CN1488698A

CN1488698A - Coating liquid for forming transparent film and base material and display device with transparent film

Info

Publication number: CN1488698A
Application number: CNA031577776A
Authority: CN
Inventors: 松田政幸; 晴; 平井俊晴; 郎; 小松通郎
Original assignee: Catalysts and Chemicals Industries Co Ltd
Current assignee: JGC Catalysts and Chemicals Ltd
Priority date: 2002-08-28
Filing date: 2003-08-28
Publication date: 2004-04-14
Anticipated expiration: 2023-08-28
Also published as: JP2004083812A; CN100478411C; KR100996052B1; KR20040019978A

Abstract

To provide a coating liquid for forming a transparent coating film having improved film strength and conductivity without causing cracking in the formation of the film and, when a conductive layer is formed as a lower layer, causing uniform shrinkage including the conductive layer to prevent the generation of cracks and provide a substrate having transparent conductive coating layer produced by using the coating liquid and a display device provided with the substrate. The coating liquid for forming a transparent coating film contains a matrix precursor composed of (i) a hydrolyzed product of a tetraalkoxysilane and (ii) a hydrolyzed product of an organic silicon compound having one or more functional groups selected from epoxy group, acrylic group and vinyl group. The ratio of the component (ii) in the matrix precursor is 0.5-50 wt.%. The matrix precursor is produced by the simultaneous hydrolysis of a mixture of the tetraalkoxysilane and the organic silicon compound having one or more functional groups selected from epoxy group, acrylic group and vinyl group.

Description

Transparent film forms body material, the display unit with coating fluid and band transparent film

Technical field

The transparent film that the present invention relates to form transparent film forms with coating fluid and has the body material of the band transparent conductive film that adopts the transparent film that this coating fluid forms, possesses the display unit of this body material.

Background technology

All the time, for the anti-charged and antireflection in the surface that makes these class transparent base materials of display panel such as cathode tube, fluorescent display tube, LCD panel, generally form a kind of transparent film with anti-charged and anti-reflective function on its surface.

And well-known, can give off hertzian wave from cathode tube etc., therefore, except original anti-charged and antireflection, preferably also want the formed electromagnetic field of shielding electromagnetic wave and electromagenetic wave radiation.

Shielding one of this electromagnetic method is to form a kind of conductive membrane that is used for shielding electromagnetic wave on the surface of display panels such as cathode tube.If the anti-charged conductive membrane of using, its surface resistivity is at least 10 ⁸Just enough about Ω/, the conductive membrane that the shielding electromagnetism is used then must have 10 ²～10 ⁴The surface resistivity that Ω/ is low like this.

If adopt the existing coating fluid that contains the stannic oxide of mixing Sb or mix this class electroconductive oxide of Indium sesquioxide of Sn to form the low conductive membrane of above-mentioned surface resistivity, compare the film of existing anti-charging property, just must increase the thickness of film.But problem has also produced thereupon, if promptly the film thickness of conductive membrane is not in the scope of 10～200nm, does not then have the effect of antireflection.Therefore, with the stannic oxide of the existing Sb of mixing or mix this class electroconductive oxide of Indium sesquioxide of Sn, be difficult to obtain that surface resistivity is low, the electromagnetic wave shielding performance is good, and the also good conductive membrane of antireflection property.

Also have, one of the method that forms the conductive membrane of low surface resistivity is to adopt the coating fluid of metal particle such as argentiferous to form the conductive membrane of low surface resistivity at substrate material surface.In this kind method, gelationus metal particle is scattered in polar solvent and the solution that obtains as coating fluid.For improving the dispersiveness of colloidal metallic particulate, the metal particle surface in this coating fluid is handled with organic stabilizers such as polyvinyl alcohol, polyvinylpyrrolidone or gelatin.But, form the conductive membrane that forms with coating fluid with the film of this containing metal particulate, because the metal particle in the film contacts by stablizer each other, intergranular resistance increases, so the surface resistivity of film can not reduce.Therefore after making film, must carry out sintering with the high temperature about 400 ℃, decompose and remove destabilizing agent, if but remove destabilizing agent at high temperature sintering for decomposing, then can produce mutual the fusing and aggegation of metal particle, thereby cause the transparency of conductive membrane and the problem of low visibility.Under situations such as cathode tube, if also there is the problem that exposes the deterioration of performance meeting at high temperature.

And metal particle is different with aforementioned electroconductive oxide, and its is originally just light tight, and therefore the conductive membrane that forms with metal particle is influenced by the density of the metal particle in the conductive membrane and film thickness etc., has the low problem of transparency.

Have again, the resistance to salt water and the scale resistance of the existing transparent conducting film that contains metal particle such as Ag are low, so metal is oxidized, ionization causes that particle increases, and can corrode under some situation, cause the electroconductibility and the transmittance of film low, have the problem of display unit poor reliability.

The present inventor is in order to improve charging preventive property and electromagnetic wave shielding performance etc., simultaneously also in order to improve film strength (hardness) and cut intensity etc., carried out deep research, found that if matrix precursor uses the coating fluid of the hydrolyzate that contains the silicoorganic compound with specific functional group, form transparent film at conductive layer surface, then can not produce the crack when transparent film forms, film toughness strengthens, and electroconductibility improves, and has finally finished the present invention thus.

The purpose of this invention is to provide a kind of transparent film formation coating fluid, when using this coating fluid to form transparent film, can not produce the crack, and when conductive layer is formed at lower floor, comprise that conductive layer shrinks together uniformly, can not form thus and can produce the transparent film that crack, film toughness and electroconductibility improve simultaneously.The body material of the band transparent conductive film that utilizes this coating fluid formation also is provided, has possessed the display unit of this body material.

Summary of the invention

It is to comprise by the hydrolyzate of (i) tetraalkoxysilane and (ii) have the matrix precursor that the hydrolyzate of silicoorganic compound of at least a kind of functional group of the epoxy group(ing) of being selected from, acryl, vinyl forms that transparent film of the present invention forms feature with coating fluid, and the ratio (ii) in the matrix precursor is pressed solid component meter in the scope of 0.5～50 weight %.

Above-mentioned matrix precursor is tetraalkoxysilane and hydrolyzate when having the mixture of silicoorganic compound of at least a kind of functional group of the epoxy group(ing) of being selected from, acryl, vinyl preferably.

Also can contain the hydrolyzate of the silicoorganic compound that (iii) have fluorine replacement organic radical in the above-mentioned matrix precursor, the ratio (iii) of this in the matrix precursor is pressed solid component meter in the scope of 0.1～30 weight %.

Above-mentioned have a hydrolyzate tetraalkoxysilane and have fluorine hydrolyzate when replacing the mixture of silicoorganic compound of organic radical preferably that fluorine replaces the silicoorganic compound of organic radical.

The body material of band transparent conducting film of the present invention is made of transparent conductivity particulate layer that contains electrically conductive microparticle on body material, the body material and the low transparent film of this transparent conductivity particulate layer of refractive index ratio that be located on this transparent conductivity particulate layer, the feature of this body material is that transparent film is formed with coating fluid by above-mentioned transparent film and forms.

The feature of display unit of the present invention is, possesses the front panel that the body material of above-mentioned band transparent conducting film forms, and transparent conducting film is formed at the outside surface of this front panel.

Embodiment

Transparent film forms uses coating fluid

The feature that transparent film of the present invention forms with coating fluid is; matrix precursor is made of the hydrolyzate of (i) tetraalkoxysilane and the hydrolyzate of silicoorganic compound that (ii) has a kind of functional group of the epoxy group(ing) of being selected from, acryl, vinyl at least, and the ratio (ii) in the matrix precursor is pressed solid component meter in the scope of 0.5～50 weight %.

Tetraalkoxysilane comprises tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes etc.

In the presence of acid catalyst, make tetraalkoxysilane in water-pure mixed solvent, add the hydrolyzate (i) that water decomposition can access tetraalkoxysilane.

