JP4420999B2 - Fluorine-containing silane compound, antifouling composition and antifouling article - Google Patents

Description

【００５２】
【発明の効果】
本発明により、優れた防汚性、耐磨耗性、膜強度を有する含フッ素化合物およびそれを被覆した防汚性物品を得る事ができる。[0001]
BACKGROUND OF THE INVENTION
A highly durable fluorine-containing silane compound that imparts a property that makes it difficult for dirt to adhere to the substrate surface and that can easily remove contaminants, an antifouling composition comprising the same as a main component, and a transparent substrate surface The present invention relates to an antifouling article coated with the antifouling composition.
[0002]
[Prior art]
A method of forming a water- and oil-repellent coating on the surface of transparent substrates such as anti-reflective surfaces used in display devices, etc., because dirt such as fingerprints easily adheres and impairs transparency and reflectivity. Attempts have been made to improve antifouling properties. As a method for obtaining such an antifouling layer, attempts to obtain a water- and oil-repellent film using a fluorine-containing compound are known. In recent years, for example, a silane compound having a perfluoroalkyl group as disclosed in JP-A-2-22372 is used. A method for forming a water- and oil-repellent layer by coating on a substrate after dissolving in a solvent has been known. However, these fluorine-containing coatings are excellent in water and oil repellency, but there are problems with the ease of attaching fingerprints and the removal of fingerprints, and the film itself is weak and the durability of the coatings is also problematic. Not satisfactory for use on display screen surfaces.
[0003]
[Problems to be solved by the invention]
When a transparent substrate used in a display device or the like is used by a person, dirt such as fingerprints, sign pens, makeup, and sweat is likely to adhere. Once attached, the dirt is difficult to remove. Therefore, in the present invention, a fluorine-containing silane compound that can be synthesized by a very simple technique that eliminates the above-mentioned drawbacks of the prior art, an antifouling composition containing the same as a main component, and an antifouling composition on the surface of a transparent substrate. It is an object of the present invention to provide an antifouling article coated with a fouling composition, in which dirt is difficult to adhere, removal of the fouling is easy, and film strength and abrasion resistance are excellent.
[0004]
[Means for Solving the Problems]
In order to achieve the above object, the antifouling composition of the present invention has the following constitution.
“(1) A reaction product of a compound A represented by the following formula, a polyfunctional amine, and an isocyanate silane or epoxy silane. The compound A and the isocyanate silane or epoxy silane are chemically structurally intercalated with the polyfunctional amine. A fluorine-containing silane compound characterized by being bonded to each other.
[0005]
Rf (COOH)_m
(Wherein Rf is an organic group containing at least one selected from a fluorine-containing oxaalkyl group, a fluorine-containing alkyl group, a fluorine-containing oxaalkylene group and a fluorine-containing alkylene group, m is an integer of 1 to 4)
(2) A reaction product of a compound A, a polyfunctional isocyanate, and a hydroxysilane, aminosilane, or carboxysilane, and the compound A and hydroxysilane, aminosilane, or carboxysilane are chemically structurally bonded via a polyfunctional isocyanate. A fluorine-containing silane compound characterized by
(3) A fluorine-containing silane compound, wherein Compound A and isocyanate silane are bonded.
(4) A fluorine-containing silane compound, wherein Compound A and aminosilane are bonded.
(5) An antifouling composition mainly comprising the same fluorine-containing silane compound as above.
(6) An antifouling article, wherein the antifouling composition is coated on a transparent substrate. "
[0006]
DETAILED DESCRIPTION OF THE INVENTION
Specific examples of the compound A of the present invention include the following as the fluorinated carboxylic acid.
[0007]
Af- (CH₂) k-COOH
HOOC- (CH₂) k-Bf- (CH₂) k-COOH
In the formula, k is an integer of 0 to 4, and l and m are integers of 1 to 15. Af is F (CF₂) n (n is an integer of 2 or more and 12 or less) or (CF₂CF (CF_Three) O), (CF₂CF₂O), (CF₂O), (CF (CF_ThreeAnd monovalent organic groups containing O) as a main component. As Bf, (CF₂) n (n is an integer of 2 or more and 12 or less) or (CF₂CF (CF_Three) O), (CF₂CF₂O), (CF₂O), (CF (CF_ThreeAnd divalent organic groups containing O) as a main component.
