CN1723237A - Method for producing resin article coated with anti-staining film - Google Patents
Method for producing resin article coated with anti-staining film Download PDFInfo
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- CN1723237A CN1723237A CNA200480001945XA CN200480001945A CN1723237A CN 1723237 A CN1723237 A CN 1723237A CN A200480001945X A CNA200480001945X A CN A200480001945XA CN 200480001945 A CN200480001945 A CN 200480001945A CN 1723237 A CN1723237 A CN 1723237A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
- C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
- C08J7/065—Low-molecular-weight organic substances, e.g. absorption of additives in the surface of the article
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/02—Polysilicates
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Abstract
The invention provides a method 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. The method can be employed 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.
Description
Technical field
The present invention relates to the manufacture method of the resin article of coated with anti-staining film.In more detail, be the manufacture method of resin article that is particularly related to the coated with anti-staining film of the transparent resin substrate of giving the display frame that is used for indicating meter or transparent resin film surface soiling.
Background technology
Have the plastics of the transparency to have optical characteristics, light weight and various advantages such as processing or attenuation easily, in the optical correlation market of relevant equipment of so-called liquid crystal or CD or the demand in film market very big.Particularly at indicating meter for example in the display frame of liquid-crystal display, the projected display, plasma display, EL indicating meter etc., the plastics with transparency are as main raw, can be with glass combination or use separately.The purpose that is used for indicating meter is to give explosion-proof auxiliaring effect, anti-static effect, adjustment transmitance effect, anti-reflection effect, anti-fouling effect etc., the film combination layer that will have so various functions is pressed on the resin molding as base material, the polylayer forest that forms is attached to the display frame substrate of making on glass, or directly above-mentioned polylayer forest is laminated on the transparent resin thin slice, it self just forms the display frame substrate.The known display frame substrate that has on the PET film lamination hard coat film, nesa coating, antireflection film, antifouling film successively form of an example wherein.Here antifouling film is meant that giving its surface is difficult to adhere to spots such as fingerprint, or in case is stained with the film of the function of also removing easily.
Technology as antifouling film, open in the flat 7-16940 communique report for the optical article that has based on the optical thin film of silicon-dioxide the spy, can on its optical thin film, form the monomer that contains perfluoroalkyl (methyl) acrylate and alkoxysilane group or the film of its polymkeric substance.
The spy opens and put down in writing in the 2000-327818 communique is being in the solution of solute with the triethoxyl silane that contains the perfluor base, adds and contains the paint of the phosphoric acid ester of perfluor base as catalyzer, it is coated on to have in skin section contain SiO
2On this antireflection film of the optical article of the antireflection film of layer, form stain-proofing layer.
Propose on the transparent film base material, to have the superiors of the antireflection film of anti-reflection layer in the Te Kaiping 2001-188102 communique, make the silane coupling agent film forming that contains holo-fluorine polyester form stain-proofing layer by vacuum evaporation.
In addition, put down in writing the manufacture method of following hydrophobicity article in the Te Kaiping 11-71682 communique: the surface is handled in advance making it possess hydrophilic property with oxygen containing plasma body or in corona atmosphere, perhaps substrate surface is shone near the ultraviolet ray of wavelength 200～300nm in oxygen containing atmosphere, surface coated at the plastic basis material of handling through wetting ability contains silane oxide (or the monomer of its hydrolysate or 19 times of polymkeric substance below the body), contains the silane compound of fluoro-alkyl and the solution of acid, the dry then hydrophobicity tunicle that forms.
But there is the low problem of production efficiency because the coating afterreaction time is long in the technology that the spy opens flat 7-16940 communique.The spy opens that the disclosed method of 2000-327818 communique and the flat 11-71682 communique of Te Kai exists or didirtresistance produce required time long or antifouling property is low or use in the problem that easily descends of didirtresistance.And the special technology of opening the 2001-188102 communique must be used the such special device of vacuum evaporation.
Summary of the invention
The method that the objective of the invention is to need not special device and the resin article of producing coated with anti-staining film is provided with high production efficiency, this antifouling film can prevent the surface of spots such as fingerprint, sebum, sweat, makeup attached to the such transparent resin base material of antireflection film, even and water droplet contact angle ambassador spot is adhered to also and is wiped easily, in addition, the characteristic that also has good, the high scuff resistance of water droplet rollability, weathering resistance.
Other purpose and advantage of the present invention can be understood by the following description.
According to the present invention, the manufacture method of the resin article by coated with anti-staining film, realize above-mentioned purpose of the present invention and advantage, it is characterized in that, prepare to have in its surface the surperficial at least transparent resin base material that constitutes stratum basale by siliceous resin or mineral compound, coating contains oxide silane, contains the silane compound of fluoro-alkyl and the coating fluid of acid, the dry then stain-proofing layer that forms on the stratum basale of this transparent resin base material.
Embodiment
In the present invention, on the surface of transparent resin base material at least the surface be siliceous and be provided with the stratum basale that constitutes by resin or mineral compound.The preferred SiO in the surface of resin base layer or mineral compound stratum basale
2Or the content of Si-O is more than 20 weight %.Form as stratum basale can be for following 5 kinds of examples.
[stratum basale 1]
It is siliceous can enumerating surperficial at least, and resin base layer is siliceous hard coat.This hard coat is the represented compound of formula (1) and contains the masking liquid of colloid silica, by 50～130 ℃ of heating several seconds～5 hour down, makes it to solidify and forms.
R
1 aR
2 bSi(OR
3)
4-a-b (1)
The R here
1Be the allyl group of the alkyl that contains epoxy group(ing) of the alkyl of carbonatoms 1～4, carbonatoms 2～12, carbonatoms 6～12 or haloalkyl, the methacryloxy alkyl of carbonatoms 5～8, the urea groups alkylidene group of carbonatoms 2～10, aromatic series urea groups alkylidene group, aromatic series alkylidene group, sulfydryl alkylidene group, R
2Be alkyl, aryl, alkenyl, haloalkyl or the halogenated aryl of carbonatoms 1～6, R
3Be alkyl, acyl group, the alkyl acyl of hydrogen atom or carbonatoms 1～4, a is 1,2 or 3, and b is 0,1 or 2.
