KR20060095442A - Method for producing resin article coated with anti-staining film - Google Patents

Abstract

A method for producing a resin article coated with an anti-staining film which comprises providing an under-layer comprising a resin or an inorganic compound and having a siliceous surface, on the surface of a transparent resin base material, and applying a coating fluid containing a silicon alkoxide, a silane compound having a fluoroalkyl group and an acid on the under-layer, followed by drying. The method can be employed for producing a resin article coated with an anti-staining film which can prevent the surface of a transparent resin base material, such as an anti- reflecting film, from being stained by a fingerprint, a skin fat, a sweat, a cosmetic or the like and allows the easy removal of such a stain in case it is attached to the film and further exhibits high resistance to marring and weathering, without the need for a special device and with high productivity.

Description

Manufacturing method of antifouling film coating resin article {METHOD FOR PRODUCING RESIN ARTICLE COATED WITH ANTI-STAINING FILM}

The present invention relates to a method for producing an antifouling film-coated resin article. More specifically, it relates to the manufacturing method of the antifouling film coating resin article which provided antifouling property to the surface of the transparent resin substrate or transparent resin film used for the display screen of a display especially.

Plastics having transparency take advantage of various advantages such as optical properties, light weight, and ease of processing and thinning, and are highly demanded in the optical market or film market such as liquid crystal-related members and optical disks. In particular, in display screens such as liquid crystal displays, projection displays, plasma displays, and EL displays, plastic materials having transparency are used alone or in combination with glass as main materials. The purpose of the display is to provide an explosion-proof auxiliary effect, an antistatic effect, a transmittance adjustment effect, an antireflection effect, an antifouling effect, etc., and a laminate formed by laminating on a resin film serving as a substrate by combining films having various functions. The sieve was attached to glass to form a display screen substrate, or the laminate was directly laminated on a transparent resin sheet to form a display screen substrate. As one example thereof, a hard coat film, a transparent conductive film, an antireflection film, and an antifouling film are laminated on this PET film in this order. Herein, the antifouling film means a film that is hard to adhere to the surface of a stain such as a fingerprint, and which has a function of easily removing the dirt even once attached.

As a technique of an antifouling film, Japanese Laid-Open Patent Publication No. Hei 7-16940 discloses an air of a monomer having perfluoroalkyl (meth) acrylate and an alkoxysilane group on this optical thin film of an optical article having an optical thin film mainly composed of silicon dioxide. It is known to form a thin film of coalescence.

Japanese Laid-Open Patent Publication No. 2000-327818 discloses an antireflection film having a SiO ₂ layer at a surface layer of a coating agent in which a perfluoro group-containing triethoxysilane is added as a solute to a solution containing perfluoro group-containing phosphate ester as a catalyst. It is described to apply | coat on this anti-reflective film of the optical article which has the thing to form an antifouling layer.

Japanese Laid-Open Patent Publication No. 2001-188102 discloses forming an antifouling layer by forming a perfluoropolyether group-containing silane coupling agent by vacuum deposition on a top layer of an antireflection film having an antireflection layer on an upper surface of a transparent film substrate. It is proposed.

Japanese Unexamined Patent Publication No. Hei 11-71682 discloses hydrophilic treatment of a surface in a plasma or corona atmosphere containing oxygen in advance, or an ultraviolet ray having a wavelength of around 200 to 300 nm in an atmosphere containing oxygen. Was applied to a surface of the plastic substrate subjected to the hydrophilization treatment, and a solution containing a silicon alkoxide (or a monomer or a polymer of 19 or less monomers), a fluoroalkyl group-containing silane compound, and an acid was applied. A method for producing a water repellent article, which is subsequently dried to form a water repellent coating, is described.

However, in the technique of JP-A-7-16940, there is a problem that the production efficiency is lowered because the reaction after application takes a long time. In the methods disclosed in Japanese Unexamined Patent Application Publication Nos. 2000-327818 and 11-71682, there is a problem in that antifouling expression takes a long time, the antifouling performance is low, or the antifouling property tends to decrease with use. In addition, in the technique of JP 2001-188102 A, a special apparatus such as a vacuum deposition apparatus is required.

Disclosure of the Invention

The present invention has a large contact angle of water droplets so as to prevent the adhesion of fingerprints, sebum, sweat, cosmetics, etc. to the surface of a transparent resin substrate such as an antireflection film, and to be wiped off easily even if attached, It is an object of the present invention to provide a resin article coated with an antifouling film which is excellent and additionally has high scratch resistance and weather resistance at high production efficiency without requiring a special apparatus.

Other objects and advantages of the present invention will become apparent from the following description.

According to this invention, the said objective and advantage of this invention prepare the transparent resin base material which has at least the base layer which consists of a siliceous resin or an inorganic compound on the surface, and on the base layer of this transparent resin base material, The coating liquid containing a silicon alkoxide, a fluoroalkyl group containing silane compound, and an acid is apply | coated, and then dried, and it is achieved by the manufacturing method of the antifouling film coating resin article characterized by forming an antifouling layer.

Preferred Embodiments of the Invention

In this invention, the underlayer which consists of a resin or inorganic compound whose surface is a silicate at least is formed on the surface of a transparent resin base material. SiO ₂ on the surface of the resin underlayer or the inorganic compound underlayer Or it is preferable that the content rate of Si-O is 20 weight% or more. The following 5 types can be mentioned as an aspect of this underlayer.