[0008]
In order to obtain higher antifouling properties, Af and Bf preferably have a structure containing the latter perfluoropolyether having a main chain having flexibility, a high molecular weight, and a high fluorine content. Among them, those having an arrangement in which the fluorine-containing polyether groups are randomly distributed can provide high antifouling property due to the flexibility of the main chain.
Specific examples of the compound A of the present invention include the following.
[0009]
F [CF (CF_ThreeCF₂O]_pCF (CF_ThreeCOOH
F [CF (CF_ThreeCF₂O]_pCF (CF_Three) CH₂OCOCF₂(OC₂F_Four)_p(OCF₂)_qOCF₂COOH
HOOCCF₂(OC₂F_Four)_p(OCF₂)_qOCF₂COOH
In the formula, p and q are 1 or more, preferably an integer of 2 to 200.
[0010]
With respect to the carboxyl group of compound A, the number is preferably 1 or 2 per molecule. When the number of carboxyl groups exceeds 3, when a compound A and a polyfunctional amine react to form an amide bond, a large amount of by-products tend to be generated.
[0011]
The molecular weight of Compound A is preferably 500 or more and 20000 or less, more preferably 1000 or more and 15000 or less. When the molecular weight is less than 500, the antifouling property decreases, and when it exceeds 20000, the film strength of the antifouling film tends to decrease and the reactivity during synthesis tends to decrease.
[0012]
The first aspect of the present invention will be described. Examples of the polyfunctional amine used for synthesizing the fluorine-containing silane compound include aliphatic, alicyclic and aromatic compounds containing two or more amino groups. Specific examples include ethylenediamine, diethylenetriamine, triethylenetetramine, diaminobenzene and the like.
[0013]
The fluorine-containing silane compound of the present invention is a compound in which Compound A and isocyanate silane or epoxy silane are bonded via a polyfunctional amine in terms of chemical structure. In this case, the compound A and the polyfunctional amine are reacted first to synthesize a terminal amine body, and then the terminal amino group is reacted with isocyanate silane or epoxy silane, or the polyfunctional amine and isocyanate silane or epoxy silane. It is possible to synthesize the compound of the present invention by a method in which the one-terminal amine compound is synthesized by first reacting with the compound A and subsequently reacted with the compound A.
[0014]
In general, a method using a condensing agent such as dicyclohexylcarbodiimide and diisopropylcarbodiimide is well known for the reaction between a carboxyl group and an amino group.
[0015]
Examples of the reaction product of compound A and polyfunctional amine suitable for the present invention obtained by such a method will be described below.
[0016]
F [CF (CF_ThreeCF₂O]_pCF (CF_Three) CONH (CH₂CH₂)_q(CH₂CH₂NH)_r(NH)_sH
(In the formula, p is 1 or more, preferably an integer of 2 to 120. q is 0 or an integer of 1 to 10. r is an integer of 0 or 1 to 6. s is 0 or 1. q and r. Are simultaneously 0, s is 0 if q is 0, and s is 1 if r is 0)
H₂NCH₂CH₂HNHOCCF₂(OC₂F_Four)_p(OCF₂)_qOCF₂CONHCH₂CH₂NH₂
(Wherein p and q are 1 or more, preferably an integer of 2 to 200)
Examples of the isocyanate silane used in the present invention include 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropylmethyldiethoxysilane.
[0017]
The reaction of these isocyanate silanes with the reaction product of the above compound A and a polyfunctional amine, that is, the reaction of isocyanate groups and amino groups easily occurs by a generally known method.
[0018]
The epoxy silane used in the present invention has at least one epoxy group, glycidyl group or alicyclic epoxy group and at least one hydrolyzable silane group such as chlorosilane group, alkoxysilane group or aminosilane group. Compounds. Specifically, 3,4-epoxybutyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) methyl Examples include dimethoxysilane, N-glycidyl-N, N-bis [3- (mailimethoxysilyl) propyl] amine, and N-glycidyl-N, N-bis “3- (trimethoxysilyl) propyl] amine.
[0019]
The reaction of these epoxy silanes with the reaction product of the above compound A and a polyfunctional amine, that is, the reaction of epoxy group and amino group easily occurs by a generally known method.
[0020]
The fluorine-containing silane compound of the present invention is a reaction product of Compound A, a polyfunctional amine, and isocyanate silane or epoxy silane, and may be used by mixing isocyanate silane and epoxy silane. In addition, the above-mentioned silanes are preferable because the trifunctional type with respect to hydrolyzability tends to increase the film strength when the antifouling film is formed.