In addition, hydrolyzate can be a partial hydrolystate, also can be the polycondensate of hydrolyzate.The hydrolyzate of this tetraalkoxysilane is known.

Used in the present invention have an epoxy group(ing) of being selected from; acryl; the silicoorganic compound of at least a kind of functional group of vinyl comprise γ-glycidoxypropyltrime,hoxysilane; γ-glycidoxy propyl group methyldiethoxysilane; γ-glycidoxy propyl-triethoxysilicane; β-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane; γ-methacryloxypropyl methyl dimethoxysilane; γ-methacryloxypropyl trimethoxy silane; γ-methacryloxypropyl methyldiethoxysilane; γ-methacryloxypropyl triethoxyl silane; vinyltrimethoxy silane; vinyltriethoxysilane; vinyl three ('beta '-methoxy oxyethyl group) silane etc.

These have the hydrolyzate of silicoorganic compound of at least a kind of functional group of the epoxy group(ing) of being selected from, acryl, vinyl, and (ii) also the hydrolyzate (i) with above-mentioned tetraalkoxysilane is the same; can be in the presence of acid catalyst, make silicoorganic compound add water decomposition and obtain at water-pure mixed solvent with functional groups such as epoxy group(ing).This hydrolyzate can be a partial hydrolystate, also can be the polycondensate of hydrolyzate.Can adopt known in the past hydrolyzate.

The molecular weight of hydrolyzate is generally 500～20000, and more preferably 600～10000.

The molecular weight of hydrolyzate is less than 500 o'clock, shrinks greatly, easily produces the crack, if the molecular weight of hydrolyzate surpasses 20000, then with the poor adhesion of body material, undercapacity is enough.The ratio of (i) is counted 50～99.5 weight % by solids component in the matrix precursor, more preferably 70～99 weight %.(ii) ratio is counted 0.5～50 weight % by solids component in the matrix precursor, more preferably 1～30 weight %.

If use the matrix precursor contain this specific hydrolyzate, then when the electrically conductive particles laminar surface formed transparent film, the crack was few, and can produce high conductive membrane body material.

If contain the hydrolyzate that possesses above-mentioned characteristic in the matrix precursor, then the crack produces few, when forming transparent film, compare with the situation that only forms electrically conductive microparticle, though it is also uncertain to form the reason of the high membrane body material of electroconductibility, but can infer, the contraction of the vertical direction of this matrix precursor film (being thickness direction) is big, in contrast, the contraction of horizontal direction (being in-plane) is little, therefore vertical (thickness) to contraction be main, the contraction during film formation can not cause fissured generation substantially like this.

Also have, because the contraction of this transparent film when forming film is longitudinally, so when the electrically conductive microparticle layer being set in lower floor, itself also shrinks the electrically conductive microparticle layer with the contraction of transparent film, reduce in gap in the electrically conductive microparticle layer, electrically conductive microparticle is filled in the electrically conductive microparticle layer densely thus, the also corresponding raising of electroconductibility.

Therefore, even reduce the thickness of transparent film, can not produce the crack yet, and can form the transparent film of the electroconductibility that can improve the electrically conductive microparticle layer.

If the ratio (ii) in the matrix precursor is pressed solid component meter less than 0.5 weight %, then when forming transparent film, may produce the crack greatly owing to the contraction of horizontal direction.Also have, when the electrically conductive microparticle laminar surface formed transparent film, little owing to shrinking longitudinally, so the raising effect of electroconductibility is insufficient, the raising effect of film hardness was also not obvious like this.

Surpass 50 weight % if the ratio (ii) in the matrix precursor is pressed solid component meter, then the effect that electroconductibility improves because above-mentioned horizontal direction and contraction longitudinally reduce is insufficient, and the raising effect of film hardness is also not obvious like this.

If the ratio (ii) in the matrix precursor is pressed solid component meter in above-mentioned scope, then under the identical situation of film thickness, electroconductibility increases, therefore the transparent conductivity particulate layer that has similar face resistance can reduce film thickness, reduce cost, in bigger wavelength region, reflectivity is low, can access the body material of the band transparent conducting film that the visual sense reflectivity is low, display performance is good simultaneously.

Matrix precursor used in the present invention is tetraalkoxysilane and hydrolyzate when having the mixture of silicoorganic compound of at least a kind of functional group of the epoxy group(ing) of being selected from, acryl, vinyl preferably.Hydrolyzate can be in the presence of acid catalyst in the time of this mixture, makes mixture add water decomposition in water-pure mixed solvent and obtains.In this case, hydrolyzate can be a partial hydrolystate, also can be the polycondensate of hydrolyzate.

If this while hydrolyzate as matrix precursor, is then compared with the situation of mixed hydrolysis thing respectively, the contraction of film can be carried out more equably, therefore just might improve film toughness, maintenance electrically conductive microparticle floor height electroconductibility.Though its reason is also not clear and definite, can infer, owing to add water decomposition simultaneously, so generated tetraalkoxysilane and epoxy is the multipolymer of silicoorganic compound.

Have again; the while hydrolyzate is used as under the situation of matrix precursor; ratio (ii) in the matrix precursor (promptly; the ratio of the hydrolyzate of the silicoorganic compound of contained at least a kind of functional group in the while hydrolyzate) counts 0.5～50 weight % by solids component, more preferably 1～40 weight % with the epoxy group(ing) of being selected from, acryl, vinyl.

Can also contain in the above-mentioned matrix precursor and (iii) have the hydrolyzate that fluorine replaces the silicoorganic compound of organic radical.When containing the hydrolyzate of the silicoorganic compound with fluorine replacement organic radical, the ratio (iii) in this matrix precursor is counted 0.1～30 weight % by solids component, more preferably 0.5～20 weight %.

Silicoorganic compound with fluorine replacement organic radical comprise 3,3,3-three fluoro propyl trimethoxy silicanes, methyl-3,3,3-three fluoro propyl group dimethoxy silane, heptadecyl three fluoro decyl methyl dimethoxysilanes, heptadecyl three fluoro decyl Trimethoxy silanes, heptadecyl three fluoro Trimethoxy silanes, n-perfluoro octyl group ethyl triethoxysilane etc.

This have fluorine replace the hydrolyzate of the silicoorganic compound of organic radical (iii) also can be in the presence of acid catalyst, make to have silicoorganic compound that fluorine replaces organic radical and in water-pure mixed solvent, add water decomposition and obtain.In this case, hydrolyzate can be a partial hydrolystate, also can be the polycondensate of hydrolyzate, can use known in the past hydrolyzate.

Ratio (iii) in the matrix precursor press solid component meter less than above-mentioned down in limited time, the raising effect of stain resistance (prevent fingerprint etc. adhere to), water-repellancy and cut intensity is insufficient.Surpass the above-mentioned upper limit if the ratio (iii) in the matrix precursor is pressed solid component meter, then film hardness (pencil-lead hardness, steel wool hardness) descends.

Matrix precursor used in the present invention is tetraalkoxysilane and have fluorine hydrolyzate when replacing the mixture of silicoorganic compound of organic radical preferably (iii).Hydrolyzate can be in the presence of acid catalyst in the time of this mixture, makes tetraalkoxysilane and have mixture that fluorine replaces the silicoorganic compound of organic radical to add water decomposition and obtain in water-pure mixed solvent.In this case, hydrolyzate can be a partial hydrolystate, also can be the polycondensate of hydrolyzate.

Contain composition (i) simultaneously, (ii) reach under (iii) the situation, it can be the mixture of hydrolyzate separately, can be (i) and the mixture of hydrolyzate and (iii) hydrolyzate (ii) the time, can also be (i) and the mixture of hydrolyzate hydrolyzate with (ii) and (iii) time the (ii) the time, or the mixture of hydrolyzate and (i) hydrolyzate (ii) and (iii) time the, or hydrolyzate (i), (ii) and (iii) the time.