[Base layer 1]

At least a silica base hard coat layer is mentioned as a resin base layer whose surface is silica. This hard coat layer is represented by following formula (1)

R ¹ _a R ² _b Si (OR ³ ) _4-ab (1)

Here, R ¹ is a hydrocarbon group having 1 to 4 carbon atoms, an epoxy group having 2 to 12 carbon atoms, an allyl group having 6 to 12 carbon atoms or a halogenated alkyl group, and methacryl having 5 to 8 carbon atoms. An oxyalkyl group, a ureidoalkylene group having 2 to 10 carbon atoms, an aromatic ureidoalkylene group, an aromatic alkylene group and a mercaptoalkylene group, R ² Is an alkyl group, aryl group, alkenyl group, halogenated alkyl group or halogenated aryl group having 1 to 6 carbon atoms, R ³ Is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, an acyl group, an alkylacyl group, a is 1, 2 or 3, b is 0, 1 or 2,

Compound,

And a coating liquid containing colloidal silica is applied to the surface of the substrate and cured by heating at 50 to 130 ° C. for several seconds to 5 hours. It is preferable that this hard coat layer has a thickness of 1-10 micrometers. As an organosilane compound represented by said Formula (1), for example, trimethylmethoxysilane, phenyl dimethyl methoxysilane, vinyl dimethyl methoxysilane, (gamma) -acryloxypropyl dimethyl methoxysilane, (gamma)-mercaptopropyl dimethyl methoxy Monofunctional silanes such as silane, N-β (aminoethyl) γ-aminopropyldimethylmethoxysilane and β- (3,4-epoxycyclohexyl) ethyldimethylmethoxysilane; Dimethyldimethoxysilane, Phenylmethyldimethoxysilane, Vinylmethyldimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-glyci Bifunctional silanes such as doxypropylmethoxydiethoxysilane and β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane: methyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, γ -Acryloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane and and trifunctional silanes such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Among them, alkyltrialkoxysilanes such as methyltrimethoxysilane, ethyltriethoxysilane, methyltriethoxysilane and ethyltrimethoxysilane are particularly preferably used.

40-900 weight part of colloidal silica is preferable with respect to 100 weight part of compounds represented by said Formula (1), and, as for the compounding ratio of each component, 250-500 weight part is more preferable. The coating liquid is adjusted as a dispersion containing a predetermined amount of the active ingredient in a liquid medium such as alcohol.

The colloidal silica is, for example, 10 to 50% by weight of SiO ₂ , preferably 1 to 200 nm in particle size, more preferably 1 to 100 nm in SiO _2. It can be derived from colloidal silica sol having particles as an active ingredient or composite oxide fine particles containing SiO ₂ in the range of 1 to 200 nm, more preferably 1 to 100 nm. This composite oxide is SiO ₂ It is a composite of a metal oxide and one or two or more metals selected from the group consisting of Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, Pd, In and Ti. And oxides thereof. Specific examples are Al ₂ 0 ₃ , SnO ₂ , Sb ₂ O ₅ , CeO ₂ , Ta ₂ O ₅ , La ₂ O ₃ , Fe ₂ O ₃ , ZnO, WO ₃ , ZrO ₂ , PdO ₂ , In ₂ O ₃ And TiO ₂ There is. As composite oxide fine particles containing SiO ₂ , composite oxide fine particles of titanium and silicon (TiO ₂ ㆍ SiO ₂ ), composite oxide fine particles of titanium, cerium and silicon (TiO ₂ · CeO ₂ ㆍ SiO ₂ ), titanium, iron and silicon Composite oxide fine particles (TiO ₂ ㆍ Fe ₂ O ₃ ㆍ SiO ₂ ), composite oxide fine particles of titanium, zirconium and silicon (TiO ₂ ㆍ ZrO ₂ ㆍ SiO ₂ ), composite oxide fine particles of titanium, aluminum and silicon (TiO ₂ Al ₂ O ₃ ㆍ SiO ₂ ) and the like.

SiO _{2 in} these composite oxide fine particles It is preferable that 5 mol% or more of components are contained.

The complex oxide may be surface modified with an organosilane compound in order to increase dispersibility in a solvent. The usage-amount of an organosilane compound becomes like this. Preferably it is 20 weight% or less with respect to the weight of a composite oxide fine particle. Surface treatment may be performed with the organosilane compound used for a process having a hydrolysis group, and may be performed after hydrolysis. Examples of the organosilane compound include trimethylmethoxysilane, phenyldimethylmethoxysilane, vinyldimethylmethoxysilane, γ-acryloxypropyldimethylmethoxysilane, γ-mercaptopropyldimethylmethoxysilane, and N-β (amino Monofunctional silanes such as ethyl) γ-aminopropyldimethylmethoxysilane and β- (3,4-epoxycyclohexyl) ethyldimethylmethoxysilane; Dimethyldimethoxysilane, Phenylmethyldimethoxysilane, Vinylmethyldimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-glyci Bifunctional silanes such as doxypropylmethoxydiethoxysilane and β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane: methyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, γ -Acryloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane and trifunctional silanes such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; Tetrafunctional silanes such as tetraethylorthosilicate and tetramethylorthosilicate. When treating a complex oxide with such a silane compound, it is preferable to carry out in water, alcohol, or another organic medium, for example.

[Base layer 2]

The said silicate hard coat layer apply | coats the hard-coat liquid containing (A) polyfunctional acrylate, (B) aminosilane, and (C) colloidal silica, and is obtained by ultraviolet irradiation. It is preferable that this hard coat layer has a thickness of 1-10 micrometers.

Each component of the said hard coat liquid is demonstrated.

The polyfunctional acrylate which is (A) component is the (meth) acrylate which has at least 2 hydroxyl group and at least 2 (meth) acryloyl group in a molecule | numerator. In addition, in this specification, acryloyl group or a methacryloyl group is referred to as a (meth) acryloyl group, an acrylate or a methacrylate (meth) acrylate, and acrylic acid or methacrylic acid are (meth) acrylic acid. . As a polyfunctional (meth) acrylate, 1, 6- hexanediol diacrylate, 1, 4- butanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, for example. , Tripropylene glycol diacrylate, neopentyl glycol diacrylate, 1,4-butanediol dimethacrylate, poly (butanediol) diacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol diacrylate Diacrylates, such as the rate, a triethylene glycol diacrylate, a triisopropylene glycol diacrylate, a polyethylene glycol diacrylate, and a bisphenol A dimethacrylate; Triacrylates such as trimethylolpropanetriacrylate, trimethylolpropanetrimethacrylate, pentaerythritol monohydroxytriacrylate, and trimethylolpropanetriethoxytriacrylate; Tetraacrylates such as pentaerythritol tetraacrylate and di-trimethylolpropane tetraacrylate; And pentaacrylates such as pentaerythritol (monohydroxy) pentaacrylate. A polyfunctional (meth) acrylate is used together 1 type or 2 types or more.