[0021]
In this invention, since a polyfunctional amine is used, an oligomer and a polymer are easy to byproduce. Therefore, in each synthesis step, it is preferable to perform purification such as distillation as necessary to separate the target compound.
[0022]
The second aspect of the present invention will be described. Examples of polyfunctional isocyanates used to synthesize fluorine-containing silane compounds include tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, etc. For this purpose, a bifunctional isocyanate is preferred. Of these, tolylene diisocyanate is preferable because it has a low molecular weight and facilitates purification and separation of by-products after the reaction.
[0023]
The reaction between the carbonyl group and the isocyanate group is relatively easy, and the compound A and the polyfunctional isocyanate can be bonded by a generally known method. Examples of compounds that can be used in the present invention are described below.
[0024]
F [CF (CF_ThreeCF₂O]_pCF (CF_Three) COHNC₆H_Three(CH_ThreeNCO
(In the formula, p is 1 or more, preferably an integer of 2 to 120)
OCNC₆H_Three(CH_ThreeNHOCCF₂(OC₂F_Four)_p(OCF₂)_qOCF₂COHNC₆H_Three(CH_Three) NCO (wherein p and q are 1 or more, preferably an integer of 2 to 200)
Examples of the hydroxysilane include compounds having at least one hydroxy group and at least one hydrolyzable silane group such as a chlorosilane group, an alkoxysilane group, or an aminosilane group. Specific examples include hydroxymethyltriethoxysilane and condensed oligomers of the same compound.
[0025]
Examples of aminosilanes include compounds having at least one amino group and at least one hydrolyzable silane group such as a chlorosilane group, an alkoxysilane group, or an aminosilane group. Specific examples include 4-aminobutyltriethoxysilane, n- (2-aminoethyl) -3-aminopropyltrimethoxysilane, aminophenyltrimethoxysilane, and 3-aminopropyltriethoxysilane.
[0026]
Examples of carboxysilane include compounds having at least one carboxy group and at least one hydrolyzable silane group such as a chlorosilane group, an alkoxysilane group, or an aminosilane group. Specific examples include carboxymethyltriethoxysilane.
[0027]
In addition, the above-mentioned silanes are preferable because the trifunctional type with respect to hydrolyzability tends to increase the film strength when the antifouling film is formed.
[0028]
The fluorine-containing silane compound of the present invention is a reaction product of compound A, polyfunctional isocyanate, hydroxysilane, aminosilane, or carboxysilane, and these can be used in combination. The fluorine-containing silane compound is a compound in which the compound A and hydroxysilane, aminosilane, or carboxysilane are chemically structurally bonded via a polyfunctional isocyanate. In this case, the compound A and the polyfunctional isocyanate are reacted first to synthesize a terminal isocyanate, and then the terminal isocyanate is reacted with hydroxysilane, aminosilane or carboxysilane, or the polyfunctional isocyanate and hydroxysilane or aminosilane are reacted. Alternatively, the compound of the present invention can be synthesized by a method in which carboxysilane is reacted first to synthesize a one-terminal isocyanate compound and subsequently react with compound A. Both reactions occur relatively easily, and generally known methods can be used.
[0029]
Since a polyfunctional isocyanate is used, an oligomer or a polymer is easily produced as a by-product regardless of which synthesis process is used. Therefore, in each synthesis step, it is preferable to perform purification such as distillation as necessary to separate the target compound.
[0030]
Next, claim 3 of the present invention will be described. Examples of isocyanate silanes used for synthesizing fluorine-containing silane compounds include compounds having at least one isocyanate group and at least one hydrolyzable silane group such as a chlorosilane group, an alkoxysilane group or an aminosilane group. It is done. Specific examples include 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropylmethyldiethoxysilane.
[0031]
The reaction between the carboxyl group of compound A and the isocyanate group of isocyanate silane occurs relatively easily, and a generally known method can be used.
[0032]
Next, claim 4 of the present invention will be described. Examples of aminosilanes used to synthesize fluorine-containing silane compounds include compounds having one or more amino groups and one or more hydrolyzable silane groups such as chlorosilane groups, alkoxysilane groups, or aminosilane groups. . Specific examples include 4-aminobutyltriethoxysilane, n- (2-aminoethyl) -3-aminopropyltrimethoxysilane, aminophenyltrimethoxysilane, and 3-aminopropyltriethoxysilane. The above-mentioned silanes are preferable because the trifunctional type with respect to hydrolyzability is likely to increase the film strength when the antifouling film is formed.