This hard coat preferred thickness is 1～10 μ m.The represented organic silane compound of above-mentioned formula (1) can list for example trimethylammonium methoxy silane, phenyl dimethyl methyl TMOS, vinyl-dimethyl methoxylsilane, γ-acryloyl-oxy propyl-dimethyl methoxy silane, γ-sulfydryl propyl-dimethyl methoxy silane, N-β (amino-ethyl) gamma-amino propyl-dimethyl methoxy silane, β-this class simple function silane of (3, the 4-epoxycyclohexyl) ethyl dimethyl methyl TMOS; Dimethyldimethoxysil,ne, phenyl methyl dimethoxy silane, vinyl methyl dimethoxysilane, γ-acryloyl-oxy propyl group methyl dimethoxysilane, γ-sulfydryl propyl group methyldiethoxysilane, gamma-amino propyl group methyl dimethoxysilane, γ-glycidoxy propyl group methoxyl group diethoxy silane and β-this class difunctionality silane of (3, the 4-epoxycyclohexyl) ethyl-methyl dimethoxy silane; Methyltrimethoxy silane, phenyl triethoxysilane, vinyltrimethoxy silane, γ-acryloyl-oxy propyl trimethoxy silicane, gamma-methyl allyl acyloxypropyl trimethoxysilane, γ-sulfydryl propyl-triethoxysilicane, gamma-amino propyl trimethoxy silicane, γ-glycidoxypropyltrime,hoxysilane and β-this class trifunctional silane of (3, the 4-epoxycyclohexyl) ethyl trimethoxy silane.Wherein, especially preferably use methyltrimethoxy silane, ethyl triethoxysilane, Union carbide A-162, this class alkyltrialkoxysilaneand of ethyl trimethoxy silane.
The proportioning of each composition, with respect to represented compound 100 weight parts of following formula (1), preferred colloid silica 40～900 weight parts, more preferably 250～500 weight parts.Masking liquid is adjusted into the dispersion liquid of the above-mentioned effective constituent that contains specified amount in the liquid medium of alcohol and so on.
Above-mentioned colloid silica for example can come from the SiO with 10～50 weight %
2, preferable particle size 1～200nm, the more preferably SiO of 1～100nm
2Particle is the colloidal silica sol of effective constituent, or particle diameter be 1～200nm, more preferably 1～100nm scope contain SiO
2Composite oxide particle.These composite oxides are SiO
2With the mixture of metal oxide, metal oxide can list the oxide compound of the metal of selecting these from Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, Pd, In and Ti more than a kind or 2 kinds, concrete example such as Al
2O
3, SnO
2, Sb
2O
5, CeO
2, Ta
2O
5, La
2O
3, Fe
2O
3, ZnO, WO
3, ZrO
2, PdO
2, In
2O
3And TiO
2Deng.Contain SiO
2Composite oxide particle can list the composite oxide particle (TiO of titanium and silicon
2SiO
2), the composite oxide particle (TiO of titanium, cerium and silicon
2CeO
2SiO
2), the composite oxide particle (TiO of titanium, iron and silicon
2Fe
2O
3SiO
2), the composite oxide particle (TiO of titanium, zirconium and silicon
2ZrO
2SiO
2), the composite oxide particle (TiO of titanium, aluminium and silicon
2Al
2O
3SiO
2) etc.
Preferably contain SiO in these composite oxide particles
2Composition is at 5 moles more than the %.
For improving the dispersiveness of above-mentioned composite oxides in solvent, also can carry out surface modification with silicoorganic compound.The weight of the relative composite oxide particle of usage quantity of silicoorganic compound is below the preferred 20 weight %.Surface treatment both can be carried out under the organic silane compound that is used to handle has the state of hydrolyzable group, also can carry out after hydrolysis.This organic silane compound can list for example trimethylammonium methoxy silane, phenyl dimethyl methyl TMOS, vinyl-dimethyl methoxylsilane, γ-acryloyl-oxy propyl-dimethyl methoxy silane, γ-sulfydryl propyl-dimethyl methoxy silane, N-β (amino-ethyl) gamma-amino propyl-dimethyl methoxy silane, β-this class simple function silane of (3, the 4-epoxycyclohexyl) ethyl dimethyl methyl TMOS; Dimethyldimethoxysil,ne, phenyl methyl dimethoxy silane, vinyl methyl dimethoxysilane, γ-acryloyl-oxy propyl group methyl dimethoxysilane, γ-sulfydryl propyl group methyldiethoxysilane, gamma-amino propyl group methyl dimethoxysilane, γ-glycidoxy propyl group methoxy ethoxy silane and β-difunctionality silane such as (3, the 4-epoxycyclohexyl) ethyl-methyl dimethoxy silane; Methyltrimethoxy silane, phenyl triethoxysilane, vinyltrimethoxy silane, γ-acryloyl-oxy propyl trimethoxy silicane, gamma-methyl allyl acyloxypropyl trimethoxysilane, γ-sulfydryl propyl-triethoxysilicane, gamma-amino propyl trimethoxy silicane, γ-glycidoxypropyltrime,hoxysilane and β-this class trifunctional silane of (3, the 4-epoxycyclohexyl) ethyl trimethoxy silane; These class four functional silanes of tetraethyl orthosilicate and original quanmethyl silicate.When handling with the silane compound that has composite oxides, preference is as carrying out in water, alcohol or other organic medium.
[stratum basale 2]
Siliceous hard coat is to contain (A) polyfunctional acrylic ester, (B) aminosilane and (C) the hard masking liquid of colloid silica by coating, gets through uviolizing again.This hard coat preferred thickness is about 1～10 μ m.
The various compositions of above-mentioned hard masking liquid below are described.
Polyfunctional acrylic ester as (A) composition is meant that intramolecularly has (methyl) acrylate of 2 hydroxyls and at least 2 (methyl) acryls at least.Need to prove that in this manual, acryl or methacryloyl are called (methyl) acryl again, acrylate or methacrylic ester are called (methyl) acrylate, acrylic or methacrylic acid is called (methyl) vinylformic acid.Multifunctional (methyl) acrylate can list as 1, the 6-hexanediyl ester, 1, the 4-butylene glycol diacrylate, glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, neopentylglycol diacrylate, 1, the 4-butylene glycol dimethacrylate, poly-(butyleneglycol) diacrylate, the TEG dimethacrylate, 1,3 butyleneglycol diacrylate, triethylene glycol diacrylate, three Isopropanediol diacrylates, the diacrylate class of polyethyleneglycol diacrylate and this class of bisphenol a dimethacrylate; The triacrylate class of Viscoat 295, trimethylolpropane trimethacrylate, tetramethylolmethane monohydroxy triacrylate and this class of trimethylolpropane tris oxyethyl group triacrylate; The tetraacrylate class of tetramethylol methane tetraacrylate and this class of ditrimethylolpropane tetraacrylate; And five esters of acrylic acids of tetramethylolmethane (monohydroxy) five these classes of acrylate.Multifunctional (methyl) acrylate can use more than a kind or 2 kinds together.
Aminosilane as (B) composition is the organoalkoxysilane that contains amino or substituted-amino, the amino organic functional silane that preferred following formula (2) is represented.
X
aSi(R
4(NHR
5)
bNR
6H)
4-a (2)
Here X is the alkoxyl group of carbonatoms 1～6, R
4, R
5Be the alkyl of identical or different divalent, R
6Be the alkyl of hydrogen atom or 1 valency, a is 1～3 integer, and b is 0 or 1～6 integer.In the formula (2), a preferred 2 or 3, and b preferred 0 or 1.