The whole silicoorganic compound that adopted when forming hydrolyzate simultaneously and have fluorine replace organic radical silicoorganic compound amount than should satisfy the ratio that makes in the matrix precursor (iii) by solid component meter in the scope of 0.1～10 weight %, be more preferably the requirement in the scope of 0.5～5 weight %.

If with this while hydrolyzate as matrix precursor (iii), then film shrinks and can carry out equably, when obtaining effect that improves electroconductibility and the effect that improves film hardness, can also obtain higher water-repellancy and cut intensity.

This hydrolyzate with silicoorganic compound of fluorine replacement organic radical also can make the silicoorganic compound with fluorine replacement organic radical add water decomposition in the presence of acid catalyst in water-pure mixed solvent and obtain.This hydrolyzate can be a partial hydrolystate, also can be the polycondensate of hydrolyzate.Can adopt known in the past hydrolyzate.

It is 5～300nm that transparent film of the present invention forms with containing median size in the coating fluid, be preferably 10～200nm, and specific refractory power is 1.28～1.42, be preferably 1.28～1.40 low-refraction particulate.

If the bottom reflection rate and the visual sense reflectivity of the body material of the band transparent conducting film that the specific refractory power of low-refraction particulate in above-mentioned scope, then obtains are low, antireflection property that can exhibit excellent.

The consumption of low-refraction particulate should satisfy following requirement, and promptly the content of the low-refraction particulate in the transparent film is converted into solids component, should be preferably in the scope of 20～80 weight % in the scope of 10～90 weight %.

This low-refraction particulate can use known in the past particulate as long as its median size and specific refractory power in above-mentioned scope, do not have special the qualification to it.For example, disclosed composite oxide sol in the Japanese patent laid-open 7-133105 of applicant application communique, disclosed in No. 00/37359 communique of WO have a tectal porous matter composite oxide particle.

In addition, transparent film of the present invention forms a spot of electrically conductive microparticle and/or the additives such as dyestuff or pigment of the particulate, the transparency that does not influence transparent film and the antireflection property that form with low-index materials such as can also containing useful magnesium fluoride in the coating fluid.

Among the present invention, can be when this transparent film of coating forms the film drying that forms with coating fluid or after the drying, heat with the temperature more than 150 ℃, or, perhaps expose to the open air in ammonia isoreactivity atmosphere gas with unhardened films of electromagnetic wave irradiation such as the short ultraviolet ray of wavelength ratio visible rays, electron beam, X ray, gamma-rays.Can promote film to form the sclerosis of composition like this, improve the hardness of gained transparent film.

The body material of band transparent conducting film

Below, describe the body material of band transparent conducting film involved in the present invention in detail.

In the body material of band transparent conducting film of the present invention, electrically conductive microparticle by median size 1～200nm on the film, thin slice and other the body materials such as formed body that constitute with glass, plastics, pottery etc. forms transparent conductivity particulate layer, form the low transparent film of this transparent conductivity particulate layer of refractive index ratio on this transparent conductivity particulate layer again, this transparent film is formed with coating fluid by above-mentioned transparent film and constitutes.

Transparent conductivity particulate layer

[electrically conductive microparticle]

Electrically conductive microparticle used in the present invention is as long as the surface resistivity of gained transparent conducting film is 10 ²～10 ⁸Get final product in the scope of Ω/, it is not had special the qualification, can adopt known in the past electrically conductive microparticle.

Electrically conductive microparticle comprises stannic oxide, mixes the stannic oxide of Sb, F or P, and Indium sesquioxide is mixed the Indium sesquioxide of Sn or F, oxide based electrically conductive microparticles such as weisspiessglanz and titanium suboxide.

The median size of oxide based electrically conductive microparticle is 1～200nm, more preferably 2～150nm.

Median size is during less than 1nm, and particle is too small, easily aggegation, and since the surface resistivity of particulate layer sharply increase, so can not obtain having the film of the low-resistance value that can reach target of the present invention.If median size surpasses 200nm, then particle is bigger, and interparticle point of contact reduces, and can not obtain sufficient electroconductibility.And film toughness reaches the binding property reduction with body material, and the turbidity of the transparent conducting film that obtains increases.

In addition, electrically conductive microparticle can use known in the past metal particle, and this metal particle can be the metal particle that has single component to constitute, and also can be the composition metal particulate that contains the metal ingredient more than 2 kinds.

The metal particle that comprises the formation of metal more than at least a kind or 2 kinds of metals such as being selected from Au, Ag, Pd, Pt, Rh, Ru, Cu, Fe, Ni, Co, Sn, Ti, In, Al, Ta, Sb specifically.

The effect metallic combination more than 2 kinds preferably that constitutes metal particle comprises Au-Cu, Ag-Pt, Ag-Pd, Au-Pd, Au-Rh, Pt-Pd, Pt-Rh, Fe-Ni, Ni-Pd, Fe-Co, Cu-Co, Ru-Ag, Au-Cu-Ag, Ag-Cu-Pt, Ag-Cu-Pd, Ag-Au-Pd, Au-Rh-Pd, Ag-Pt-Pd, Ag-Pt-Rh, Fe-Ni-Pd, Fe-Co-Pd, Cu-Co-Pd etc.

The median size of metal particle is 1～200nm, more preferably 2～70nm.If be in this particle size range, then the conductive layer of Xing Chenging is transparent.If the median size of metal particle surpasses 200nm, then the photoabsorption of metal increases, and the transmittance of particulate layer reduces, and turbidity increases simultaneously.If with the front panel of membrane body material as cathode tube, then the exploring degree of display image reduces.Under the situation of median size less than 1nm of metal particle,, therefore can not obtain having the film of the low-resistance value that can reach target of the present invention because the surface resistivity of particulate layer sharply increases.

This electrically conductive microparticle layer can adopt conductive membrane to form and make with coating fluid.

Conductive membrane forms with containing above-mentioned electrically conductive microparticle and polar solvent in the coating fluid.

Conductive membrane forms and comprises water with employed polar solvent in the coating fluid, alcohols such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, Pyranton, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, hexylene glycol, ester such as methyl acetate, ethyl acetate class, ethers such as ether, methyl glycol, glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, ethyl carbitol, Isopropanediol, ketones such as acetone, butanone, methyl ethyl diketone, acetylacetic ester etc.These solvents both can use separately, can mix use more than 2 kinds again.

If using oxycompound is the coating fluid of electrically conductive microparticle, then can forms and have 10 ²～10 ⁸The transparent conductivity layer of the surface resistivity about Ω/, this layer show anti-charged effect and electromagnetic shielding effect.When using oxide based electrically conductive microparticle to form conductive layer, the concentration that conductive membrane forms with the oxide based electrically conductive microparticle in the coating fluid is 0.2～5 weight %, more preferably 1～5 weight %.

If the amount that the oxide based electrically conductive microparticle in the coating fluid is used in conductive membrane formation is less than above-mentioned lower limit, therefore the film thining that then obtains can not obtain sufficient electroconductibility.If oxide based electrically conductive microparticle surpasses the above-mentioned upper limit, increase as thickness, the not only turbidity deterioration of film, and outward appearance is variation also.

If use the coating fluid contain the metal particle that replaces the oxide conducting particulate, then can form and have 10 ²～10 ³The transparent conductivity layer of the surface resistivity about Ω/, this layer show anti-charged effect and electromagnetic shielding effect.When using metal particle formation electromagnetic shielding to use conductive layer, contained metal particle, the concentration that forms with the metal particle in the coating fluid with conductive membrane is 0.05～5 weight %, especially 0.1～2 weight % is good.

If conductive membrane formation uses the amount of the metal particle in the coating fluid less than 0.05 weight %, as the film thining that obtains, therefore can not obtain sufficient electroconductibility.If metal particle surpasses 5 weight %, then thickness increases, and transmittance reduces, transparency variation, and also variation of outward appearance.

Form with in the coating fluid at conductive membrane, can contain tinting material, matrix precursor and organic stabilizer etc. as required.