The aminosilane which is (B) component is an alkoxysilane which has an amino group or a substituted amino group. Preferably the following formula (2)

X _a Si (R ⁴ (NHR ⁵ ) _b NR ⁶ H) _4-a (2)

X is an alkoxyl group having 1 to 6 carbon atoms, R ⁴ and R ⁵ are the same or different divalent hydrocarbon groups, R ⁶ is a hydrogen atom or a monovalent hydrocarbon group, and a is an integer of 1 to 3 , b is 0 or an integer of 1 to 6,

It is an amino organic functional silane represented by. In Formula (2), a is preferably 2 or 3, and b is preferably 0 or 1.

As aminosilane represented by Formula (2), for example, n- (2-aminoethyl-3-aminopropyl) trimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl)- (gamma) -aminopropylmethyldimethoxysilane hydrochloride and (gamma) -anilinopropyl trimethoxysilane.

As colloidal silica which is (C) component, the same thing as what was mentioned above can be used.

It is preferable that this hard-coat liquid contains the photoinitiator for superposition | polymerization of polyfunctional (meth) acrylate. As a photoinitiator, a radical photoinitiator, a cationic photoinitiator, etc. can be used, for example. As a radical photoinitiator, benzophenone, [2-hydroxy-2-methyl-1-phenylpropane-1-one], [1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane- 1-one], [4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propylketone], [2,2-dimethoxy-1,2-diphenylethan-1-one] , [1-hydroxycyclohexyl-phenyl-ketone], [2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one], [bis (2,6- Dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphineoxide], [2-benzyl-2-dimethylamino-1-1- (4-morpholinophenyl) -butanone-1] Moreover, as a cationic photoinitiator, it is phenyl- [m- (2-hydroxy tetradicyclo) phenyl] iodonium hexafluoro antimonate, dialkyl iodonium, tetrakis (pentafluoro phenyl) borate Etc. can be illustrated.

As for the quantity of a photoinitiator, 0.1-30 weight part is preferable with respect to 100 weight part of polyfunctional (meth) acrylates of a hard-coat composition, More preferably, it is 1-15 weight part.

It is preferable that this hard coat liquid contains the hydrolysis catalyst for hydrolysis and condensation polymerization of an aminosilane (B). As the hydrolysis catalyst, for example, acid catalysts such as formic acid, acetic acid, propionic acid, butanoic acid, oxalic acid, (meth) acrylic acid, hydrochloric acid, nitric acid and sulfuric acid, and basic catalysts such as ammonia, sodium hydroxide and aqueous potassium hydroxide solution are used. Among them, acid catalysts in the form of an aqueous solution such as acetic acid and (meth) acrylic acid are preferably used. It is preferable that the quantity of the acid catalyst to add is 5-30 weight part with respect to 100 weight part of aminosilane (B).

The hard coat liquid is preferably 1.5 to 50 parts by weight of the amino organic functional silane (B), more preferably 8 to 25 parts by weight, and colloidal to 100 parts by weight of the polyfunctional (meth) acrylate (A). Silica (C) is a solid content, Preferably it is 10-150 weight part, More preferably, it contains 40-85 weight part.

[Base layer 3]

In the present invention, an antireflection film can be cited as an inorganic compound underlayer whose at least surface is silica. As the anti-reflection film, at least one inorganic compound film layer (silicon oxide film in the case of one layer and silicon oxide film in the case of two or more layers) has a film thickness of 20 nm to 50 μm (in the case of two or more layers, the total film). Thickness) can be formed. Inorganic compounds include, for example, silicon oxide (silicon dioxide, silicon monoxide), metal oxides such as aluminum oxide, magnesium oxide, titanium oxide, tin oxide, zirconium oxide, thorium oxide, antimony oxide, indium oxide, bismuth oxide, yttrium oxide Cerium oxide, zinc oxide, ITO (indium-tin oxide) and the like; Metal halides such as magnesium fluoride, calcium fluoride, sodium fluoride, lanthanum fluoride, cerium fluoride, lithium fluoride, thorium fluoride and the like. Examples of the method for forming the antireflection film include chemical vapor deposition (CVD) and physical vapor deposition (PVD). Examples of the CVD method include a plasma CVD method, a PVD method, a vacuum vapor deposition method, a reactive vapor deposition method, an ion beam assist method, a sputtering method, an ion plating method, and the like.

As a structure of a specific inorganic compound film layer, the following are mentioned, for example.

TiO ₂ / SiO ₂ by vacuum deposition, sputtering or plasma CVD Formation of laminated film (Lamination of SiO ₂ layer on TiO ₂ layer. 2-layer antireflection film).

TiO ₂ / SiO ₂ / TiO ₂ / SiO ₂ by vacuum deposition, sputtering or plasma CVD Formation of a laminated film (4-layer antireflection film).

Formation of a film of a SiO ₂ / TiO ₂ / SiO ₂ / TiO ₂ / SiO ₂ laminated film by vacuum deposition, sputtering or plasma CVD (5-layer antireflection film).

Formation of a SiOx film by plasma CVD (single layer antireflection film).

[Base layer 4]

As a base layer of the inorganic compound whose surface is a silicate at least, the single layer reflection prevention layer which consists of silica fine particles is mentioned. This single layer antireflection layer can be formed to a thickness of 70 to 350 nm by applying and heating the following low reflection layer solution.

The low reflection layer solution is hydrolyzed as (1) raw material fine particles comprising at least one of non-aggregated silica fine particles having an average particle diameter of 40 to 1,000 nm and chain-shaped aggregated silica fine particles having an average primary particle diameter of 10 to 100 nm, and (2) a binder. One or more species of alkoxysilanes and possible oligomers or alkoxysilanes represented by the following formula (4), and water and a solvent are mixed, and the (2) binder is hydrolyzed in the presence of the fine particles and the catalyst. Then, it is the liquid which added the curing catalyst.

As said hydrolyzable alkoxysilane, tetraalkoxysilane like tetraethoxysilane is used, for example, What is represented by following formula (3) as another alkoxysilane is mentioned.

R ⁷ _a R ⁸ _b Si (OR ⁹ ) _4-ab (3)

Here, R <^7> is a C1-C4 alkyl group, a C6-C12 allyl group or a halogenated alkyl group, a C5-C8 methacryloxyalkyl group, a C2-C10 ureidoalkyl An alkylene glycol group having an alkyl group at one end, an aromatic ureidoalkylene group, an aromatic alkylene group, or a mercaptoalkylene group, and R ⁸ is an alkyl group having 1 to 6 carbon atoms , An aryl group, an alkenyl group, a halogenated alkyl group or a halogenated aryl group, R ⁹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an acyl group or an alkylacyl group, a = 1, 2 or 3, b = 0 , 1 or 2. And a + b is 1, 2 or 3.