The represented aminosilane of formula (2) can list the Trimethoxy silane as n-(2-amino-ethyl-3-aminopropyl), the 3-aminopropyltriethoxywerene werene, the 3-aminopropyltriethoxywerene werene, γ-(2-amino-ethyl) TSL 8330, γ-(2-amino-ethyl) aminopropyl methyl dimethoxysilane, the 3-TSL 8330, N-β-(N-vinyl benzyl amino-ethyl)-gamma-amino propyl group methyl dimethoxysilane hydrochloride and γ-anilino propyl trimethoxy silicane.
Can use as hereinbefore compound as the colloid silica of (C) composition.
This hard masking liquid preferably contains the Photoepolymerizationinitiater initiater that makes multifunctional (methyl) acrylic ester polymerization.Photoepolymerizationinitiater initiater can use as radical photopolymerization initiator, cationic photopolymerization initiator etc.Can list benzophenone as the radical photopolymerization initiator, [2-hydroxy-2-methyl-1-phenylpropyl alcohol-1-ketone], [1-(4-isopropyl phenyl)-2-hydroxy-2-methyl third-1-ketone], [4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group ketone)], [2,2-dimethoxy-1,2-hexichol second-1-ketone], [1-hydroxyl-cyclohexyl-phenyl-ketone], [2-methyl isophthalic acid [4-(first sulfydryl) phenyl]-2-morpholino third-1-ketone], [two (2,6-dimethoxy benzoyl)-2,4,4-trimethylammonium-amyl group phosphine oxide], [2-benzyl-2-dimethylamino-1-1-(4-morpholino phenyl)-butanone-1].In addition, the cationic photopolymerization initiator can list phenyl-[-(2-hydroxyl tetradecyl) phenyl] iodine hexafluoro antimonate, dialkyl group iodine, four (pentafluorophenyl group) boric acid ester etc.
The amount of Photoepolymerizationinitiater initiater is with respect to 100 weight parts of multifunctional (methyl) acrylate of hard coating composition, preferred 0.1～30 weight part, more preferably 1～15 weight part.
The hydrolyst that this hard masking liquid preferably contains the hydrolysis that is useful on aminosilane (B), polycondensation is basic catalyst such as acid catalyst such as formic acid, acetate, propionic acid, butyric acid, oxalic acid, (methyl) vinylformic acid, hydrochloric acid, nitric acid, sulfuric acid or ammonia, sodium hydroxide, potassium hydroxide aqueous solution for example.An acidic catalyst that wherein preferably uses aqueous solution is acetate, (methyl) vinylformic acid for example.Add the amount of acid catalyst, with respect to aminosilane (B) 100 weight parts, preferred 5～30 weight parts.
In this hard masking liquid, with respect to above-mentioned multifunctional (methyl) acrylate (A) 100 weight parts, preferably contain amino organofunctional silane (B) 1.5～50 weight parts, more preferably 8～25 weight parts, colloid silica preferably contains 10～150 weight parts, more preferably 40～85 weight parts with solids component.
[stratum basale 3]
Among the present invention, be siliceous mineral compound stratum basale, can enumerate antireflection film as the surface.This antireflection film forms the mineral compound film (be silicon oxide film 1 layer time, the superiors are silicon oxide film more than 2 layers the time) of a bed thickness 20nm～50 μ m (more than 2 layers time for add up to thickness) at least.Mineral compound can be enumerated for example silicon oxide (silicon-dioxide, silicon monoxide), and metal oxide can be enumerated for example aluminum oxide, magnesium oxide, titanium oxide, stannic oxide, zirconium white, Thorotrast, weisspiessglanz, Indium sesquioxide, bismuth oxide, yttrium oxide, cerium oxide, zinc oxide, ITO (indium-tin-oxide) etc.; The metal halides can be enumerated for example magnesium fluoride, Calcium Fluoride (Fluorspan), Sodium Fluoride, lanthanum fluoride, cerium fluoride, lithium fluoride, thorium fluoride etc.The formation method of antireflection film can be enumerated for example chemical Vapor deposition process (CVD method), physical vaporous deposition (PVD method).The CVD method can be enumerated for example plasma CVD method, and the PVD method can be enumerated for example vacuum vapour deposition, reactive vapour deposition method, Assisted by Ion Beam method, splash method, ion plating method etc.
The formation of concrete mineral compound rete can be for following example.
Form TiO by vacuum vapour deposition, splash method or plasma CVD method
2/ SiO
2Laminated film (at TiO
2The top lamination SiO of layer
2Layer.2 layers of antireflection film).
Form TiO by vacuum vapour deposition, splash method and plasma CVD method
2/ SiO
2/ TiO
2/ SiO
2Multilayer film (4 layers of antireflection film).
Form SiO by vacuum vapour deposition, splash method or plasma CVD method
2/ TiO
2/ SiO
2/ TiO
2/ SiO
2Multilayer film (5 layers of antireflection film).
Form SiOx film (individual layer antireflection film) by plasma CVD method.
[stratum basale 4]
As surface at least is the stratum basale of siliceous mineral compound, can enumerate the individual layer anti-reflection layer that is made of silicon dioxide microparticle.By being coated with following low reflection layer liquid, heating and can form this individual layer anti-reflection layer that thickness is 70～350nm.
Low reflection layer liquid contains (1), and to be the feed particles that constitutes of one of the non-aggegation silicon dioxide microparticle of 40～1000nm and chain aggegation silicon dioxide microparticle of average primary particle diameter 10～100nm, (2) by median size at least be selected from a kind of in the represented organoalkoxysilane of hydrolyzable organoalkoxysilane and its oligopolymer or following formula (4) or several as containing of tackiness agent, mixed again water and solvent, make tackiness agent hydrolysis in the presence of above-mentioned particulate, catalyzer of above-mentioned (2), add the solution that curing catalysts forms then.
Above-mentioned hydrolyzable organoalkoxysilane can use for example tetraalkoxysilane of this class of tetraethoxysilane, and other organoalkoxysilane can be enumerated as shown in the formula (3) represented compound.
R
7 aR
8 bSi(OR
9)
4-a-b (3)
In the formula, R
7The one-sided end of the alkyl that replaces for the urea groups alkylidene group of the methacryloyl oxyalkyl of the aryl of the alkyl of carbonatoms 1～4, carbonatoms 6～12 or haloalkyl, carbonatoms 5～8, carbonatoms 2～10, with glycidoxy has aklylene glycol base, aromatic series urea groups alkylidene group, aromatic series alkylidene group or the sulfydryl alkylidene group of alkyl, R
8Be alkyl, aryl, alkenyl, haloalkyl or the halogenated aryl of carbonatoms 1～6, R
9Be alkyl, acyl group or the alkyl acyl of hydrogen atom, carbonatoms 1～4, a=1,2 or 3, b=0,1 or 2.Then a+b is 1,2 or 3.