Tinting material comprises that particulate carbon black, titanium are black, dyestuff, pigment etc.Contain the display unit that this based colorant can obtain excellent contrast.

In forming with coating fluid, conductive membrane can also contain matrix precursor.This class matrix precursor is preferably formed by silicon-dioxide.The silicic acid polycondensate that comprises the hydrolytie polycondensation thing of silicoorganic compound such as organoalkoxysilane specifically, obtains by the alkalimetal silicate dealkalize or coating resin etc.This matrix forms composition and presses solid component meter, contains 0.01～0.5 weight part corresponding to 1 weight part electrically conductive microparticle, more preferably 0.03～0.3 weight part.The tackiness agent of the electrically conductive microparticle after this matrix precursor forms as film uses.

Organic stabilizer comprises polycarboxylic acid and salt thereof such as gelatin, polyvinyl alcohol, polyvinylpyrrolidone, oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, sebacic acid, toxilic acid, fumaric acid, phthalic acid, citric acid, heterogeneous ring compound or their mixture etc.

This organic stabilizer is effective especially to the situation of containing metal particulate, and its content is generally 0.005～0.5 weight part corresponding to metal particle 1 weight part, more preferably 0.01～0.2 weight part.If the content of organic stabilizer then can not obtain the dispersiveness of sufficient metal particle less than 0.005 weight part,, then can have influence on electroconductibility if surpass 0.5 weight part.

Transparent conductivity particulate layer is that the above-mentioned transparent conducting film of coating forms and use coating fluid on body material, then drying and the transparent conductivity particulate layer that forms on body material.

The method that forms the transparent conductivity particulate comprises with methods such as pickling process, spinning method, spraying method, roller painting, flexographic printing methods after the coating transparent film forms with coating fluid on the body material, carries out drying in the temperature range of normal temperature～about 90 ℃.

Transparent conducting film forms when containing above-mentioned matrix precursor in the coating fluid, can carry out the hardening treatment of matrix precursor.

For example, can be when this transparent film of coating forms the film drying that forms with coating fluid or after the drying, heat with the temperature more than 150 ℃, or, perhaps expose to the open air in ammonia isoreactivity atmosphere gas with unhardened films of electromagnetic wave irradiation such as the short ultraviolet ray of wavelength ratio visible rays, electron beam, X ray, gamma-rays.Can promote film to form the sclerosis of composition like this, the hardness of gained film is increased.

The film thickness of the transparent conductivity particulate layer that is formed by aforesaid method is in the scope of 5～200nm, be more preferably in the scope of 10～150nm, film thickness just can access the body material of the good band transparent conducting film of anti-charging property and electromagnetic wave shielding as long as in this scope.

If the film thickness of transparent conductivity particulate layer surpasses 200nm, then transmittance reduces, and forms hole on the film easily, and turbidity increases.

Transparent film

In the body material of band transparent conducting film of the present invention, on above-mentioned transparent conductivity particulate layer, formed the low transparent film of the above-mentioned transparent conductivity particulate of refractive index ratio layer.

Transparent film can adopt wet type film forming methods such as pickling process, spinning method, spraying method, roller painting, flexographic printing method to be coated with above-mentioned transparent film and form and use coating fluid, and carries out drying as required and form.

The thickness of the transparent film of this moment is generally 50～300nm, more preferably 80～200nm.

If the thickness of transparent film surpasses the upper limit of above-mentioned scope, then can produce the crack on the film, film strength reduces, and the too thick meeting of film causes antireflection property insufficient.If the thickness of transparent film is less than above-mentioned lower limit, then film strength and antireflection property are relatively poor.

As previously mentioned, this film that forms with coating fluid of forming by the coating transparent film is when drying or after the drying, heat with the temperature more than 150 ℃, or, perhaps expose to the open air in ammonia isoreactivity atmosphere gas with unhardened films of electromagnetic wave irradiation such as the short ultraviolet ray of wavelength ratio visible rays, electron beam, X ray, gamma-rays.Can promote film to form the sclerosis of composition like this, the hardness of gained transparent film is improved.

Display unit

The body material of band transparent conducting film of the present invention have anti-charged, electromagnetic shielding is required about 10 ²～10 ⁸The surface resistivity of Ω/, and transparency is good, and in visible-range and near infrared range, have sufficient antireflection property, be suitable as the front panel of display unit.

Display unit of the present invention is the electrical means of cathode-ray picture tube (CRT), fluorescent display tube (FIP), plasm display device (PDP), liquid crystal indicator display images such as (LCD), and has been equipped with the front panel that the body material by above-mentioned band transparent conducting film constitutes.

The display unit that is equipped with existing front panel is when work, because the film hardness of transparent conducting film, cut intensity etc. are insufficient, so easy damaged, easily fuzzy, sometimes be difficult to see picture.

In the display unit of the present invention, front panel is made of the body material of the good band transparent conducting film of above-mentioned leakless and film toughness, grease, fingerprint etc. are difficult to attached to top, so must the wiping grease etc., can not damage thus, therefore display performance is good, can also prevent charged, and shielding electromagnetic wave and electromagnetic field that electromagenetic wave radiation produced effectively.

If the front panel in display unit has reflected light, then be difficult to see clearly the image of demonstration.But display unit of the present invention because front panel is made of the body material of the band transparent conducting film that has sufficient antireflection property in visible-range and near infrared range, therefore can prevent catoptrical generation effectively.

The present invention can provide a kind of transparent film to form with coating fluid and have body material with the band transparent conducting film of the transparent film of this coating fluid formation, and the display unit that is equipped with this body material.This transparent film forms with coating fluid owing to contain as the tetraalkoxysilane hydrolyzate of matrix precursor and the hydrolyzate of the silicoorganic compound of at least a kind of functional group with the epoxy group(ing) of being selected from, acryl, vinyl; and the hydrolyzate of the silicoorganic compound of the fluorine-containing replacement organic radical that adds as required; therefore when forming film, can form leakless, film toughness and excellent conductivity and water-repellancy and cut good strength, can prevent the body material of the band transparent conducting film of grease stain such as fingerprint.

Also have,, therefore can provide the body material of the good band transparent conducting film of a kind of antireflection property because transparent film is lower than electrically conductive microparticle layer specific refractory power.

During as the front panel of display unit, can provide a kind of charging preventive property, capability of electromagnetic shielding and antireflection property etc. good with the body material of this band transparent conducting film, and also good display unit such as weather resistance, water-repellancy.

Below, by embodiment the present invention is described, but the present invention is not limited to these embodiment.

[manufacturing embodiment]

A) modulation of electrically conductive microparticle dispersion liquid

The dispersion liquid of the electrically conductive microparticle that method modulation present embodiment as described below and comparative example are used.

Mix the modulation of Indium sesquioxide (ITO) particulate (P-1) dispersion liquid of Sn

Modulation indium nitrate 79.9g is dissolved in the solution that potassium hydroxide solution that the solution that obtains in the 686g water and potassium stannate 12.7g be dissolved in concentration 10 weight % obtains, and with 2 hours these solution is added in the 1000g pure water that temperature remains on 50 ℃.During this, keeping the pH value in the reaction system is 11, after the Indium sesquioxide hydrate of Sn is mixed in filtration from the Indium sesquioxide hydrate dispersion liquid of mixing Sn that obtains, washing, be distributed to once more in the water, modulating solid component concentration is the metal oxide precursor oxyhydroxide dispersion liquid of 10 weight %.Under 100 ℃ temperature, this dispersion liquid is carried out spraying drying, modulate the metal oxide precursor hydroxide powder.Under nitrogen atmosphere gas, with this powder of 550 ℃ temperature heat treated 2 hours.

This powder is scattered in the ethanol, makes concentration reach 30 weight %, with aqueous nitric acid the pH value is transferred to 3.5 after, this mixed solution is remained on 30 ℃, and pulverized 0.5 hour with skin grinder, modulate colloidal sol.Then, add Indium sesquioxide particulate (P-1) dispersion liquid of mixing Sn that ethanol modulates concentration 20 weight %.