R ¹⁰ 0-((RO) ₂ -Si-O) _n -R ¹⁰ (4)

Here, R ¹⁰ is an alkyl group having 1 to 4 carbon atoms, n = 1 to 20, and the structure of the condensate includes a chain structure, a branched structure, and a cyclic structure.

The silica fine particles and the binder are blended in a weight ratio, preferably in a ratio of 60:40 to 95: 5. Further, the non-aggregated silica fine particles in the low reflection layer liquid preferably have a ratio between the major axis length and the minor axis length of 1.0 to 1.2, and the primary particle diameter standard deviation is preferably 1.0 to 1.5.

[Base layer 5]

The hard coat layer of a silicon resin is mentioned at least as a base layer of resin whose surface is silica. This hard coat layer is the following formula (5)

R ¹ _a R ² _b Si (OR ³ ) _4-ab (5)

Here, R ¹ is a hydrocarbon group having 1 to 4 carbon atoms, an epoxy group having 2 to 12 carbon atoms, an allyl group having 6 to 12 carbon atoms or a halogenated alkyl group, and methacryl having 5 to 8 carbon atoms. An oxyalkyl group, a ureidoalkylene group having 2 to 10 carbon atoms, an aromatic ureidoalkylene group, an aromatic alkylene group and a mercaptoalkylene group, R ² Is an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkenyl group, a halogenated alkyl group or a halogenated aryl group, R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, an acyl group or an alkylacyl group, and a is 1 , 2 or 3, b is 0, 1 or 2,

Compound,

And a coating liquid containing tetraalkoxysilane, followed by curing by heating at 50 to 130 ° C. for several seconds to 5 hours. It is preferable that this hard coat layer has a thickness of 1-10 micrometers. About the compound of said Formula (5), description about Formula (1) in the said base layer 1 is applicable as it is. As tetraalkoxysilane, tetramethoxysilane, tetraethoxysilane, its polymer (preferably 19 monomers or less), or these hydrolyzate are mentioned.

40-900 weight part of tetraalkoxysilanes are preferable with respect to 100 weight part of compounds represented by said Formula (5), and, as for the compounding ratio of each component, 250-500 weight part is more preferable. It is adjusted as a liquid containing a predetermined amount of the active ingredient in a liquid medium such as alcohol.

These underlayers 1 to 5 form an antireflection layer such as underlayers 3 and 4 as a layer directly below the antifouling layer, for example, and a hard coat layer such as underlayers 1 and 2 as the lower layer. , 5 can be formed.

Surfactant, an alkali metal salt, electroconductive fine particles, or a charge transfer complex can be added to these base layers 1-5 as needed, and an antistatic property or electroconductivity can be provided further to a base layer by this.

As surfactant, for example, "electro stripper QN" (anionic), "electro stripper ACz" (positive), "electro stripper F", "electro stripper EA" (nonionic), "Armit 302" (non-ionic) Warmth), `` homogenol) L-18 '' (special polymer), `` homogenol L1820 '' (special polymer) (both manufactured by Kaou Corporation) and `` FZ-2105 '' by Nihon Unika Co., Ltd., `` L-7604 "," L-77 "," L-7001 "," FZ-2123 ", and" FZ-2162 "(all nonionic) are mentioned. The amount of addition is preferably 0.05 to 50 parts by weight based on 100 parts by weight of the active ingredient of the membrane.

Examples of the conductive fine particles include metals such as ATO (antimony-tin oxide) having a particle diameter of 1 to 100 nm, a metal oxide of ITO, and silver, and are usually in the form of a dispersion. The addition amount is preferably 1 to 80 parts by weight based on 100 parts by weight of the active ingredient of the membrane. As microparticles | fine-particles, the thing of spherical shape, an elliptical shape, a fibrous form, and flaky shape is used. In order to improve electroconductive efficiency, it is preferable that it is fibrous form and flaky shape.

Examples of the charge transfer complex include hyborone, which is a boron-based antistatic agent manufactured by Boron International. The addition amount is preferably 1 to 20 parts by weight based on 100 parts by weight of the active ingredient of the membrane.

In the present invention, the antifouling coating liquid is coated on the above-described base layer, and dried at room temperature for 10 seconds to 10 minutes, preferably 10 to 100 nm thick, more preferably 10 to 30 nm thick. Form an antifouling layer. This antifouling coating liquid contains a silicon alkoxide, a fluoroalkyl group-containing silane compound, and an acid. As the silicon alkoxide, tetraalkoxysilanes such as tetraethoxysilane and tetramethoxysilane or polymers thereof (preferably 19 monomers or less) or hydrolyzates thereof are preferably used.

As a fluoroalkyl group containing silane compound, the silane compound containing a fluoroalkyl group and also containing an alkoxy group, an alkoxyl group, or a chloro group can be used preferably. For example, the compound represented by following General formula (6) and (7) is mentioned. Among these, it can be used individually or in combination of some compound.

CF _3- (CF ₂ ) _n -R ¹¹ -SiX _p Y _{3 -p} (6)

(Wherein n is an integer from 0 to 12, preferably an integer from 3 to 12, R ¹¹ is a divalent organic group having 1 to 10 carbon atoms (e.g., methylene group, ethylene group), or silicon atom and oxygen A group containing an atom, X is a monovalent hydrocarbon group having 1 to 4 carbon atoms (e.g., alkyl group, cycloalkyl group, allyl group) or a substituent selected from these derivatives, or hydrogen, p is 0, 1 or 2, Y Is an alkoxyl group or alkoxyl group having 1 to 4 carbon atoms)

CF _3- (CF ₂ ) _n -R ¹² -SiX _p Cl _{3 -p} (7)

(Wherein n is an integer from 0 to 12, preferably 3 to 12, R ¹² is a methylene group, an ethylene group, or a group containing a silicon atom and an oxygen atom, X is H or an alkyl group, a cycloalkyl group, An allyl group or a substituent selected from these derivatives, p is 0, 1 or 2)

As the silane represented by the formulas (6) and (7), for example, C ₈ F ₁₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , C ₈ F ₁₇ CH ₂ CH ₂ Si (CH ₃ ) (OCH ₃ ) ₂ Particular preference is given to C ₈ F ₁₇ CH ₂ CH ₂ SiCl ₃ (3-heptadecafluorodecyltrichlorosilane) and C ₈ F ₁₇ CH ₂ CH ₂ Si (CH ₃ ) C ₁₂ .