R
10O-((RO)
2-Si-O)
n-R
10 (4)
In the formula, R
10Be the alkyl of carbonatoms 1～4, n=1～20 comprise chain-like structure, divide dendritic structure, ring texture as the structure of condenses.
The weight ratio of silicon dioxide microparticle and tackiness agent preferably cooperates with 60: 40～95: 5 ratio.And the ratio of the preferred major and minor axis length of non-aggegation silicon dioxide microparticle in the above-mentioned low reflection layer liquid is 1.0～2.0, preferably the primary particle size standard deviation is 1.0～1.5.
[stratum basale 5]
As surface at least is the hard coat that the stratum basale of siliceous resin can be enumerated silicone resin.This hard coat is that coating contains the represented compound of following formula (5) and contains the masking liquid of tetraalkoxysilane, then 50～130 ℃ down heating several seconds～5 hour make it to solidify and obtain.
R
1 aR
2 bSi(OR
3)
4-a-b (5)
In the formula, R
1Be the aryl of the alkyl that epoxy group(ing) is arranged of the alkyl of carbonatoms 1～4, carbonatoms 2～12, carbonatoms 6～12 or haloalkyl, the methacryloxy alkyl of carbonatoms 5～8, the urea groups alkylidene group of carbonatoms 2～10, aromatic series urea groups alkylidene group, aromatic series alkylidene group, sulfydryl alkylidene group, R
2Be alkyl, aryl, alkenyl, haloalkyl or the halogenated aryl of carbonatoms 1～6, R
3Be alkyl, acyl group, the alkyl acyl of hydrogen atom or carbonatoms 1～4, a is 1,2 or 3, and b is 0,1 or 2.This hard coat preferred thickness is 1～10 μ m.The explanation of above-mentioned stratum basale 1 Chinese style (1) also is applicable to the compound of above-mentioned formula (5).Tetraalkoxysilane can be enumerated for example tetramethoxy-silicane, tetraethoxysilane or its polymkeric substance (preferred 19 times of bodies are following) or their hydrolyzate.
The cooperation ratio of each composition, with respect to represented compound 100 weight parts of above-mentioned formula (5), preferred tetraalkoxysilane 40～900 weight parts, more preferably 250～500 weight parts.In this class I liquid I solvent of alcohol, be modulated into the solution that contains quantitative above-mentioned effective constituent.
Above-mentioned stratum basale 1～5 constitutes by 2 layers, and the anti-reflection layer that is provided with as the tight lower floor as stain-proofing layer, as stratum basale 3,4 is set is as its hard coat of lower floor more, as stratum basale 1,2,5 can be set.
Above-mentioned stratum basale 1～5 can add tensio-active agent, an alkali metal salt, electrically conductive microparticle or electric charge as required and move title complex, can further give stratum basale static electricity resistance or electroconductibility like this.
For example can enumerate [FZ-2105], [L-7604], [L-77], [L-7001], [FZ-2123], [FZ-2162] (being the nonionic class) that [ELEC-QN] (anionic property), [ELEC-ACz] (both sexes), [ELEC-F], [ELEC-EA] (nonionic), [AMIET-302] (non-example), [HOMOGENOL L-18] (special polymer), [HOMOGENOL L1820] (special polymer) (being colored king (strain) system) or Japanese UNICAR (strain) make as tensio-active agent.
Can enumerate as metals such as the metal oxide of ATO (antimony-tin-oxide) with particle diameter 1～100nm or ITO or silver as electrically conductive microparticle.Be generally the dispersion liquid form.Addition is with respect to film effective constituent 100 weight parts, preferred 1～80 weight part.Particulate can use and be shaped as sphere, ellipse, fibrous, lepidiod particulate.For improving electric conductivity, optimum fiber shape and flakey.
It is antistatic agent HIBORON etc. that electric charge moves the boron that title complex can enumerate as (strain) BORON INTERNATIONAL system.Addition is with respect to film effective constituent 100 weight parts, preferred 1～20 weight part.
Among the present invention, coating anti-pollution coating fluid on above-mentioned stratum basale, at room temperature dry 10 seconds～10 minutes, the formation preferred thickness was 10～100nm, the more preferably stain-proofing layer of 10～30nm.This is antifouling to contain silane oxide, contains the silane compound and the acid of fluoro-alkyl with coating fluid.Silane oxide preferably uses tetraethoxysilane, this class tetraalkoxysilane of tetramethoxy-silicane or its polymkeric substance (preferred 19 times of bodies are following) or their hydrolyzate.
The silane compound that contains fluoro-alkyl preferably uses as containing fluoro-alkyl and containing the silane compound of alkoxyl group, acryloxy or chlorine.For example can enumerate following formula (6), (7) represented compound.Can use wherein a kind of or several are used in combination.
CF
3-(CF
2)
nR
11-SiX
pY
3-p (6)
(in the formula, n is 0 to 12 integer, preferred 3 to 12 integer, R
11Be the divalent organic group (as methylene radical, ethylene group) of carbonatoms 1～10 or the group of silicon atoms and Sauerstoffatom, X is the monovalence alkyl (as alkyl, cycloalkyl, allyl group) of carbonatoms 1～4 or substituting group or the hydrogen that is selected from these derivatives, p is 0,1 or 2, Y is the alkoxyl group or the acryloxy of carbonatoms 1～4)
CF
3-(CF
2)
n-R
12-SiX
pCl
3-p (7)
(in the formula, n is 0 to 12 integer, preferred 3 to 12 integer, R
12Be the group of methylene radical, ethylene group or silicon atoms and hydrogen atom, X is H or alkyl, cycloalkyl, allyl group or the substituting group that is selected from these derivatives, and p is 0,1 or 2)
Following formula (6), (7) represented silane especially preferably use for example C
8F
17CH
2CH
2Si (OCH
3)
3, C
8F
17CH
2CH
2Si (CH
3) (OCH
3)
2, C
8F
17CH
2CH
2SiCl
3(3-17 fluorine decyltrichlorosilanes) and C
8F
17CH
2CH
2Si (CH
3) Cl
2
Antifoulingly preferably use for example hydrochloric acid, nitric acid, this class volatile acid of acetate with the contained acid of coating fluid.
The antifouling preferred alcohols hydrophilic solvent of solvent, ketone hydrophilic solvent etc. with coating fluid.Wherein alcohols for example the such carbonatoms of methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol at the monohydroxy-alcohol below 3, at normal temperatures evaporation rate greatly thereby more preferably, the hydrophilic solvent of ketone can be enumerated for example acetone or methyl ethyl ketone.