The electroconductive oxide particulate (P-1) that obtains is measured its median size by the following method.

The results are shown in Table 1.

Electrically conductive microparticle is taken the TEM photo, measure the particle diameter of 20 particles, get its mean value, see Table 1 as median size.

Mix the modulation of stannic oxide (ATO) particulate (P-2) dispersion liquid of Sb

Tin chloride 57.7g and antimony chloride 7.0g be dissolved in the 100g methyl alcohol modulate solution.With 4 hours synthetic solution is added into 90 ℃, stirs among the pure water 1000g down and add water decomposition, filter, the post precipitation of washing generation, be distributed to once more in the water, modulate the metal oxide precursor oxyhydroxide dispersion liquid of solid component concentration 10 weight %.Under 100 ℃ temperature, this dispersion liquid is carried out spraying drying, modulate the metal oxide precursor hydroxide powder.Then, under nitrogen atmosphere gas, with this powder of 550 ℃ temperature heat treated 2 hours.This powder of 30g is added in the potassium hydroxide aqueous solution (containing KOH 3.0g) of 70g, mixeding liquid temperature is remained on 30 ℃, and pulverized 3 hours, modulate colloidal sol with skin grinder.Follow usefulness, this colloidal sol of ion exchange resin treatment adds pure water and modulates stannic oxide particulate (P-2) dispersion liquid of mixing Sb that concentration is 20 weight % after the dealkalize.Measure its median size, the results are shown in Table 1.

The modulation of the dispersion liquid of silver palladium alloy particulate (P-3)

By whenever obtaining the requirement that alloy particle 1 weight part adds 0.01 weight part, trisodium citrate is added in the 100g pure water in advance, adding Silver Nitrate and palladium nitrate aqueous solution therein makes concentration be scaled 10 weight % by metal, the weight ratio of silver and palladium is 8: 2, the aqueous solution of the ferrous sulfate of the mole numbers such as total mole number of interpolation and Silver Nitrate and Palladous nitrate again, under nitrogen atmosphere gas, stirred 1 hour, obtained the dispersion liquid of silver palladium alloy particulate.Then, the gained dispersion liquid is washed with centrifuge separator, remove impurity after, redispersion is in water, modulating concentration is the dispersion liquid of the silver palladium alloy particulate (P-3) of 4 weight %.The median size of silver palladium alloy particulate is 8nm.

[embodiment 1]

Transparent conducting film forms the modulation with coating fluid (C-1)

(68: 12: 8: mixed solvent 8: 4 weight ratios), modulating electrically conductive microparticle concentration was the transparent conducting film formation coating fluid (C-1) of 3.5 weight % for the particulate that obtains more than the mixing (P-1) dispersion liquid and ethanol/n-propyl alcohol/ethyl cellosolve/Isopropanediol/diacetone alcohol.

Transparent film forms with coating fluid (B-1) modulation

The mixing solutions of concentrated hydrochloric acid 1.0g and pure water 31.9g is added ethyl orthosilicate (SiO as tetraalkoxysilane ₂: 28.8 weight %) 31.3g, be γ-glycidoxypropyltrime,hoxysilane (SHIN-ETSU HANTOTAI's chemistry (strain) system: KBM-403) in the mixing solutions of 3.9g and ethanol 31.9g of silicoorganic compound as epoxy, stirred 2 hours at 60 ℃, modulating solid component concentration is the mixing solutions that contains matrix precursor (M-1) of 11.6 weight %.

Then, (72: 12: 6: mixed solvent 6: 4 weight ratios), modulating solid component concentration was the transparent film formation coating fluid (B-1) of 1.5 weight % to add ethanol/n-propyl alcohol/ethyl cellosolve/Isopropanediol/diacetone alcohol in mixing solutions (M-1).

The manufacturing of the face glass of band transparent conducting film

(surface of 17 ") remains under 40 ℃ the temperature; form with coating fluid (C-1) with spinning method above-mentioned transparent conducting film of coating under 100rpm, 90 seconds condition; the thickness of the conductive layer of this moment is measured in dry back, the results are shown in Table 1 with face glass with cathode-ray picture tube.

Then, on the transparent conductivity particulate layer of above formation, the same spinning method coating transparent film under 150rpm, 90 seconds condition that adopts forms with coating fluid (B-1), and dry back obtains the body material with transparent conducting film 160 ℃ sintering temperature 30 minutes.The thickness of the transparent film that form this moment reaches 50nm.

(Mitsubishi's oiling (strain) system: the LORESTA) surface resistivity of the body material of the above-mentioned band transparent conducting film of mensuration, (Japanese electric look (strain) is made: 3000A) measure turbidity with hazemeter to adopt the surface resistivity meter.Reflectivity is then used albedometer (Da mound electronics (strain) system: MCPD-2000) measure, the bottom reflection rate represents that with the reflectivity under the minimum wavelength of the scope internal reflection rate of wavelength 400～700nm the visual sense reflectivity is to represent at the average reflectance of wavelength 400～700nm scope.The results are shown in Table 1.

Also estimate eraser hardness, scratch hardness and fingerprint tack, the results are shown in Table 1.

Eraser hardness

On the body material of band transparent conducting film, place eraser (lion king (strain) system: 1K), apply the load of 1 ± 0.1Kg, with the wiping 25 times repeatedly of the distance of about 25mm.The rubber crumb high pressure gas that each wiping produces are removed.

After the rubber repetition wiping 25 times, under the illumination of 1000 luxs, carry out the visual observation on surface at distance transparent film surface 45cm place.

A: do not observe scuffing,

B: (becoming redness from purple) appears changing in reflected colour under luminescent lamp,

C: reflected colour under luminescent lamp, do not occur, observe scuffing,

D: can see substrate (body material).

Scratch hardness

Test pin ((strain) ロ Star Network ウュ Le system: hardness HRC-60, φ: 0.5mm) sets up standard on the transparent film of the body material of being with transparent conducting film, apply the load of 1 ± 0.3Kg, after the range sweep with 30～40mm, under the illumination of 1000 luxs, carry out the visual observation on surface at distance transparent film surface 45cm place.

A: do not observe scuffing,

B: observe desultory crackle,

C: observe light successive crackle,

D: observe tangible successive crackle.

The fingerprint tack

Firmly by on the transparent film surface of the body material of being with transparent conducting film, make fingerprint on finger attached to top.After dried cloth wiping 5 times, the tonal variation of visual observation film by following standard evaluation, the results are shown in Table 1.

Zero: confirm that color does not change (non-cohesive fingerprint or remove easily),

△: confirm that color changes slightly,

*: confirm color considerable change (affirmation has interference color).

[embodiment 2]

Transparent film forms the modulation with coating fluid (B-2)

Except that being that silicoorganic compound use γ-glycidoxypropyltrime,hoxysilane (SHIN-ETSU HANTOTAI's chemistry (strain) system: KBM-403) the 0.8g, other operation is all identical with embodiment 1, modulates transparent film and forms usefulness coating fluid (B-2) as epoxy.

The manufacturing of the face glass of band transparent conducting film

Identical with embodiment 1, the coating transparent conducting film forms with coating fluid (C-1), and dry.

Then, adopt equally the spinning method on the transparent conductivity particulate layer with 100rpm, 90 seconds condition under, the coating transparent film forms with coating fluid (B-2), dry back obtains the body material with transparent conducting film 160 ℃ sintering temperature 30 minutes.The thickness of the transparent film that form this moment reaches 50nm.

Estimate surface resistivity, turbidity, transmitance, bottom reflection rate, visual sense reflectivity and eraser hardness, scratch hardness, the fingerprint tack of the body material of gained band transparent conducting film.The results are shown in Table 1.