As the acid contained in the antifouling coating liquid, for example, volatile acids such as hydrochloric acid, nitric acid and acetic acid are preferably used.

As a solvent of the antifouling coating liquid, an alcohol type hydrophilic solvent, a ketone type hydrophilic solvent, etc. are used preferably. Among them, chain-type saturated monohydric alcohols having 3 or less carbon atoms such as methanol, ethanol, 1-propanol and 2-propanol are more preferably used because of their high evaporation rate at room temperature. As a ketone hydrophilic solvent, acetone, methyl ethyl ketone, etc. are mentioned, for example.

The antifouling coating liquid is preferably,

(A) 0.01-2 wt% of silicon alkoxide or its hydrolyzate (in terms of silica),

(B) 0.00001 to 0.15% by weight of a fluoroalkyl group-containing silane compound (in terms of silica),

(C) 0.001-3 acid, and

(D) 0 to 5% by weight of water

It contains. More preferably,

(A) 0.01-2 wt% of silicon alkoxide or its hydrolyzate (in terms of silica),

(B) 0.00001 to 0.15% by weight of a fluoroalkyl group-containing silane compound (in terms of silica),

(C) hydrochloric acid 0.001 to 3, and

(D) 0-5 weight% of water,

Provided that the weight ratio of acid / water is at least 0.002, preferably at least 0.02.

The antifouling coating liquid can be prepared by dissolving the components (A) to (C) in an alcohol solvent, but the chlorosilyl group-containing compound and the fluoroalkyl group-containing silane compound are dissolved in a solvent containing alcohol and / or water. It is also possible to prepare by replacing the chloro group of the chlorosilyl group-containing compound with an alkoxyl group or hydroxyl group.

In this invention, in order to improve the adhesiveness of the above-mentioned base layer and a transparent resin base material, a primer layer can be formed between a base layer and a transparent resin base material. Moreover, an antistatic layer can be formed between a base layer and a transparent resin base material.

Although it does not specifically limit as this primer layer, For example, what used the urethane type, acryl type, urethane acrylate type, or partially silanized as a main component, and adjusted the density with the organic solvent is used. As a commercial item, the silicone acrylic primer liquid (CP710, Nippon ARC Co., Ltd.) and urethane primer liquid (CP620, Nippon ARC Co., Ltd. product) can be used. As a processing method, it is obtained by apply | coating the processing liquid for primer layers to the transparent resin base material surface, and drying it. The preferable thickness of this primer layer is 0.5-5 micrometers. As a solvent of the treatment liquid for primer layers, although organic solvents, such as alcohol, are used, water may be sufficient.

When forming a transparent conductive film in the antifouling film coating resin article in this invention, a film of ITO (indium tin oxide) can be formed by sputtering etc. just under the above-mentioned base layer, for example.

As a structure of the antifouling | stain-resistant film coating resin article obtained by this invention, the following can be illustrated.

(1) Transparent resin base material / primer / hard coat / transparent conductive film / antireflection film / antifouling film.

(2) Transparent resin base material / hard coat / transparent conductive film / antireflection film / antifouling film.

(3) Transparent resin base material / hard coat / antireflection film / antifouling film.

(4) Transparent resin base material / antireflection film / antifouling film.

(5) Transparent resin base material / primer / antireflection film / antifouling film.

(6) Transparent resin base material / hard coat / antifouling film.

(7) Transparent resin base material / primer / hard coat / antifouling film.

(8) Transparent resin base material / hard coat / antireflection (antistatic) / antifouling film.

(9) Transparent resin base material / hard coat (conductive) / antireflection / antifouling film.

In the present invention, the material of the transparent resin substrate is, for example, triacetyl cellulose resin, polymethyl methacrylate resin, polycarbonate resin, polyethylene resin, polyethylene terephthalate resin, polystyrene resin, cycloolefin polymer, polyether sulfone resin, allyl Transparent resins, such as a diglycol carbonate resin, are mentioned. These transparent resin sheets, films, and the like are used as the substrate.

The present invention is, for example, a light diffusion processing film of a mobile phone light guide plate, a display such as a notebook personal computer, a monitor, a PDP, a front panel of a projection TV, an outermost surface processing film of a PDA, an outermost surface processing film of a touch panel monitor, a portable It is used to form antifouling films on windows of telephones, areas requiring high optical characteristics, and transparent parts for automobiles.

According to the present invention, as described above, a resin article coated with an antifouling film having high scratch resistance and weather resistance, which prevents dirt from adhering to the surface of the transparent resin substrate and is easily wiped even when attached, does not require a special device. Is obtained with high production efficiency.

An Example is given to the following and embodiment of this invention is described concretely.

The base material used in the Example and the comparative example, the formation method of an antireflection layer, the formation method of various coat layers, the evaluation method, etc. are as follows.

Resin Base:

(1) Polycarbonate (PC) (Trade name: Polykaace, Part No .: ECK-100, Chuchu Naka Plastic Industries, Ltd.) Sheet thickness 2 mm. (2) Polyethylene terephthalate resin (PET) (brand name: Cosmoshine A4300, Toyobo Co., Ltd. product), film thickness 188 micrometers. (3) Cycloolefin polymer (COP) (brand name: ZEONOR, part number: 1600, Nippon Xeon Corporation make), film thickness 188 micrometers. (4) Polymethyl methacrylate (PMMA) (trade name: Acrylite Mitsubishi Rayon Co., Ltd.), sheet thickness 2 mm.

Formation of Anti-Reflection Layer 1:

SiO ₂ was formed in a sputtering gas into a high frequency magnetron sputtering method by Ar gas, and the film to a 1.2 ㎛ / hr. SiO ₂ The refractive index of the film was 1.46. In addition, and TiO ₂ are formed in the sputter gas with a DC magnetron sputtering method in mixed gas of Ar and O _2, and the film at a rate of 1.4 ㎛ / hr. TiO ₂ The refractive index of the film was 2.30.