Antifoulingly preferably contain with coating fluid:
(A) silane oxide or its hydrolyzate
(converting) 0.01～2 weight % with silicon
(B) contain the silane compound of fluoro-alkyl
(converting) 0.00001～0.15 weight % with silicon
(C) acid 0.001～3 equivalent and
(D) water 0～5 weight %
More preferably contain:
(A) silane oxide or its hydrolyzate
(converting) 0.01～2 weight % with silicon
(B) contain the silane compound of fluoro-alkyl
(converting) 0.00001～0.15 weight % with silicon
(C) haloid acid 0.001～3 equivalent and
(D) water 0～5 weight %
Wherein the weight ratio of acid/water is more than 0.002, and is preferred more than 0.02.
Antifoulingly can prepare by above-mentioned (A)～(C) composition is dissolved in the alcoholic solvent with coating fluid, also the compound of chloride silyl and the silane compound that contains fluoro-alkyl can be dissolved in the solvent that contains alcohol and/or contain moisture, and the chlorine of the compound of above-mentioned chloride silyl be substituted by alkoxyl group or hydroxyl prepares.
Among the present invention,, can between stratum basale and transparent resin base material, the priming paint layer be set for improving the binding property between above-mentioned stratum basale and transparent resin base material.Can also between stratum basale and transparent resin base material, antistatic backing be set.
This priming paint layer does not have particular determination, for example can use with polyurethanes, acrylic acid or the like, urea groups esters of acrylic acid or part silanization thing to be principal constituent, adjusts the material that forms after the concentration with organic solvent.Commercially available product can be used for example silane acrylic acid or the like priming paint liquid (CP710, Japanese ARC (strain) system), polyurethanes priming paint liquid (CP620, Japanese ARC (strain) system).Treatment process is: the priming paint layer is coated transparent resin base material surface with treatment solution, be drying to obtain.This priming paint layer preferred thickness is 0.5～5 μ m.The priming paint layer can use organic solvents such as alcohol with the solvent of treatment solution, also can water.
When on the resin article of coated with anti-staining film, nesa coating being set among the present invention, for example can use the splash method, below above-mentioned stratum basale is tight, make the film of ITO (indium-tin-oxide).
But the structure illustration of the resin article of the coated with anti-staining film that makes by the present invention is as follows:
(1) transparent resin base material/priming paint/hard coat/nesa coating/antireflection film/antifouling film.
(2) transparent resin base material/hard coat/nesa coating/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/priming paint/antireflection film/antifouling film.
(6) transparent resin base material/hard coat/antifouling film.
(7) transparent resin base material/priming paint/hard coat/antifouling film.
(8) transparent resin base material/hard coat/antireflection film (anti-electrostatic)/antifouling film
(9) transparent resin base material/hard coat (electroconductibility)/antireflection film/antifouling film
The material of transparent resin base material can list as transparent resins such as tri acetyl cellulose resin, plexiglass, polycarbonate resin, polyvinyl resin, pet resin, polystyrene resin, cyclic olefin polymer, polyethersulfone resin, allyl diglycolcarbonate resins among the present invention.Thin slice of these transparent resin systems or film can use as base material.
The present invention can be used for the light DIFFUSION TREATMENT film, indicating meter of mobile telephone light guiding plate for example, as the surface treatment film of the surface treatment film of the front panel of subnotebook PC, watch-dog, PDP, projection TV, PDA, touch pad watch-dog, the form of mobile telephone, the position that requires high optical characteristics, automobile with the antifouling film that forms in the transparent component etc.
According to the present invention as mentioned above, can be under the condition that does not need special device, produce the resin article of the coated with anti-staining film with good scuff resistance, weathering resistance expeditiously, it can prevent spot attached to transparent resin base material surface, even and adhere to also wiping easily.
Embodiment
Specify embodiments of the present invention by enumerating embodiment.
The formation method of the employed base material of embodiment and comparative example, the formation method of anti-reflection layer, various retes, evaluation method etc. are following described.
Resin base material:
(1) polycarbonate (PC) (trade(brand)name: POLICASE goods number: the thick 2mm of plastics industry in the ECK-100 tube (strain) film-making.(2) pet resin (PET) (trade(brand)name: (strain) system is spun by COSMOSHINE A4300, Japan), thickness 188 μ m.(3) cyclic olefin polymer (COP) (trade(brand)name: ZEONOR goods number: 1600 Japanese ZEON (strain) make), thickness 188 μ m.(4) plexiglass (PMMA) (trade(brand)name: the beautiful sun of ACRYLITE Mitsubishi (strain) is made), the thick 2mm of sheet.
The formation of anti-reflection layer 1:
Using high frequency magnetron splash method, is splash gas with Ar, makes SiO with the speed of 1.2 μ m/hr
2Film forming.SiO
2The refractive index of film is 1.46.In addition, use DC magnetron splash method, with Ar and O
2Mixed gas be splash gas, make TiO with the speed of 1.4 μ m/hr
2Film forming.TiO
2The refractive index of film is 2.30.
Since the 1st layer, be followed successively by TiO
2(nd=60nm)/SiO
2(nd=40nm)/TiO
2(nd=110nm)/SiO
2(nd=140nm) 4 layers of structure.Need to prove the value of expression blooming (refractive index n * physics thickness d) in the bracket.
The formation of anti-reflection layer 2:
Identical with the formation of above-mentioned anti-reflection layer 1, since the 1st layer, be followed successively by SiO
2(40nm)/TiO
2(20nm)/SiO
2(40nm)/TiO
2(300nm)/SiO
25 layers of structure (90nm).Need to prove, be blooming in the bracket.
The formation of anti-reflection layer 3:
(mean value of the standard deviation 1.3 of median size 110nm, particle diameter, major and minor axis length ratio is 1.03, solids component 15%, Japanese catalyst (strain) system, シ-ホ ス -KE-W10) 50g adds propylene glycol monomethyl ether 20g and concentrated hydrochloric acid 1g while stirring with the silicon dioxide microparticle dispersion liquid, add ethyl silicate 48 (mean polymerisation degree n=8, COLCOAT (strain) system) 5.3g then, stir after 2 hours, leave standstill and made it reaction in 24 hours.Afterwards, add propylene glycol monomethyl ether 164g, add the curing catalysts sodium acetate again, stir.Then, add conductive surface promoting agent FZ-2105 (Japanese UNICAR (strain) system) 4g, obtain low reflection layer solution.
Be coated with this low reflection layer solution with method of spin coating, at room temperature dry, making thickness is 110nm.
The formation of anti-reflection layer 4:
56g adds ethanol 20g, concentrated hydrochloric acid 1g while stirring with chain aggegation silicon dioxide microparticle dispersion liquid (average primary particle diameter 25nm, mean length 100nm, solids component 15%, daily output chemistry (strain) system ス ノ-テ Star Network ス OUP), add tetraethoxysilane 5.2g then, stir after 2 hours, leave standstill and made it reaction in 24 hours.Afterwards, add propylene glycol monomethyl ether 164g, add the curing catalysts aluminium acetylacetonate again, stir.Add ペ イ Star De 19 (DOWCORNING ASIA system) 4g again, obtain low reflection layer solution.Be coated with this low reflection layer solution with method of spin coating, at room temperature dry, making thickness is 110nm.