[embodiment 3]

Transparent film forms the modulation with coating fluid (B-3)

Except that being that silicoorganic compound use γ-glycidoxypropyltrime,hoxysilane (SHIN-ETSU HANTOTAI's chemistry (strain) system: KBM-403) the 7.9g, other operation is all identical with embodiment 1, modulates transparent film and forms usefulness coating fluid (B-3) as epoxy.

The manufacturing of the face glass of band transparent conducting film

Then, adopt the spinning method to form with coating fluid (B-3) with 100rpm, 90 seconds condition coating transparent film on transparent conductivity particulate layer equally, dry back obtains the body material with transparent conducting film 160 ℃ temperature sintering 30 minutes.The thickness of the transparent film that form this moment reaches 50nm.

[embodiment 4]

Transparent film forms the modulation with coating fluid (B-4)

Identical with embodiment 1, modulate the mixing solutions (M-1) that contains matrix precursor.

In addition, the mixing solutions of concentrated nitric acid 1.0g and pure water 49.9g is added ethyl orthosilicate (SiO as tetraalkoxysilane ₂: 28.8 weight %) 17.4g, as heptadecyl three fluoro Trimethoxy silanes (SHIN-ETSU HANTOTAI's chemistry (strain) system: KBM-7803) in the mixing solutions of 1.6g and ethanol 251g of the silicoorganic compound of fluorine-containing replacement organic radical, after 2 hours, modulating solid component concentration is the mixing solutions that contains matrix precursor (M-2) of 2 weight % 60 ℃ of stirrings.

Then, mixing solutions (M-1) and mixing solutions (M-2) are mixed, (72: 12: 6: mixed solvent 6: 4 weight ratios) modulated transparent film and forms with coating fluid (B-4) to add ethanol/n-propyl alcohol/ethyl cellosolve/Isopropanediol/diacetone alcohol.

With the transparent manufacturing of leading the face glass of do as one likes film

Then, adopt the spinning method to form with coating fluid (B-4) with 100rpm, 90 seconds condition coating transparent film on transparent conductivity particulate layer equally, dry back obtains the body material with transparent conducting film 160 ℃ sintering temperature 30 minutes.The thickness of the transparent film that form this moment reaches 50nm.

[embodiment 5]

Transparent film forms the modulation with coating fluid (B-5)

(SHIN-ETSU HANTOTAI's chemistry (strain) system: KBM-7803) the 8.2g, other operation is all identical with embodiment 4, modulates transparent film and forms with coating fluid (B-5) except that the silicoorganic compound as fluorine-containing replacement organic radical use heptadecyl three fluoro Trimethoxy silanes.

The manufacturing of the face glass of band transparent conducting film

Then, adopt the spinning method to form with coating fluid (B-5) with 100rpm, 90 seconds condition coating transparent film on transparent conductivity particulate layer equally, dry back obtains the body material with transparent conducting film 160 ℃ sintering temperature 30 minutes.The thickness of the transparent film that form this moment reaches 50nm.

[embodiment 6]

Transparent conducting film forms the modulation with coating fluid (C-2)

(68: 12: 8: mixed solvent 8: 4 weight ratios), modulating electrically conductive microparticle concentration was the transparent conducting film formation coating fluid (C-2) of 3.5 weight % to mix the above-mentioned particulate that obtains (P-2) dispersion liquid and ethanol/n-propyl alcohol/ethyl cellosolve/Isopropanediol/diacetone alcohol.

The manufacturing of the face glass of band transparent conducting film

Identical with embodiment 1, the coating transparent conducting film forms with coating fluid (C-2), and dry.

[embodiment 7]

Transparent conducting film forms the modulation with coating fluid (C-3)

(68: 12: 8: mixed solvent 8: 4 weight ratios), modulating electrically conductive microparticle concentration was the transparent conducting film formation coating fluid (C-3) of 0.35 weight % to mix the above-mentioned particulate that obtains (P-3) dispersion liquid and ethanol/n-propyl alcohol/ethyl cellosolve/Isopropanediol/diacetone alcohol.

The manufacturing of the face glass of band transparent conducting film

Identical with embodiment 1, the coating transparent conducting film forms with coating fluid (C-3), and dry.

[embodiment 8]

Transparent film forms the modulation with coating fluid (B-8)

Except that the silicoorganic compound as fluorine-containing replacement organic radical use n-perfluoro octyl group ethyl triethoxysilane (East レダウコ one ニ Application グシリコ one Application (strain) system: AY43-158E) the 1.6g, other operation is all identical with embodiment 4, modulates transparent film and forms with coating fluid (B-8).

The manufacturing of the face glass of band transparent conducting film

Then, adopt the spinning method to form with coating fluid (B-8) with 100rpm, 90 seconds condition coating transparent film on transparent conductivity particulate layer equally, dry back obtains the body material with transparent conducting film 160 ℃ sintering temperature 30 minutes.The thickness of the transparent film that form this moment reaches 50nm.

[embodiment 9]

Transparent film forms the modulation with coating fluid (B-9)

Except that as epoxy being γ-methacryloxypropyl trimethoxy silane (SHIN-ETSU HANTOTAI's chemistry (strain) system: KMB-403) the 4.1g that silicoorganic compound use propylene system, other operation is all identical with embodiment 4, modulates transparent film and forms with coating fluid (B-9).

The manufacturing of the face glass of band transparent conducting film

Then, adopt the spinning method to form with coating fluid (B-9) with 100rpm, 90 seconds condition coating transparent film on transparent conductivity particulate layer equally, dry back obtains the body material with transparent conducting film 160 ℃ sintering temperature 30 minutes.The thickness of the transparent film that form this moment reaches 50nm.

[embodiment 10]

Electrically conducting transparent spare film forms the modulation with coating fluid (B-10)

The mixing solutions of concentrated hydrochloric acid 1.0g and pure water 31.9g is added methyl orthosilicate (SiO as tetraalkoxysilane ₂: 51 weight %) 17.7g, be γ-glycidoxypropyltrime,hoxysilane (SHIN-ETSU HANTOTAI's chemistry (strain) system: KBM-403) in the mixing solutions of 3.9g and ethanol 45.5g of silicoorganic compound as epoxy, stirred 2 hours at 60 ℃, modulating solid component concentration is the mixing solutions that contains matrix precursor (M-3) of 11.6 weight %.

In addition, the mixing solutions with concentrated hydrochloric acid 1.0g and pure water 49.9g joins methyl orthosilicate (SiO ₂: 51 weight %) 10g, as 17 fluoro decyl Trimethoxy silanes (SHIN-ETSU HANTOTAI's chemistry (strain) system: KBM-7803) in the mixing solutions of 1.6g and ethanol 263.6g, stirred 2 hours, modulate SiO of the silicoorganic compound of fluorine-containing replacement organic radical at 60 ℃ ₂Concentration is the mixing solutions that contains matrix precursor (M-4) of 1.5 weight %.

Then, mixing solutions (M-3) and mixing solutions (M-4) are mixed, (72: 12: 6: mixed solvent 6: 4 weight ratios), modulating solid component concentration was the transparent film formation coating fluid (B-10) of 1.5 weight % to add ethanol/n-propyl alcohol/ethyl cellosolve/Isopropanediol/diacetone alcohol again.

The manufacturing of the face glass of band transparent conducting film

[embodiment 11]

Transparent film forms the modulation with coating fluid (B-11)

Except that as epoxy being γ-methacryloxypropyl trimethoxy silane (SHIN-ETSU HANTOTAI's chemistry (strain) system: KMB-503) the 4.1g that silicoorganic compound use propylene system, other operation is all identical with embodiment 10, modulates transparent film and forms with coating fluid (B-11).

The manufacturing of the face glass of band transparent conducting film

Then, adopt the spinning method to form with coating fluid (B-11) with 100rpm, 90 seconds condition coating transparent film on transparent conductivity particulate layer equally, dry back obtains the body material with transparent conducting film 160 ℃ sintering temperature 30 minutes.The thickness of the transparent film that form this moment reaches 50nm.