[0033]
For the reaction between the carboxyl group of compound A and the amino group of aminosilane, a method using a condensing agent such as dicyclohexylcarbodiimide or diisopropylcarbodiimide is generally well known.
[0034]
The fluorine-containing silane compounds corresponding to the above-mentioned claims 1, 2, 3, and 4 can achieve the present invention even if they are used as they are without being hydrolyzed, but they may be hydrolyzed or hydrolyzed and condensed in advance. good. Hydrolysis or hydrolytic condensation is achieved by adding and stirring pure water or an acidic aqueous solution such as hydrochloric acid, acetic acid, phosphoric acid, nitric acid or sulfuric acid with or without dissolving the above compound in a solvent. The Furthermore, the degree of hydrolysis can be controlled by adjusting the amount of pure water or acidic aqueous solution added. In hydrolyzing, addition of a hydrolyzable group and an equimolar amount or more and a triple amount or less of pure water or an acidic aqueous solution is particularly preferable in terms of acceleration of curing.
[0035]
In the present invention, for the purpose of increasing the film strength, in addition to the above-mentioned fluorine-containing silane compounds corresponding to claims 1, 2, 3, and 4, methyl silicate, ethyl silicate, n-propyl silicate, i- Tetraalkoxysilanes such as propyl silicate, n-butyl silicate, sec-butyl silicate and t-butyl silicate, methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, methyltributoxysilane, Silane compounds such as ethyltrimethoxysilane, ethyltriethoxysilane, methyltrichlorosilane, ethyltrichlorosilane, dimethyldichlorosilane, and heptadecafluorodecyltrichlorosilane can also be blended. These polyfunctional organosilicon compounds or hydrolysates thereof may be added in an amount of 1 to 100 parts by weight, preferably 5 to 50 parts by weight, per 100 parts by weight of the fluorine-containing silane compound or the hydrolyzate thereof. . When the addition amount is less than 1 part by weight, the effect of improving the film strength is small, and when it exceeds 100 parts by weight, the antifouling performance tends to be lowered.
[0036]
In this way, an antifouling composition comprising a fluorine-containing silane compound as a main component is formed. An antifouling transparent article can be obtained by coating the antifouling composition itself or a solution dissolved in a solvent or a dispersion medium on a transparent substrate. Examples of the coating method include a wet process and a dry process.
[0037]
The wet process is not particularly limited, but a coating containing a fluorine-containing silane 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, and gravure coating. Then, the solvent is removed, and curing is performed at room temperature or by heating as necessary. The solvent used is preferably a general polar solvent or a fluorine-based solvent such as perfluorohexane, perfluorooctane, or trifluoroxylene.
[0038]
In addition, hydrolyzing alkoxysilane groups in the molecule and promoting condensation by siloxane bonds, pure water or acidic aqueous solutions such as hydrochloric acid, acetic acid, phosphoric acid, nitric acid or sulfuric acid, or aluminum acetylacetonate to accelerate curing The metal alkoxide may be added. In addition, a surfactant such as a fluorine-based surfactant or a silicon-based surfactant may be added in order to improve antifouling performance, optical performance, and surface performance.
[0039]
In addition, 1 to 200 parts by weight of inorganic compound fine particles or organic compound spherical fine particles selected from silica, aluminum oxide, magnesium oxide and calcium carbonate with respect to 100 parts by weight of the antifouling composition to improve the hardness of the coating. However, preferably 5 to 100 parts by weight may be added. When the transparent substrate is a resin such as polymethyl methacrylate, it is preferable to provide a hard coat layer on the substrate for the purpose of increasing the surface hardness.
[0040]
The dry process is not particularly limited, but the antifouling composition is coated on the transparent substrate by vapor deposition such as vacuum deposition, ion beam assisted deposition, ion plating, sputtering, and CVD. The method of doing is mentioned. Of these, the vacuum deposition method is preferred because the antifouling film can be continuously formed after the antireflection film is formed by the vacuum deposition method.
[0041]
The preferred film thickness of the film of the antifouling composition is 1 nm to 100 nm, more preferably 10 nm to 50 nm. If the film 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.