The formation of undercoat 1:
Silane acrylic acid or the like primary coat liquid uses weathering resistance priming paint (CP710, Japanese ARC (strain) system).This primary coat liquid is coated with into method of spin coating thickness is about 2 μ m after the curing, 110 ℃ down heating made undercoat 1 in 30 minutes.
The formation of undercoat 2:
Polyurethanes primary coat liquid uses common primary coat liquid (CP620, Japanese ARC (strain) system).This primary coat liquid is coated with into method of spin coating thickness is about 2 μ m after the curing, 50 ℃ down heating made undercoat 2 in 30 minutes.
The formation of hard coat 1:
With median size is colloid silica " ス ノ-テ Star Network ス O-40 " (daily output chemistry (strain) system: nonvolatile component 40%) after 150g and the methyltrimethoxy silane 183g reaction of 20nm, add Virahol 648g, acetate 18g, sodium acetate 1g and Flow Control agent " PAINTADDITIVE 19 " (DOW CORNING corporate system) 0.1g, stir, obtain giving anti-abrasive hard masking liquid 1.
Being coated with into hard masking liquid 1 usefulness method of spin coating thick after the curing is about 3 μ m, and 120 ℃ of heating promptly got hard coat 1 in 30 minutes.
Adding as 1,6 hexanediol diacrylate 12.4g, the gamma-amino propyl trimethoxy silicane 1.6g of polyfunctional acrylic ester, 2-methoxypropanol 6.3g, acetate 4.0g, as Photoepolymerizationinitiater initiater benzophenone 0.8g, colloid silica " NPC-ST-30 " (daily output chemistry (strain) system, the silicon dioxide microparticle of median size 20nm just is being dispersed in-propyl cellosolve in.Dioxide-containing silica is 30 weight %) 26.0g, give the film pliability and improve epoxy acrylate " epoxy ester 3002M " (common prosperity society chemistry (strain)) 5.0g, the butylacetate 14.5g of film hardness.Then, add Flow Control agent [PAINTADDO 19 DOW CORNING (strain) system] 0.1g, add 2-methoxypropanol 100g again, stirring makes it to be uniformly dispersed, and promptly gets the hard masking liquid 2 that is used to give scuff resistance.
Hard masking liquid 2 usefulness method of spin coating being coated with into thickness is about 5 μ m after the curing, thereafter, is the ultra violet lamp 1 second～30 seconds of 120W/cm with output rating, makes its total energy of accepting uviolizing reach 1000 (mJ/cm
2), will promptly get hard coat 2 after the coating fluid curing.Need to prove that the value of uviolizing total energy is measured (model: UIT-102USHIO Electric Co., Ltd system) with the accumulation quantorecorder.
The formation of nesa coating:
Using high frequency (RF) magnetron spraying and splashing facility, is target, Ar+O with ITO
2For splash gas, base material temperature are that 130 ℃, film formation speed are about 1 μ m/hr, form the ITO film.
The formation of stain-proofing layer 1:
In 100g ethanol (water ratio 0.35 weight %), add 3-17 fluorine decyl Trimethoxy silane (CF
3(CF
2)
7(CH
2)
2Si (OCH
3)
3, the SILICONE of SHIN-ETSU HANTOTAI (strain) system) 0.02g, stirred 30 minutes, add tetrachloro silicane (SiCl then while stirring
4, the SILICONE of SHIN-ETSU HANTOTAI (strain) system) 1.0g, obtain waterproof didirtresistance tunicle and form and use solution.This solution represents with weight part, and with respect to from the Si in the tetrachloro silicane 100, the Si that contains from 3-17 fluorine decyl Trimethoxy silanes is the moisture concentration of 0.6, about 0.2 normal concentration of hydrochloric acid and 0.35 weight %, and pH is about 0.7.Then the polymerization degree of the polymkeric substance of the tetraethoxysilane in this solution is 1～3.With this solution under humidity 30%, room temperature with the coating of streaming coating method, at room temperature dry 1 minute, the resin article of the coated with anti-staining film of the thick stain-proofing layer 1 of about 60nm that obtains being covered.
The formation of stain-proofing layer 2:
In 100g ethanol (water ratio 0.35 weight %), add 3-17 fluorine decyl Trimethoxy silane (CF
3(CF
2)
7(CH
2)
2Si (OCH
3)
3, the SILICONE of SHIN-ETSU HANTOTAI (strain) system) 0.02g, stirred 30 minutes, add tetraethoxysilane (Si (OCH then while stirring
2CH
3)
4) 1.2g, continue to add while stirring concentrated hydrochloric acid (35 weight %, Northeast chemistry (strain) system) 2g and obtain waterproof didirtresistance tunicle formation solution.With respect to from the Si in the tetraethoxysilane 100, then to contain the Si from 3-17 fluorine decyl Trimethoxy silanes be 0.6, about 0.2 normal concentration of hydrochloric acid and 1.6 weight % moisture concentrations to this solution, and pH is about 0.7.Then the polymerization degree of the polymkeric substance of the tetraethoxysilane in this solution is 1～3.
With this solution under humidity 30%, room temperature with the coating of streaming coating method, at room temperature dry 1 minute, the resin article of the coated with anti-staining film of the thick stain-proofing layer 2 of about 60nm that obtains being covered.
Evaluation method:
The oil resistant China ink of the resin article of the coated with anti-staining film of each embodiment gained shown below, anti-finger printing, scuff resistance, contact angle, the evaluation method that tumbles angle, reflectivity and surfaceness are as follows.
1. oil resistant China ink
(a). the tack of ink pens
With ink pens (ZEBRA/marky is superfine) draw back and forth several times, draw at substrate surface long for the straight line of 1cm, estimate it and adhere to complexity or conspicuous complexity, criterion is as follows.
Zero: printing ink person's handwriting bullet globulate
*: the printing ink person's handwriting is bullet not, can write.
(b). the erasability of printing ink person's handwriting
With the oiliness person's handwriting of Mierocrystalline cellulose system non-woven fabrics (BEMCOT M-3: Asahi Chemical Industry's (strain) makes) wipe substrate surface attachment, estimate its wiping complexity.Judging criterion is as follows.Measure the number of times of wiped clean in addition.
Zero: the printing ink person's handwriting is wiped clean fully
△: printing ink person's handwriting wiping vestige has residual
*: the printing ink person's handwriting can't be wiped.
2. anti-finger printing
(BEMCOT M-3: Asahi Chemical Industry's (strain) system) wiping is attached to the fingerprint of substrate surface, estimates it and wipes complexity with Mierocrystalline cellulose system non-woven fabrics.Judging criterion is as follows.Measure the number of times till having wiped in addition.