[comparative example 1]

Transparent film forms the modulation with coating fluid (RB-1)

The mixing solutions of concentrated hydrochloric acid 1.0g and pure water 31.9g is joined ethyl orthosilicate (SiO as tetraalkoxysilane ₂: 28.8 weight %) in the mixing solutions of 34.7g and ethanol 132.4g, stirred 2 hours, modulate SiO at 60 ℃ ₂Concentration is the mixing solutions that contains matrix precursor (RM-1) of 5 weight %.

Then, (72: 12: 6: mixed solvent 6: 4 weight ratios) modulated transparent film and forms with coating fluid (RB-1) to add ethanol/n-propyl alcohol/ethyl cellosolve/Isopropanediol/diacetone alcohol in mixing solutions (RM-1).

The manufacturing of the face glass of band transparent conducting film

Then, adopt the spinning method to form with coating fluid (RB-1) with 100rpm, 90 seconds condition coating transparent film on transparent conductivity particulate layer equally, dry back obtains the body material with transparent conducting film 160 ℃ sintering temperature 30 minutes.The thickness of the transparent film that form this moment reaches 50nm.

[comparative example 2]

Transparent film forms the modulation with coating fluid (RB-2)

It is γ-glycidoxypropyltrime,hoxysilane (SHIN-ETSU HANTOTAI's chemistry (strain) system: KBM-403) in the mixing solutions of 39.4g and ethanol 193.3g of silicoorganic compound that the mixing solutions of concentrated hydrochloric acid 1.0g and pure water 31.9g is joined as epoxy, stirred 24 hours at 50 ℃, modulating solid component concentration is the mixing solutions that contains matrix precursor (M-6) of 10 weight %.

Then, (72: 12: 6: mixed solvent 6: 4 weight ratios), modulating solid component concentration was the transparent film formation coating fluid (RB-2) of 1.5 weight % to add ethanol/n-propyl alcohol/ethyl cellosolve/Isopropanediol/diacetone alcohol in mixing solutions (M-6).

The manufacturing of the face glass of band transparent conducting film

Then, adopt the spinning method to form with coating fluid (RB-2) with 100rpm, 90 seconds condition coating transparent film on transparent conductivity particulate layer equally, dry back obtains the body material with transparent conducting film 160 ℃ sintering temperature 30 minutes.The thickness of the transparent film that form this moment reaches 40nm.

[comparative example 3]

Transparent film forms the modulation with coating fluid (RB-3)

Identical with embodiment 4, modulating solid component concentration is the mixing solutions that contains matrix precursor (M-2) of 2 weight %.

Then, (72: 12: 6: mixed solvent 6: 4 weight ratios) modulated transparent film and forms with coating fluid (RB-3) to add ethanol/n-propyl alcohol/ethyl cellosolve/Isopropanediol/diacetone alcohol in mixing solutions (M-2).

The manufacturing of the face glass of band transparent conducting film

Then, adopt the spinning method to form with coating fluid (RB-3) with 100rpm, 90 seconds condition coating transparent film on transparent conductivity particulate layer equally, dry back obtains the body material with transparent conducting film 160 ℃ sintering temperature 30 minutes.The thickness of the transparent film that form this moment reaches 30nm.

[comparative example 4]

The manufacturing of the face glass of band transparent conducting film

Identical with embodiment 6, the coating transparent conducting film forms with coating fluid (C-2), and dry.

Then, the same spinning method that adopts forms with coating fluid (RB-1) with 100rpm, 90 seconds condition coating and the comparative example 1 the same transparent film that obtains on transparent conductivity particulate layer, dry back obtains the body material with transparent conducting film 160 ℃ of sintering 30 minutes.The thickness of the transparent film that form this moment reaches 30nm.

[comparative example 5]

The manufacturing of the face glass of band transparent conducting film

Then, the same spinning method that adopts forms with coating fluids (RB-2) with 100rpm, 90 seconds condition coating and comparative example 2 the same transparent films that obtain on transparent conductivity particulate layer, dry back obtains the body material with transparent conducting film 160 ℃ of sintering 30 minutes.The thickness of the transparent film that form this moment reaches 30nm.

[comparative example 6]

The manufacturing of the face glass of band transparent conducting film

Then, the same spinning method that adopts forms with coating fluids (RB-3) with 100rpm, 90 seconds condition coating and comparative example 3 the same transparent films that obtain on transparent conductivity particulate layer, dry back obtains the body material with transparent conducting film 160 ℃ of sintering 30 minutes.The thickness of the transparent film that form this moment reaches 30nm.

[comparative example 7]

The manufacturing of the face glass of band transparent conducting film

Identical with embodiment 7, the coating transparent conducting film forms with coating fluid (C-3), and dry.

[comparative example 8]

The manufacturing of the face glass of band transparent conducting film

[comparative example 9]

