of Si (OCH ₃ ) ₃ and 0.005 g of sodium methoxide (catalyst) were mixed, stirred at 100 ° C. for 1 hour, reacted at 150 ° C. for 4 hours while gradually increasing the temperature, and then further reduced under reduced pressure of 20 torr. When the reaction was performed at a temperature of 1 hour, a yellow viscous liquid was obtained.

(Synthesis Example 4) HO-CH ₂ CH ₂ (OH) CH ₂ O-CF ₂ (OC ₂ F
_{4) p (OCF 2) qOCF} 2 -CH 2 -OCH 2 CH (OH) CH 2 -OH ( Ausimont FOMBLIN Z TETRAOL number average molecular weight 2000; p / q = 1) and 15mmol of ethyl silicate 8mmol and sodium methoxide ( (Catalyst) 0.005 g was mixed in 20 g of DMF, stirred at 100 ° C. for 1 hour, and gradually heated to 15
After reacting at 0 degree for 4 hours, the mixture was further reacted at 150 degree under reduced pressure of 20 torr for 1 hour, and the solvent was distilled off to obtain a yellow viscous liquid.

[0032] By IR in each of the reaction to track the progress of the reaction, the reaction was confirmed by a decrease in characteristic absorption based on OH groups appearing in the vicinity of 3000cm ^-1 ~3600cm ^-1.

(Preparation of Antireflection Film) An inorganic antireflection film was prepared by the following method.

An ethanol solution mainly containing silica sol (135 parts by weight), a hydrolyzate of γ-glycidoxypropyltriethoxysilane (129 parts by weight), and a hydrolyzate of γ-chloropropyltrimethoxysilane (70 parts) was used. An inorganic substance, ZrO ₂ / SiO ₂ / TiO ₂ / SiO, was applied to both sides of a polycarbonate plate and cured to form a hard coat film.
₂ were coated in this order by a vacuum deposition method so that the outermost layer would be SiO ₂ with a film thickness of λ / 4 (λ = 540 nm).

(Examples 1 to 4) The substances synthesized in Synthesis Examples 1 to 4 were respectively coated on the above-mentioned inorganic antireflection films by vacuum evaporation to obtain antifouling antireflection articles.

Comparative Example 1 HO-CH ₂ was coated on an inorganic anti-reflection film.
-CF ₂ (OC ₂ F ₄ ) p (OCF ₂ ) qOCF ₂ -CH ₂ -OH (Ausimont FOM
BLIN Z DOL An antifouling antireflective article having a coating having a number average molecular weight of 2000; p / q = 1) was formed by vacuum evaporation.

(Comparative Example 2) An antifouling antireflection article was obtained in which a film of perfluorooctylethyltrimethoxysilane was formed on the inorganic antireflection film by a vacuum evaporation method.

The antifouling antireflection articles obtained in the above Examples and Reference Examples were evaluated by the following evaluation means.

A. Fingerprint wiping property: A finger was pressed against the surface for 3 seconds to attach a fingerprint, a tissue paper was reciprocated to wipe the fingerprint, and the ease of wiping the fingerprint was determined. The criteria are as follows.

A: A fingerprint can be completely wiped off in about 10 round trips. A: A fingerprint can be completely wiped out in about 20 round trips. Δ: Can be wiped out in about 30 round trips. b. Steel wool (SW) hardness: Steel wool # 0
Use No. 000 and reciprocate at a load of 250 g / cm ² . The criteria are as follows. ：: No scratches after 20 reciprocations ○: No scratches after 10 reciprocations △: Several scratches after 10 reciprocations ×: Scratches after 10 reciprocations XX: Surface peeled after 10 reciprocations c. Scratch resistance: Cleaning cloth (Bencott M3:
(Made by Asahi Kasei) 100 reciprocations with a load of ² kg / cm ² . The criteria are as follows. ◎: no change ：: slight change in contact angle △: slight change in reflectance ×: change in reflected color XX: peeling The evaluation results are shown in the following table.

[0041]

[Table 1]

[0042]

According to the present invention, an antifouling article which does not easily adhere dirt, easily removes contaminants, and has excellent coating adhesion, film strength and abrasion resistance, and a fluorine-containing compound suitable therefor. Could be provided.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (Reference) C08G 65/22 C08G 65/22 65/336 65/32 Q C09D 5/16 C09D 5/16 183/08 183/08 C09K 3/00 112 C09K 3/00 112D 112E 112F // C09K 3/18 102 3/18 102 104 104 F F-term (reference) 4H020 BA11 BA12 BA32 BA36 4H049 VN01 VP01 VQ02 VQ11 VQ19 VQ20 VR11 VR12 VR21 VR22 VR42 VR43 VR44 VS02 VS02 VU17 VU21 VW02 4J005 AA09 BD08 4J038 DL071 NA05 PB11 PC03 PC08

Claims (11)

[Claims] 1. A method according to claim 1, wherein at least one fluorine-containing alcohol compound represented by the following general formula and R ¹ -A ^f -R ¹ (A ^f : a linear or branched divalent fluorine-containing organic group, R ¹ :-( CH ₂ ) _a -OR ² (R ² is a hydrogen atom or-(CH ₂ CH (O
H) CH ₂ O) _b H, or - (wherein _{CH 2 CH 2 O) c -H} , a is an integer from 1 to 4, b is an integer of 1 to 3, c is an integer of 1 to 15. ), A fluorine-containing compound obtained by reacting at least one silane compound represented by the following general formula. Si (R3) _i (R4) _j (OR5) _{4- (i + j)} (wherein R3 and R4 are organic groups containing at least one selected from carbon, hydrogen, oxygen and fluorine atoms, and R5 is aliphatic , At least one selected from alicyclic and aromatic residues, i represents 0 or 1, and j represents an integer of 0 or 1.) 2. ^Af is (OCF ₂ ), (OC ₂ F ₄ ), (O
C ₃ F ₆₎ fluorine-containing compound according to claim 1, characterized in that the main component a fluorine-containing polyether group selected from. 3. The fluorine-containing compound according to claim 1, wherein the silane compound is a fluorine-containing silane compound. 4. A fluorine-containing alcohol 100 represented by the formula 1.
The silane compound represented by the formula 2 is used in an amount of 50 mol to
The fluorine-containing compound according to any one of claims 1 to 3, which is obtained by polycondensation by a dealcoholization reaction after adding 400 moles. 5. A curable composition comprising the fluorine-containing compound according to claim 1 as a main component. 6. A paint containing the fluorine-containing compound according to claim 1. 7. An antifouling article comprising a transparent substrate coated with the fluorine-containing compound according to any one of claims 1 to 4. 8. A transparent substrate having a monolayer or multilayer antireflection film of an organic or inorganic component, and further thereon.
The antifouling article according to claim 7, which is coated with the fluorine-containing compound according to any one of (1) to (4). 9. The antifouling article according to claim 8, wherein the outermost layer of the antireflection film is a layer mainly composed of silicon dioxide. 10. The antifouling article according to claim 8, wherein a hard coat layer is provided between the transparent substrate and the antireflection film. 11. The antifouling article according to claim 7, wherein the fluorine-containing compound is coated by a vacuum deposition method.