[0042]
As a preferred embodiment of the present invention, there is a mode in which the antifouling composition is provided on an organic or inorganic component single layer or multilayer antireflection film. Usually, an antireflection film using an organic component as a binder is formed on a transparent substrate by a wet process, and an antireflection film of an inorganic component is formed on a transparent substrate by a dry process. Among these, an antireflection film that is composed mainly of silicon dioxide as the outermost layer of the antireflection film and can be chemically bonded to the antifouling composition of the present invention is preferable in view of film strength and adhesion. Although the present invention is not limited, the antireflection film is preferably obtained by single layer or multilayer coating of inorganic oxide, inorganic nitride, fluorine-containing inorganic compound and the like. Examples of inorganic compounds used include silicon monoxide, silicon dioxide, zirconium oxide, aluminum oxide, yttrium oxide, ytterbium oxide, cerium oxide, hafnium oxide, tin oxide, titanium oxide, ITO and other oxides, and inorganic nitride such as silicon nitride And fluorine-containing inorganic compounds such as magnesium fluoride, calcium fluoride, sodium fluoride, cesium fluoride, and lithium fluoride.
[0043]
A method for forming the inorganic antireflection film is not particularly limited, and it is formed by a vacuum deposition method, an ion beam assisted deposition method, an ion plating method, a sputtering method, or the like.
[0044]
Furthermore, as a preferred embodiment of the present invention, when the transparent substrate is a resin, a hard coat layer is provided on the substrate, an antireflection film is provided thereon, and further, the antifouling composition of the present invention is coated. There is a way.
[0045]
By coating the transparent substrate with the antifouling composition comprising the fluorine-containing silane compound as a main component having the excellent antifouling property, abrasion resistance and film strength of the present invention on the transparent substrate as described above. Antifouling articles can be obtained.
[0046]
【Example】
EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
(Synthesis Example 1)
F [CF (CF_ThreeCF₂O]_nCF (CF_Three) COOH (n: average 18) 94.6g and H₂N (CH₂)₁₂NH₂3.5 g was dissolved in 100 ml of N, N-dimethylformamide (hereinafter abbreviated as DMF), a mixed solution of 9.3 g of dicyclohexylcarbodiimide and 20 ml of DMF was added dropwise in an ice bath, the ice bath was removed, and the mixture was stirred for 10 hours. To do. After the reaction, the generated urea was filtered off, and DMF was distilled off and purified to purify F [CF (CF_ThreeCF₂O]_nCF (CF_Three) CONH (CH₂)₁₂NH₂(N: average 18) was obtained.
(Synthesis Example 2)
HOOC-CF₂(OC₂F_Four) p (OCF₂qOCF₂-COOH (number average molecular weight 2000; p / q = 1) to 60 g in a nitrogen atmosphere at 50 ° C. with 1 drop of triethylamine and OCN-C₆H_Three(CH_Three) -NCO₂After 5.2 g was added dropwise and stirred for 24 hours, purification was performed and OCN-C₆H_Three(CH_Three) -NHCO-CF₂(OC₂F_Four) p (OCF₂qOCF₂-CONH-C₆H_Three(CH_Three) -NCO (p / q = 1) was obtained.
(Synthesis Example 3)
Substance F [CF (CF (CF synthesized in Synthesis Example 1)_ThreeCF₂O]_nCF (CF_Three) CONH (CH₂)₁₂NH₂(N: average 18) 42.5 g and isocyanate propyltriethoxysilane (OCN-CH) under a nitrogen atmosphere at 70 ° C.₂CH₂CH₂-Si (OCH₂CH_Three)_Three) 3.7 g and DBTDL (dibutyltin dilaurate: catalyst) 0.01 g were added dropwise, followed by stirring and reaction for 10 hours to obtain a yellow viscous liquid.
(Synthesis Example 4)
Substance F [CF (CF (CF synthesized in Synthesis Example 1)_ThreeCF₂O]_nCF (CF_Three) CONH (CH₂)₁₂NH₂(N: average 18) 42.5 g and 3-glycidoxypropyltrimethoxysilane (Ep-CH under 70 ° C. nitrogen atmosphere)₂OCH₂CH₂CH₂Si (OMe)_Three: Ep represents an epoxy group) 3.5 g and DBTDL (dibutyltin dilaurate: catalyst) 0.01 g were added dropwise, followed by stirring and reaction for 10 hours to obtain a yellow viscous liquid.