The manufacturing of the face glass of band transparent conducting film

Table 1

	Transparent film								Transparent conductivity particulate layer			The body material of band transparent conducting film
	Transparent film								Transparent conductivity particulate layer			The body material of band transparent conducting film								Coating fluid No.	Hydrolyzate (i)		Hydrolyzate (ii)		Hydrolyzate (iii)		Thickness nm	Thickness nm	Electrically conductive microparticle		Thickness (total) nm	Surface resistivity Ω/ * 10 ³	Film toughness ケシ go system	Film toughness cut intensity	Bottom reflection rate %	Visual sense reflectivity %	Turbidity %	The fingerprint tack
	Kind	Ratio weight %	Kind	Ratio weight %	Kind	Ratio weight %	Kind	Median size nm													Hydrolyzate (i)		Hydrolyzate (ii)		Hydrolyzate (iii)				Electrically conductive microparticle
	Kind	Ratio weight %	Kind	Ratio weight %	Kind	Ratio weight %	Kind	Median size nm	Embodiment 1	?B-1	?TEOS	?77.9	?KBM-403	?22.1	???-	??-	?50	?130	?P-1		?20	?180	?2.0	?A	?A	?1.2			?1.7	?0.1									△
Embodiment 2	?B-2	?TEOS	?74.5	?KBM-403	?5.5	???-	??-	?50	Embodiment 1	?B-1	?TEOS	?77.9	?KBM-403	?22.1	???-	??-	?50	?130	?P-1	?130	?20	?180	?2.0	?A	?A	?1.2	?P-1	?20	?1.7	?0.1	?180	?2.5	?A	?B	?1.3	?1.8	?0.1	△	△
Embodiment 2	?B-2	?TEOS	?74.5	?KBM-403	?5.5	???-	??-	?50	Embodiment 3	B 1	?TEOS	?64.2	?KBM-403	?35.8	???-	??-	?50	?130	?P-1	?130	?20	?180	?2.3	?B	?B	?1.2	?P-1	?20	?1.6	?0.2	?180	?2.5	?A	?B	?1.3	?1.8	?0.1	△	△
Embodiment 4	?B-4	?TEOS	?77.9	?KBM-403	?21.3	?KBM-7803	??0.8	?50	Embodiment 3	B 1	?TEOS	?64.2	?KBM-403	?35.8	???-	??-	?50	?130	?P-1	?130	?20	?180	?2.3	?B	?B	?1.2	?P-1	?20	?1.6	?0.2	?180	?2.1	?A	?A	?1.2	?1.7	?0.1	○	△
Embodiment 4	?B-4	?TEOS	?77.9	?KBM-403	?21.3	?KBM-7803	??0.8	?50	Embodiment 5	?B-5	?TEOS	?77.9	?KBM-403	?17.7	?KBM-7803	??4.5	?50	?130	?P-1	?130	?20	?180	?2.8	?B	?A	?1.0	?P-1	?20	?1.5	?0.2	?180	?2.1	?A	?A	?1.2	?1.7	?0.1	○	○
Embodiment 6	?B-6	?TEOS	?77.9	?KBM-403	?21.3	?KBM-7803	??0.8	?50	Embodiment 5	?B-5	?TEOS	?77.9	?KBM-403	?17.7	?KBM-7803	??4.5	?50	?130	?P-1	?130	?20	?180	?2.8	?B	?A	?1.0	?P-2	?15	?1.5	?0.2	?180	?200	?A	?A	?1.2	?1.6	?0.1	○	○
Embodiment 6	?B-6	?TEOS	?77.9	?KBM-403	?21.3	?KBM-7803	??0.8	?50	Embodiment 7	?B-7	?TEOS	?77.9	?KBM-403	?21.3	?KBM-7803	??0.8	?50	?30	?P-3	?130	?8	?80	?0.6	?A	?A	?0.1	?P-2	?15	?0.3	?0.1	?180	?200	?A	?A	?1.2	?1.6	?0.1	○	○
Embodiment 8	?B-8	?TEOS	?77.9	?KBM-403	?21.3	?AY43-158E	??0.8	?50	Embodiment 7	?B-7	?TEOS	?77.9	?KBM-403	?21.3	?KBM-7803	??0.8	?50	?30	?P-3	?130	?8	?80	?0.6	?A	?A	?0.1	?P-1	?20	?0.3	?0.1	?180	?2.2	?A	?A	?1.1	?1.6	?0.1	○	○
Embodiment 8	?B-8	?TEOS	?77.9	?KBM-403	?21.3	?AY43-158E	??0.8	?50	Embodiment 9	?B-9	?TEOS	?77.9	?KBM-503	?21.3	?KBM-7803	??0.8	?50	?130	?P-1	?130	?20	?180	?2.2	?A	?A	?1.2	?P-1	?20	?1.7	?0.1	?180	?2.2	?A	?A	?1.1	?1.6	?0.1	○	○
Embodiment 10	?B-10	?TMOS	?77.9	?KBM-403	?21.3	?KBM-7803	??0.8	?50	Embodiment 9	?B-9	?TEOS	?77.9	?KBM-503	?21.3	?KBM-7803	??0.8	?50	?130	?P-1	?130	?20	?180	?2.2	?A	?A	?1.2	?P-1	?20	?1.7	?0.1	?180	?1.8	?A	?A	?1.1	?1.6	?0.1	○	○
Embodiment 10	?B-10	?TMOS	?77.9	?KBM-403	?21.3	?KBM-7803	??0.8	?50	Embodiment 11	?B-11	?TMOS	?77.9	?KBM-503	?21.3	?KBM-7803	??0.8	?50	?130	?P-1	?130	?20	?180	?2.0	?A	?A	?1.2	?P-1	?20	?1.6	?0.1	?180	?1.8	?A	?A	?1.1	?1.6	?0.1	○	○
Comparative example 1	?RB-1	?TEOS	?100	?-	?-	???-	??-	?50	Embodiment 11	?B-11	?TMOS	?77.9	?KBM-503	?21.3	?KBM-7803	??0.8	?50	?130	?P-1	?130	?20	?180	?2.0	?A	?A	?1.2	?P-1	?20	?1.6	?0.1	?180	?4.0	?C	?B	?1.5	?2.0	?0.1	△	○
Comparative example 1	?RB-1	?TEOS	?100	?-	?-	???-	??-	?50	Comparative example 2	?RB-2	?-	?-	?KBM-403	?100	???-	??-	?40	?130	?P-1	?130	?20	?170	?10	?D	?D	?1.7	?P-1	?20	?2.2	?0.6	?180	?4.0	?C	?B	?1.5	?2.0	?0.1	△	△
Comparative example 3	?RB-3	?TEOS	?77.2	?-	?-	?KBM-7803	??22.8	?30	Comparative example 2	?RB-2	?-	?-	?KBM-403	?100	???-	??-	?40	?130	?P-1	?130	?20	?170	?10	?D	?D	?1.7	?P-1	?20	?2.2	?0.6	?160	?4.5	?C	?B	?1.2	?1.6	?0.2	○	△
Comparative example 3	?RB-3	?TEOS	?77.2	?-	?-	?KBM-7803	??22.8	?30	Comparative example 4	?RB-1	?TEOS	?100	?-	?-	???-	??-	?30	?130	?P-2	?130	?15	?160	?400	?C	?B	?1.5	?P-1	?20	?2.0	?0.1	?160	?4.5	?C	?B	?1.2	?1.6	?0.2	○	△

Comparative example 5	?RB-2	?-	?-	??KBM-403	??100	??-	??-	?30	?130	?P-2	?15	?160	?800	?D	?D	?1.8	?2.4	?0.7	△
Comparative example 5	?RB-2	?-	?-	??KBM-403	??100	??-	??-	?30	?130	?P-2	?15	?160	?800	?D	?D	?1.8	?2.4	?0.7	△	Comparative example 6	?RB-3	?TEOS	?77.2	??-	??-	??KBM-7803	??22.8	?30	?130	?P-2	?15	?160	?500	?C	?B	?1.2	?1.7	?0.3	○
Comparative example 7	?RB-1	?TEOS	?100	??-	??-	??-	??-	?30	?30	?P-3	?8	?60	?0.7	?C	?B	?0.2	?0.4	?0.1	△	Comparative example 6	?RB-3	?TEOS	?77.2	??-	??-	??KBM-7803	??22.8	?30	?130	?P-2	?15	?160	?500	?C	?B	?1.2	?1.7	?0.3	○
Comparative example 7	?RB-1	?TEOS	?100	??-	??-	??-	??-	?30	?30	?P-3	?8	?60	?0.7	?C	?B	?0.2	?0.4	?0.1	△	Comparative example 8	?RB-2	?-	?-	??KBM-403	??100	??-	??-	?30	?30	?P-3	?8	?60	?1.0	?D	?D	?0.5	?0.9	?0.5	△
Comparative example 9	?RB-3	?TEOS	?77.2	??-	??-	??KBM-7803	??22.8	?30	?30	?P-3	?8	?60	?0.9	?C	?B	?0.1	?0.4	?0.3	○	Comparative example 8	?RB-2	?-	?-	??KBM-403	??100	??-	??-	?30	?30	?P-3	?8	?60	?1.0	?D	?D	?0.5	?0.9	?0.5	△

Claims

1, transparent film forms and uses coating fluid; it is characterized in that; comprise by the hydrolyzate of (i) tetraalkoxysilane and (ii) have the matrix precursor that the hydrolyzate of silicoorganic compound of at least a kind of functional group of the epoxy group(ing) of being selected from, acryl, vinyl forms, and the ratio (ii) in the matrix precursor is pressed solid component meter in the scope of 0.5～50 weight %.

2, transparent film as claimed in claim 1 forms and uses coating fluid; its feature also is, hydrolyzate when above-mentioned matrix precursor is the mixture of silicoorganic compound of tetraalkoxysilane and at least a kind of functional group with the epoxy group(ing) of being selected from, acryl, vinyl.

3, transparent film as claimed in claim 1 or 2 forms and uses coating fluid, its feature also is, above-mentioned matrix precursor also contains the hydrolyzate of the silicoorganic compound that (iii) have fluorine replacement organic radical, and the ratio (iii) in the matrix precursor is pressed solid component meter in the scope of 0.1～30 weight %.

4, transparent film as claimed in claim 3 forms and uses coating fluid, its feature also is, above-mentioned to have hydrolyzate that fluorine replaces the silicoorganic compound of organic radical be tetraalkoxysilane and have fluorine hydrolyzate when replacing the mixture of silicoorganic compound of organic radical.

5, the body material of band transparent conducting film, described material is made of transparent conductivity particulate layer that contains electrically conductive microparticle on body material, the body material and the low transparent film of this transparent conductivity particulate layer of refractive index ratio that be located on this transparent conductivity particulate layer, it is characterized in that transparent film is formed with coating fluid by each described transparent film in the aforesaid right requirement item 1～4 and forms.

6, display unit is characterized in that, possesses the front panel that the body material by claim item 5 described band transparent conducting films constitutes, and transparent conducting film is formed at the outside surface of this front panel.