In order from the first layer, TiO ₂ (nd = 60 nm) / SiO ₂ (nd = 40 nm) / TiO ₂ It was a four-layer structure of (nd = 110 ㎚) / SiO 2 (nd = 140 ㎚). In addition, the parenthesis has shown the value of optical film thickness (refractive index (n) x physical film thickness (d)).

Formation of Anti-Reflection Layer 2:

In the same manner as in the formation of the anti-reflection layer 1, in order from the first layer, SiO ₂ (40 nm) / TiO ₂ (20 nm) / SiO ₂ (40 nm) / TiO ₂ (300 nm) / SiO ₂ (90 Nm) to a five-layer structure. In addition, the parenthesis is an optical film thickness.

Formation of antireflective layer 3:

While stirring 50 g of silica fine particle dispersion (average particle diameter 110nm, standard deviation 1.3 of particle diameter, average value of major axis length and uniaxial length ratio 1.03, solid content 15%, Nippon Shokubai Co., Ltd. Shihostar KE-W10) 50g 20 g of glycol monomethyl ether and 1 g of concentrated hydrochloric acid are added, followed by 5.3 g of ethyl silicate 48 (average degree of polymerization n = 8, manufactured by Colcot Co., Ltd.), stirred for 2 hours, and then left to stand for 24 hours for reaction. I was. Thereafter, 164 g of propylene glycol monomethyl ether is added, and sodium acetate is further added as a curing catalyst, followed by stirring to make it uniform. Thereafter, 4 g of FZ-2105 (manufactured by Nihon Unika Co., Ltd.) was added as the conductive surfactant to obtain a low reflection layer solution.

This low reflection layer liquid was apply | coated by spin coating, it dried at room temperature, and the film thickness was 110 nm.

Formation of Anti-Reflection Layer 4:

20 g of ethanol and 1 g of concentrated hydrochloric acid were added while stirring 56 g of the chain-like aggregated silica fine particle dispersion (average primary particle diameter 25 nm, average length 100 nm, solid content 15%, Nissan Chemical Co., Ltd., Snowtex OUP) Then, 5.2 g of tetraethoxysilane was added and stirred for 2 hours, after which the reaction was allowed to stand for 24 hours. Thereafter, 164 g of propylene glycol monomethyl ether is added, and aluminum acetylacetone is further added as a curing catalyst, and stirred to make it uniform. Thereafter, 4 g of Painted 19 (manufactured by Dow Corning Asia) was added to obtain a low reflection layer solution. This low reflection layer liquid was apply | coated by spin coating, it dried at room temperature, and the film thickness was 110 nm.

Formation of Primer Layer 1:

A weather resistant primer (CP710, manufactured by Nippon ARC Co., Ltd.) was used as the silicone acrylic primer solution. The primer solution was applied by spin coating to a film thickness after curing of about 2 μm, and then heated at 110 ° C. for about 30 minutes to prepare a primer layer 1.

Formation of Primer Layer 2:

As a urethane-based primer solution, a general primer (CP620, manufactured by Nippon ARC Co., Ltd.) was used. The primer liquid was applied by spin coating to the film thickness after curing to be about 2 μm, and the primer layer 2 was prepared by heating at 50 ° C. for 30 minutes.

Formation of Hard Coat Layer 1:

As a colloidal silica having an average particle diameter of 20 nm, 150 g of `` Snowtex O-40 '' (40% non-volatile matter manufactured by Nissan Gaku Co., Ltd.) and 183 g of methyltrimethoxysilane were reacted, followed by 648 g of isopropyl alcohol. 0.1 g of "Paint Additive 19" (made by Dow Corning) was added as 18 g of acetic acid, 1 g of sodium acetate, and a flow control agent, and it stirred, and obtained the hard-coat liquid 1 for providing abrasion resistance.

The hard coat solution 1 was applied by a spin coat method such that the film thickness after curing was 3 μm, and the hard coat layer 1 was heated at a temperature of 120 ° C. for 30 minutes.

Formation of hard coat layer 2:

12.4 g of 1,6-hexanediol diacrylate as polyfunctional acrylate, 1.6 g of gamma -aminopropyltrimethoxysilane, 6.3 g of 2-methoxypropanol, 4.0 g of acetic acid, 0.8 g of benzophenone as a photopolymerization initiator, colo 26.0 g of "NPC-ST-30" (Nissan Gaku Co., Ltd. make, n-propyl cellosolve disperse silica fine particles having an average particle diameter of 20 nm. It added and 5.0g and 14.5g of butyl acetates were added for "epoxy ester 3002M" (Kyoeisha Chemical Co., Ltd.) as an epoxy acrylate for improving the hardness of a film | membrane. Next, 0.1 g of a flow control agent (manufactured by Painted 19 Dow Corning) was added. Thereafter, 100 g of 2-methoxypropanol was added, and the mixture was stirred and homogeneously dispersed to obtain a hard coat liquid 2 for imparting scratch resistance.

The hard coat solution 2 was applied by spin coating to obtain a film thickness of 5 μm, and then 1 second to 30 so that the total ultraviolet irradiation energy was 1,000 (mJ / cm 2) by an ultraviolet lamp having an output of 120 W / cm. It irradiated for second and hardened the coating film, and the hard coat layer 2 was obtained. In addition, this total ultraviolet irradiation energy value was measured with the integrated photometer (form | type: UIT-102 Ushio Denki Co., Ltd. product).

Formation of transparent conductive film:

In the high frequency (RF) -magnetron sputtering apparatus, ITO was used as a target, Ar + O ₂ was used as the sputtering gas, and the substrate temperature was 130 ° C., and an ITO film was formed at a film formation rate of about 1 μm / hr. .

Formation of antifouling layer 1:

To 100 g of ethanol (containing 0.35% by weight of moisture), 3-heptadecafluorodecyltrimethoxysilane (CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , manufactured by Shin-Etsu Silicone Co., Ltd.)) 0.02 g was added and stirred for 30 minutes, and then 1.0 g of tetrachlorosilane (SiCl ₄ , manufactured by Shin-Etsu Silicone Co., Ltd.) was added while stirring to obtain a solution for forming a water repellent antifouling film. This solution is represented by weight ratio and contains Si derived from 3-heptadecafluorodecyltrimethoxysilane in the ratio of 0.6 with respect to Si 100 derived from tetrachlorosilane, and the hydrochloric acid concentration of about 0.2 prescribed | regulated, 0.35 weight It had a water concentration of% and a pH of about 0.7. And the polymerization degree of the polymer of tetraethoxysilane in this solution was 1-3. This solution was apply | coated by the flow coat method at 30% of humidity, and room temperature, and it dried for about 1 minute at room temperature, and obtained the antifouling film coating resin article by which the antifouling layer 1 of about 60 nm thickness was coat | covered.