Zero: fingerprint can be wiped fully
△: fingerprint trace has residual
*: fingerprint trace enlarges, can't wipe.
3. wear-resisting wiping
Use heavy burden 250g/cm
2Mierocrystalline cellulose system non-woven fabrics (BEMCOT M-3: Asahi Chemical Industry's (strain) system) surface 50 times of the resin article of wiping gained coated with anti-staining film back and forth, carry out wear-resisting wiping experiment, range estimation has or not scar then.Judging criterion is as follows.
Zero: no scar.
△: some scars occur.
*: remarkable scar appears.
Contact angle, tumble the measuring method at angle
The resin article of measuring made coated with anti-staining film with contact angle meter (CA-DT, consonance interface science (strain) system) leaves standstill contact angle (following sometimes also note make CA) by what the water droplet of 2mg weight produced.The value of this contact angle is big more, shows that static hydrophobicity is that didirtresistance (spot is adhered to complexity) is good more.
Place the water droplet of diameter 5mm then on the surface of the resin article of the coated with anti-staining film of horizontal positioned, the resin article of coated with anti-staining film is slowly tilted, the angle of inclination when measuring its surperficial globule and beginning to roll (critical inclination angle, tumble the angle).It is more little to tumble the angle, illustrates that dynamic hydrophobicity is that didirtresistance (complexity that spot drops) is good more.
5. reflectivity
Optical characteristics is measured: measure visible reflectance (%) according to JIS R3212.The more for a short time antireflection property that shows of this value is high more.
6. surfaceness
The antifouling film tunicle of the resin article of the coated with anti-staining film that the present invention makes has the very good characteristics of surface smoothness.The surfaceness of the resin article of coated with anti-staining film is measured by arithmetic average roughness (Ra) and 10 mean roughness (Rz).Surface roughness characteristics Ra, Rz can measure by two dimension definition JIS B 0601-1982 are expanded as three-dimensional method.
7. surperficial fluorine concentration
The fluorine concentration on the antifouling film surface of the resin article of the coated with anti-staining film that the present invention makes is measured the atomic ratio (F/Si) of F and Si with X linear light electronics optical spectroscopy (ESCA).The condition determination of X linear light electronics optical spectroscopy is: the K α line with single aluminum chloride is the X source, anode energy: 1486.6ev, anode output rating: 150W, acceleration voltage: 14kV, the X line is to the input angle of sample: 45 degree, analyze area: and the circle of diameter 800 μ m, measure thickness: number nm.
Embodiment 1
On above-mentioned polycarbonate sheet base material, form undercoat 1, form hard coat 1 then thereon, form stain-proofing layer 2 more thereon, promptly make the resin article of the coated with anti-staining film that constitutes by PC layer/undercoat 1/ hard coat 1/ stain-proofing layer 2.Measure these article initial stage contact angle (degree), tumble angle (degree), surperficial fluorine concentration (F/Si), visible reflectance (%), oil resistant China ink (wiping property (being erasing times in the bracket) and tack), anti-finger printing (wiping property), surfaceness (arithmetic average roughness Ra (nm) and 10 mean roughness Rz (nm) and scuff resistance (and scar adhere to and frictional experiment after contact angle), the result is as shown in table 1.
Embodiment 2～8
On the resin base material shown in the table 1, form undercoat as shown in table 1, hard coat, functional layer (transparency conducting layer), anti-reflection layer, stain-proofing layer successively, make the resin article of coated with anti-staining film, equally with embodiment 1 measure various performances, its result is as shown in table 1.
Change into and form the hard masking liquid 2 that hard coat 2 uses among the embodiment 2, in hard masking liquid 2, add 30g boron class antistatic agent " HIBORON KB212 " (effective constituent 10%, Proninternational system) again, obtain the hard masking liquid of anti-electrostatic, other equally makes the resin article of coated with anti-staining film with embodiment 2.Static electricity resistance is 10
11～10
12Ω/.Other performance is almost completely identical with the embodiment 2 that does not have static electricity resistance.
Change among the embodiment 5 form that anti-reflection layer 4 uses low reflection layer solution, in the modulation of this low reflection layer solution, add " Paintaddo19 " 4g, add tensio-active agent " FZ-2105 " (Japanese Unika system) 5g, use the resin article of the same coated with anti-staining film of the preparation of this antireflection (anti-electrostatic) liquid and embodiment 5.Static electricity resistance is 10
12～10
13Ω/.Other performance is almost completely identical with the embodiment 5 that does not have the anti-electrostatic functionality.
Comparative example 1
Change among the embodiment 1 stain-proofing layer 1 that forms, coating into by containing useful [R
fSi (OEt)
3: Rf is that perfluor base, Et are ethyl] silane material that the contains the perfluor base 0.2 weight % of expression and with [(H
2RfPO
4): Rf is the perfluor base] coating fluid formed of the ethanolic soln of the phosphoric acid ester that the contains the perfluor base 7.0 weight % of expression, form stain-proofing layer 66 ℃ of dry down backs, other operation is identical with embodiment 2, make the resin article of coated with anti-staining film, equally measure various performances with embodiment 2, the result is as shown in table 1.
Comparative example 2
Change the hard coat 2 that forms among the embodiment 8 into, do not form hard coat, surface oxygen containing Cement Composite Treated by Plasma in advance, make the resin wetting abilityization, other forms resin article with the same coated with anti-staining film of embodiment 8 to use this resin manufacture, equally measure various performances with embodiment 8, the result is as shown in table 1.