(Synthesis Example 5)
Substance OCN-C synthesized in Synthesis Example 2₆H_Three(CH_Three) -NHCO-CF₂(OC₂F_Four) p (OCF₂qOCF₂-CONH-C₆H_Three(CH_Three) -NCO 30g to hydroxymethyltriethoxysilane (HOCH under nitrogen atmosphere at 70 ° C)₂Si (OEt)_Three) 5.8 g and DBTDL (catalyst) 0.01 g were added dropwise, and after stirring and reaction for 10 hours, a yellow viscous liquid was obtained.
(Synthesis Example 6)
Substance OCN-C synthesized in Synthesis Example 2₆H_Three(CH_Three) -NHCO-CF₂(OC₂F_Four) p (OCF₂qOCF₂-CONH-C₆H_Three(CH_Three) -NCO 30 g and 3-aminopropyltriethoxysilane (H₂N (CH₂)_ThreeSi (OEt)_Three) 6.6 g and DBTDL (catalyst) 0.01 g were added dropwise, followed by stirring and reaction for 10 hours to obtain a yellow viscous liquid.
(Synthesis Example 7)
Substance OCN-C synthesized in Synthesis Example 2₆H_Three(CH_Three) -NHCO-CF₂(OC₂F_Four) p (OCF₂qOCF₂-CONH-C₆H_Three(CH_Three) -NCO 30g to carboxymethyltriethoxysilane (HOOCCH under nitrogen atmosphere at 70 ° C)₂Si (OEt)_Three) 6.7 g and 0.01 g of DBTDL (catalyst) were added dropwise, and after stirring and reacting for 10 hours, a yellow viscous liquid was obtained.
(Synthesis Example 8)
HOOC-CF₂(OC₂F_Four) p (OCF₂qOCF₂-COOH (number average molecular weight 2000; p / q = 1) to 70 g of isocyanate propyltriethoxysilane (OCN-CH) under a nitrogen atmosphere at 70 ° C₂CH₂CH₂-Si (OCH₂CH_Three)_Three7.4 g and DBTDL (catalyst) 0.01 g were added dropwise, and after stirring and reaction for 10 hours, a pale yellow viscous liquid was obtained.
(Synthesis Example 9)
HOOC-CF₂(OC₂F_Four) p (OCF₂qOCF₂-COOH (number average molecular weight 2000; p / q = 1) 30 g and 3-aminopropyltriethoxysilane (H₂N (CH₂)_ThreeSi (OEt)_Three) 6.6 g is dissolved in 100 ml of DMF, a mixed solution of 3.1 g of dicyclohexylcarbodiimide and 20 ml of DMF is added dropwise in an ice bath, the ice bath is removed, and the mixture is stirred for 10 hours. After the reaction, generated urea was filtered off, and DMF was distilled off to obtain a yellow viscous liquid.
[0047]
The progress of the reaction was traced by IR in each reaction, and for Synthesis Examples 3, 5, 6, 7, and 8, 2300 cm^-1Disappearance of characteristic absorption based on isocyanate groups appearing in the vicinity, 3000 cm for Synthesis Example 4^-1Disappearance of characteristic absorption based on epoxy group appearing in the vicinity, about 1600 cm for Synthesis Example 9^-1Disappearance of characteristic absorption based on carboxylate appearing in the vicinity and 1680 cm^-1The reaction was confirmed by the occurrence of characteristic absorption based on the amide appearing in the vicinity.
(Creation of antireflection film)
An inorganic antireflection film was prepared by the following method.
[0048]
An ethanol solution mainly composed of silica sol (135 parts by weight), hydrolyzate of γ-glycidoxypropyltriethoxysilane (129 parts by weight), and hydrolyzate of γ-chloropropyltrimethoxysilane (70 parts by weight) was added to the polycarbonate plate. ZrO, an inorganic substance, is applied on both sides and hardened to form a hard coat film.₂/ SiO₂/ TiO₂/ SiO₂The outermost layer is SiO in this order by vacuum evaporation.₂Thus, the film thickness was set to λ / 4 (λ = 540 nm), respectively, and multilayer coating was performed.
(Examples 1-7)
On the inorganic antireflection film, the materials synthesized in Synthesis Examples 3 to 9 were coated by vacuum deposition to obtain an antifouling antireflection article.