Formation of antifouling layer 2:

To 100 g of ethanol (containing 0.35% by weight of moisture), 3-heptadecafluorodecyltrimethoxysilane (CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , manufactured by Shin-Etsu Silicone Co., Ltd.)) 0.02 g was added and stirred for 30 minutes, and then 1.2 g of tetraethoxysilane (Si (OCH ₂ CH ₃ ) ₄ ) was added with stirring, followed by concentrated hydrochloric acid (35 wt%, manufactured by Kantogagaku Co., Ltd.). 2g was added stirring, and the solution for water repellent antifouling film formation was obtained. This solution contains Si derived from 3-heptadecafluorodecyltrimethoxysilane at a ratio of 0.6 to Si 100 derived from tetraethoxysilane, and the hydrochloric acid concentration of about 0.2 It had a water concentration and a pH of about 0.7. And the polymerization degree of the polymer of tetraethoxysilane in this solution was 1-3.

This solution was apply | coated by the flow coat method at 30% of humidity, and room temperature, and it dried for about 1 minute at room temperature, and obtained the antifouling film coating resin article by which the antifouling layer 2 of about 60 nm thickness was coat | covered.

Assessment Methods :

With respect to the antifouling film-coated resin articles obtained in each of the examples shown below, evaluation methods of oil ink resistance, fingerprint resistance, wear resistance, contact angle, falling angle, reflectance and surface roughness are as follows.

1. Oily ink resistant

(a) Adhesiveness of the oil ink pen

Number of wipes A straight line having a length of 1 cm was drawn on the surface of the substrate using an oil ink pen (ZEBRA / Extreme Fine), and it was visually judged for its ease of attachment or easily visible. Judgment criteria are shown below.

(Circle): The oil-based ink pen is aggregated in spherical shape.

X: The oil-based ink pen does not agglomerate and can be used.

(b) Wipeability of oil ink pen

The oil pen attached to the surface of the substrate was wiped with a cellulose nonwoven fabric (Bencott M-3: manufactured by Asahi Kasei Co., Ltd.), and visually determined whether it was easily wiped. Judgment criteria are shown below. In addition, the number of times until wiping was measured.

(Circle): The oil ink pen can be wiped off completely.

(Triangle | delta): The trace which wiped off the oil ink pen remains.

X: The oil ink pen cannot be wiped off.

2. Fingerprint Resistant

The fingerprint attached to the surface of the base material was wiped off with a cellulose nonwoven fabric [Bencott M-3: Asahi Kasei Co., Ltd.], and visually determined whether it was wiped easily. Judgment criteria are shown below. In addition, the number of times until wiping was measured.

(Circle): A fingerprint can be wiped off completely.

(Triangle | delta): The trace which wiped off the fingerprint remains.

X: The trace which wiped off the fingerprint spreads and cannot be wiped off.

3. Wear resistance

Abrasion resistance test was performed by rubbing the surface of the obtained antifouling film-coated resin article with a cellulose nonwoven fabric (Bencott M-3: manufactured by Asahi Kasei Co., Ltd.) at a load of 250 g / cm 2 for 50 round trips, and thereafter the presence of scratches. Visually judged. Judgment criteria are shown below.

○: no scratch.

(Triangle | delta): It is a little scratched.

X: Remarkably scratches.

Moreover, the contact angle after the abrasion resistance test was measured.

4. Measuring method of contact angle and tumble angle

For the obtained antifouling film-coated resin article, the contact angle of water was written using a contact angle meter (CA-DT, manufactured by Kyowa Chemical Industry Co., Ltd.), and a static contact angle with water drops of 2 mg weight (hereinafter referred to as "CA"). Occasions). The larger the value of this contact angle, the better the static water repellency, that is, the antifouling property (difficult to attach dirt).

In addition, water droplets having a diameter of 5 mm are placed on the surface of the antifouling film-coated resin article arranged horizontally, and the antifouling film-coated resin article is gradually inclined, and the inclination angle (critical inclination angle, drop angle) when the water droplets placed on the surface begins to roll. ) Was measured. The smaller the tumble angle, the better the dynamic water repellency, that is, the antifouling property (easiness of dropping dirt).

5. Reflectance

Optical characteristic measurement: The visible light reflectance (%) was measured based on JISR3212. Smaller values indicate higher antireflection performance.

6. Surface Roughness

The antifouling film film of the antifouling film coating resin article obtained in the present invention has a feature that the surface smoothness is very excellent. The surface roughness of the antifouling film-coated resin article is measured by arithmetic mean roughness Ra and ten point average roughness Rz. Surface roughness characteristics Ra and Rz can be measured by the method which extended JIS B 0601-1982 defined in two dimensions to three dimensions.

7. Surface Fluorine Concentration

The fluorine concentration of the antifouling film surface of the antifouling film coating resin article obtained in the present invention was measured by X-ray photoelectron spectroscopy (ESCA) as an atomic ratio (F / Si) of F and Si. The test conditions of X-ray photoelectron spectroscopy (ESCA) include anode energy; 1486.6 eV, anode output; 150 W, acceleration voltage; 14 kV, X-ray incident angle to the sample; 45 degree, analysis area; Circle with a diameter of 800 µm, measuring thickness; Several nm.

Example 1

A primer layer 1 was formed on the polycarbonate sheet base material, and then a hard coat layer 1 was formed thereon, and an antifouling layer 2 was formed thereon again, thereby forming a PC sheet / primer layer 1 / hard coat layer 1 / antifouling layer 2. An antifouling film coating resin article was prepared. Initial contact angle (degrees), tumble angle (degrees), surface fluorine concentration (F / Si), visible light reflectance (%), oily ink resistance (wipes (the number of wipes in parentheses) and adhesion) for this article; Fingerprint resistance (wipe), surface roughness (arithmetic mean roughness (Ra) (nm) and ten-point average roughness (Rz) (nm)) and abrasion resistance (scratch incidence and contact angle after abrasion test) were measured, and the results were measured. 1 is shown.