Table 1
| Embodiment, comparative example NO | The substrate resin kind | The undercoat numbering | The hard coat numbering | The sense film | Anti-reflection layer | The stain-proofing layer numbering | ||
| Numbering | Method for making | Film is formed | ||||||
| Embodiment 1 | The PC sheet | 1 | 1 | - | - | - | - | 2 |
| Embodiment 2 | The PC film | - | 2 | - | 1 | The splash of high frequency magnetron | SiO 2 | 1 |
| Embodiment 3 | The PET film | 2 | 1 | - | 2 | The splash of high frequency magnetron | SiO 2/TiO 2/SiO 2/ TiO 2/SiO 2 | 2 |
| Embodiment 4 | The COP film | - | 2 | Conducting film (ITO) | 3 | Colloidal gel method | SiO 2Particulate | 1 |
| Embodiment 5 | The COP film | 1 | - | - | 4 | Colloidal gel method | SiO 2The chain particulate | 1 |
| Embodiment 6 | The PMMA film | - | 2 | - | 3 | Colloidal gel method | SiO 2Particulate | 2 |
| Embodiment 7 | The COP film | - | - | - | 2 | The splash of high frequency magnetron | SiO 2/TiO 2/SiO 2/ TiO 2/SiO 2 | 1 |
| Embodiment 8 | The PC film | - | 2 | - | - | - | - | 1 |
| Comparative example 1 | The PC film | - | 2 | - | 1 | The splash of high frequency magnetron | SiO 2 | 1 |
| Comparative example 2 | The PC film | - | - | - | - | - | - | 1 |
Table 1 is continuous
| Embodiment, comparative example NO | Initial performance | Reflectivity | The oil resistant China ink | Anti-finger printing | Surfaceness | Rub resistance | |||||
| Contact angle) | Tumble angle (degree) | F/Si | (％) | Wiping property | Tack | Wiping property | Ra(nm) | Rz(nm) | Cut | Friction back contact angle (degree) | |
| Embodiment 1 | 110 | 5 | 1.1 | 8 | ○ | ○ | ○(3) | 0.4 | 3.0 | ○ | 107 |
| Embodiment 2 | 111 | 4 | 1.2 | 0.3 | ○ | ○ | ○(3) | 0.3 | 3.2 | ○ | 104 |
| Embodiment 3 | 109 | 6 | 1.1 | 0.2 | ○ | ○ | ○(3) | 0.3 | 4.0 | ○ | 103 |
| Embodiment 4 | 111 | 12 | 1.2 | 0.8 | ○ | ○ | ○(5) | 20 | 45.0 | ○ | 105 |
| Embodiment 5 | 110 | 5 | 1.2 | 0.5 | ○ | ○ | ○(5) | 10 | 29.0 | ○ | 103 |
| Embodiment 6 | 112 | 13 | 1.1 | 0.8 | ○ | ○ | ○(5) | 18 | 40.0 | ○ | 106 |
| Embodiment 7 | 110 | 5 | 1.2 | 0.2 | ○ | ○ | ○(3) | 0.4 | 4.0 | ○ | 102 |
| Embodiment 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)
1. the preparation method of the resin article of coated with anti-staining film, it is characterized in that, has surface at least on the preparation surface and is the transparent resin base material of the stratum basale that forms by siliceous resin or mineral compound, coating contains silane oxide, contains the silane compound of fluoro-alkyl and the coating fluid of acid, the dry then stain-proofing layer that forms on the stratum basale of this transparent resin base material.
2. the described method of claim 1, wherein, above-mentioned coating fluid is that the compound of chloride silyl and the silane compound that contains fluoro-alkyl are dissolved in the solvent that contains alcohol and/or water, replaces the chlorine of above-mentioned chloride silyl compound and the material that obtains with alkoxyl group or hydroxyl.
3. the described method of claim 1, wherein, above-mentioned coating fluid is tetraalkoxysilane or its polymkeric substance or their hydrolyzate, the silane compound that contains fluoro-alkyl and acid are dissolved in the alcoholic solvent and get.
4. the described method of claim 1, wherein, the stratum basale of above-mentioned mineral compound is with the antireflection film of silicon-dioxide for top layer.
5. the described method of claim 1, wherein, the antireflection film that the stratum basale of above-mentioned mineral compound is made up of silicon dioxide microparticle.
6. the described method of claim 1, wherein, the stratum basale of above-mentioned resin is the hard coat film that contains colloid silica.
7. the described method of claim 1, wherein, the hard coat film that the stratum basale of above-mentioned resin is made up of silicone resin.
8. wherein, also there is undercoat in the described method of claim 1 between above-mentioned transparent resin base material and the above-mentioned stratum basale.
9. wherein, also there are hard coat in claim 4 or 5 described methods between above-mentioned transparent resin base material and the above-mentioned antireflection film.
10. wherein, also there is nesa coating in the described method of claim 9 between above-mentioned hard coat and the above-mentioned antireflection film.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP361737/2003 | 2003-10-22 | ||
| JP2003361737 | 2003-10-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1723237A true CN1723237A (en) | 2006-01-18 |
Family
ID=34463498
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200480001945XA Pending CN1723237A (en) | 2003-10-22 | 2004-10-22 | Method for producing resin article coated with anti-staining film |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR20060095442A (en) |
| CN (1) | CN1723237A (en) |
| TW (1) | TW200514811A (en) |
| WO (1) | WO2005037901A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102019730A (en) * | 2010-12-21 | 2011-04-20 | 苏州禾盛新型材料股份有限公司 | Antifouling fingerprint-resistant and Newton Ring-resistant transparent conductive composite plate |
| CN102455822A (en) * | 2010-10-15 | 2012-05-16 | 株式会社日立显示器 | Manufacturing method of touch panel and touch panel |
| CN102962183A (en) * | 2012-12-10 | 2013-03-13 | 昆山伟翰电子有限公司 | Organic silicon product surface oil-seal method |
| CN113166920A (en) * | 2018-11-13 | 2021-07-23 | Ａｇｃ株式会社 | Substrate with water-and oil-repellent layer, vapor deposition material, and method for producing substrate with water-and oil-repellent layer |
| CN113260463A (en) * | 2018-12-26 | 2021-08-13 | Ａｇｃ株式会社 | Substrate with water-and oil-repellent layer, vapor deposition material, and method for producing substrate with water-and oil-repellent layer |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3411009B2 (en) * | 2000-06-16 | 2003-05-26 | 株式会社麗光 | Anti-reflection film |
-
2004
- 2004-10-20 TW TW093131829A patent/TW200514811A/en unknown
- 2004-10-22 KR KR1020057019230A patent/KR20060095442A/en not_active Application Discontinuation
- 2004-10-22 CN CNA200480001945XA patent/CN1723237A/en active Pending
- 2004-10-22 WO PCT/JP2004/016055 patent/WO2005037901A1/en active Application Filing
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102455822A (en) * | 2010-10-15 | 2012-05-16 | 株式会社日立显示器 | Manufacturing method of touch panel and touch panel |
| CN102019730A (en) * | 2010-12-21 | 2011-04-20 | 苏州禾盛新型材料股份有限公司 | Antifouling fingerprint-resistant and Newton Ring-resistant transparent conductive composite plate |
| CN102962183A (en) * | 2012-12-10 | 2013-03-13 | 昆山伟翰电子有限公司 | Organic silicon product surface oil-seal method |
| CN113166920A (en) * | 2018-11-13 | 2021-07-23 | Ａｇｃ株式会社 | Substrate with water-and oil-repellent layer, vapor deposition material, and method for producing substrate with water-and oil-repellent layer |
| CN113260463A (en) * | 2018-12-26 | 2021-08-13 | Ａｇｃ株式会社 | Substrate with water-and oil-repellent layer, vapor deposition material, and method for producing substrate with water-and oil-repellent layer |
| CN113260463B (en) * | 2018-12-26 | 2023-09-22 | Ａｇｃ株式会社 | Substrate with water-repellent oil-repellent layer, vapor deposition material, and method for producing substrate with water-repellent oil-repellent layer |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20060095442A (en) | 2006-08-31 |
| WO2005037901A1 (en) | 2005-04-28 |
| TW200514811A (en) | 2005-05-01 |
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