(Comparative Example 1)
Substance F [CF (CF (CF) synthesized in Synthesis Example 1 on an inorganic antireflection film_ThreeCF₂O]_nCF (CF_Three) CONH (CH₂)₁₂NH₂Thus, an antifouling antireflective article in which the above film was formed by vacuum deposition was obtained.
(Comparative Example 2)
The substance OCN-C synthesized in Synthesis Example 2 on an inorganic antireflection film₆H_Three(CH_Three) -NHCO-CF₂(OC₂F_Four) p (OCF₂qOCF₂-CONH-C₆H_Three(CH_ThreeAn antifouling antireflective article having a film of) -NCO formed by vacuum deposition was obtained.
(Comparative Example 3)
An antifouling antireflective article in which a film of perfluorooctylethyltrimethoxysilane was formed on an inorganic antireflective film by vacuum deposition was obtained.
[0049]
In addition, the antifouling antireflection articles obtained in the above Examples and Reference Examples were evaluated by the following evaluation means.
[0050]
a. Fingerprint wiping property: A finger was pressed against the surface for 3 seconds to attach the fingerprint, and the tissue paper was reciprocated to wipe the fingerprint, and the ease of fingerprint wiping was determined. Judgment criteria are as follows.
A: Fingerprints can be wiped off completely in 10 round trips
○: Fingerprints can be completely wiped off in about 20 round trips
Δ: Wipe off in about 30 round trips
×: Wipe left after 30 round trips
XX: Cannot be taken at all
b. Steel wool (SW) hardness: Use steel wool # 0000, 250g / cm²Reciprocate with load. Judgment criteria are as follows.
◎: No scratches after 20 round trips
○: 10 round trips without scratches
Δ: 10 round trips with several scratches
×: 10 round trips with scratches
XX: The surface peels after 10 reciprocations
c. Scratch resistance: 2 kg / cm of cleaning cloth (Bencot M3: manufactured by Asahi Kasei)²100 reciprocations with load. Judgment criteria are as follows.
A: No change
○: Some change in contact angle
Δ: Some change in reflectivity
×: Reflection color changes
XX: Peel
The evaluation results are shown in the following table.
[0051]
[Table 1]

[0052]
【The invention's effect】
According to the present invention, a fluorine-containing compound having excellent antifouling properties, abrasion resistance and film strength and an antifouling article coated therewith can be obtained.

Claims (11)

It is a reaction product of the compound A represented by the following formula, a polyfunctional amine, and an isocyanate silane or an epoxy silane, and the compound A and the isocyanate silane or the epoxy silane are chemically structurally bonded via a polyfunctional amine. A fluorine-containing silane compound characterized by comprising:
Rf (COOH) _m
(In the formula, Rf is an organic group mainly composed of at least one fluorine-containing polyether group selected from (OC ₂ F ₄ ), (OCF ₂ ) and (OC ₃ F ₆ )) , and m is an integer of 1 to 4. ) It is a reaction product of the compound A, a polyfunctional isocyanate, and a hydroxysilane, aminosilane, or carboxysilane, and the compound A and hydroxysilane, aminosilane, or carboxysilane are chemically structurally bonded via a polyfunctional isocyanate. The fluorine-containing silane compound according to claim 1 . The fluorine-containing silane compound according to claim 1, wherein the compound A and isocyanate silane are bonded. The fluorine-containing silane compound according to claim 1, wherein the compound A and aminosilane are bonded to each other. The fluorine-containing silane compound according to any one of claims 1 to 4 , wherein the compound A has one or two carboxyl groups per molecule. The antifouling composition which has as a main component the fluorine-containing silane compound in any one of Claims 1-5 . An antifouling article obtained by coating the antifouling composition according to claim 6 on a transparent substrate. Have a single-layer or multi-layer anti-reflection film of an organic or inorganic component on a transparent substrate, further claim 7, wherein the antifouling composition according to claim 6, wherein is characterized by comprising coated thereon Antifouling goods. 9. The antifouling article according to claim 8 , wherein the outermost layer of the antireflection film is a layer mainly composed of silicon dioxide. The antifouling article according to any one of claims 8 to 9 , wherein a hard coat layer is provided between the transparent substrate and the antireflection film. The antifouling article according to any one of claims 7 to 10 , wherein the antifouling composition according to claim 7 is coated using a vacuum deposition method.