Examples 2 to 8

In the resin base material shown in Table 1, as shown in Table 1, a primer layer, a hard coat layer, a functional film (transparent conductive layer), an antireflection layer, and an antifouling layer were formed in this order to produce an antifouling film coating resin article, and Various performances were measured similarly to Example 1, and the result is shown in Table 1.

In addition, instead of the hard coat liquid 2 used in the formation of the hard coat layer 2 in Example 2, in addition to the hard coat liquid 2, a boron-based antistatic agent "hyborone KB212" (10% active ingredient, manufactured by Boron International) was added. Except for using the antistatic hard coat liquid obtained by adding 30g, it carried out similarly to Example 2, and manufactured the antifouling film coating resin article. Antistatic performance, 10 ^11-10 showed a ¹² Ω / □. The other performances showed substantially the same performances as in Example 2 which did not impart antistatic.

Moreover, instead of the low reflection layer liquid used in formation of the antireflection layer 4 in Example 5, instead of 4 g of "Painted 19" added by preparation of this low reflection layer liquid, surfactant "FZ-2105" (Nihon Unika) The antifouling film coating resin article was manufactured like Example 5 except having used the antireflection (antistatic) liquid which added 5 g). Antistatic 10 ^12-10 showed a ¹³ Ω / □. The other performances showed substantially the same performance as in Example 5 without providing antistatic.

Comparative Example 1

Instead of the antifouling layer 1 formed in Example 1, 0.2% by weight of a silicon-based material and a perfluoro group represented by [RfSi (OEt) ₃ : Rf is a perfluoro group, Et is an ethyl group] containing a perfluoro group containing [(H ₂ RfPO _4): Rf is a perfluoroalkyl group] by coating a coating solution consisting of an alcohol solution containing a phosphoric acid ester 7.0% by weight, represented by, and dried at 66 ℃ except for forming the antifouling layer, An antifouling film-coated resin article was produced in the same manner as in Example 2, and various performances were measured in the same manner as in Example 2, and the results are shown in Table 1.

Comparative Example 2

Instead of the hard coat layer 2 formed in Example 8, the surface was treated with a plasma containing oxygen in advance and a hydrophilic resin substrate was used in the same manner as in Example 8 except that the hard coat layer was not formed. To prepare an antifouling film-coated resin article, and carried out similarly to Example 8 to measure various performances, and the results are shown in Table 1 below.

Example, Comparative Example No Base resin type Primer layer number Hard Court Floor Number Function curtain Antireflection layer Antifouling floor number number quite Membrane composition Example 1 PC sheet One One - - - - 2 Example 2 PC film - 2 - One High frequency magnetron sputter SiO ₂ One Example 3 PET film 2 One - 2 High frequency magnetron sputter SiO ₂ / TiO ₂ / SiO ₂ / TiO ₂ / SiO ₂ 2 Example 4 COP film - 2 Conductive Film (ITO) 3 Sol-gel method SiO ₂ fine particles One Example 5 COP film One - - 4 Sol-gel method SiO ₂ Annular particulates One Example 6 PMMA film - 2 - 3 Sol-gel method SiO ₂ Particulate 2 Example 7 COP film - - - 2 High frequency magnetron sputter SiO ₂ / TiO ₂ / SiO ₂ / TiO ₂ / SiO ₂ One Example 8 PC film - 2 - - - - One Comparative Example 1 PC film - 2 - One High frequency magnetron sputter SiO ₂ One Comparative Example 2 PC film - - - - - - One

Example, Comparative Example No Initial performance reflectivity Oil-based ink resistant Fingerprint resistant Surface roughness Wear resistance Contact angle (degree) Tumble angle (degrees) F / Si (%) Wipe off Adhesion Wipe off Ra (nm) Rz (nm) Scratch Contact angle after wear (degrees) Example 1 110 5 1.1 8 ○ ○ ○ (3) 0.4 3.0 ○ 107 Example 2 111 4 1.2 0.3 ○ ○ ○ (3) 0.3 3.2 ○ 104 Example 3 109 6 1.1 0.2 ○ ○ ○ (3) 0.3 4.0 ○ 103 Example 4 111 12 1.2 0.8 ○ ○ ○ (5) 20 45.0 ○ 105 Example 5 110 5 1.2 0.5 ○ ○ ○ (5) 10 29.0 ○ 103 Example 6 112 13 1.1 0.8 ○ ○ ○ (5) 18 40.0 ○ 106 Example 7 110 5 1.2 0.2 ○ ○ ○ (3) 0.4 4.0 ○ 102 Example 8 111 7 1.2 8 ○ ○ ○ (3) 0.4 4.5 ○ 103 Comparative Example 1 95 - - 0.5 △ △ ○ (5) - - ○ 70 Comparative Example 2 95 - - 8 △ △ ○ (5) - - ○ 60

Claims (10)

A transparent resin substrate having at least a surface layer of a siliceous resin or an inorganic compound on the surface thereof is prepared, and a silicon alkoxide, a fluoroalkyl group-containing silane compound and an acid are contained on the substrate layer of the transparent resin substrate. A coating liquid to be applied is applied, and then dried to form an antifouling layer. The said coating liquid dissolves the chlorosilyl group containing compound and the fluoroalkyl group containing silane compound in the solvent containing alcohol and / or water, The chloro group of the said chlorosilyl group containing compound is an alkoxyl group or a hydroxyl group. Method prepared by substituting for. The said coating liquid is a method in which the tetraalkoxy silane or its polymer or its hydrolyzate, a fluoroalkyl group containing silane compound, and an acid were dissolved in the alcohol solvent. The method according to claim 1, wherein the base layer of the inorganic compound is an antireflection film containing silica as the outermost layer. The method according to claim 1, wherein the base layer of the inorganic compound is an antireflection film made of silica fine particles. The method according to claim 1, wherein the underlayer of the resin is a hard coat film containing colloidal silica. The method according to claim 1, wherein the base layer of the resin is a hard coat film made of silicon resin. The method of claim 1, wherein a primer layer is further present between the transparent resin substrate and the base layer. The method according to claim 4 or 5, wherein a hard coat layer is further present between the transparent resin substrate and the antireflection film. 10. The method of claim 9, wherein a transparent conductive film is further present between the hard coat layer and the antireflective film.