CN106029798A

CN106029798A - Coating solution for forming transparent film, and method for forming substrate with transparent film

Info

Publication number: CN106029798A
Application number: CN201580008556.8A
Authority: CN
Inventors: 二神涉; 松田政幸; 村口良
Original assignee: GC CATALYSTS AND CHEMICALS LT
Current assignee: GC CATALYSTS AND CHEMICALS LT
Priority date: 2014-02-14
Filing date: 2015-02-12
Publication date: 2016-10-12
Anticipated expiration: 2035-02-12
Also published as: KR20160121522A; KR102245165B1; JP6470695B2; TW201534670A; WO2015122453A1; JPWO2015122453A1; TWI645000B; CN106029798B

Abstract

This coating solution for forming transparent film is obtained by dispersing fine inorganic oxide particles and a resin emulsion in a dispersion medium containing water and/or an organic solvent. The coating solution has a total solid concentration of 0.03-70wt%, the concentration (CP) of fine inorganic oxide particles in the coating solution is 0.0009-56wt% as solids, and the concentration (CR) of the resin emulsion as solids falls within the range 0.006-68wt%. The total solids concentration of alkali metals contained in the fine inorganic oxide particles does not exceed 1000ppm as oxides (Me2O, Me = Li, Na, K). It is possible to provide a substrate with transparent film, whereby even if this coating solution is coated on a substrate and subsequently stretched, or if the coating solution is applied while the substrate is being stretched, the surface is flat, and the substrate is free from spots and film irregularities (sea-island structures).

Description

For forming the coating fluid of transparent coating and there is the manufacture method of base material of transparent coating

Technical field

The present invention relates to the coating fluid for forming transparent coating and use this coating fluid there is transparent coating The manufacture method of base material.

Background technology

So far, various transparent coatings are formed at the base material table of glass, plastic plate, resin molding, plastic lens etc. Used on face.Such as, organic resin film or inoranic membrane it are formed with on substrate surface as hard coat Film.And then, in organic resin film or inoranic membrane, the inorganic particulate such as blending resin particle or silicon dioxide carries High marresistance.

The applicant discloses the hardcoat film being only made up of organic resin and is coated to containing oxidized antimony Porous silica silicon particle (or inside have cavity silicon dioxide microparticle) antireflection prevent charged Structure (the Japanese Patent Laid-Open 2005-119909 publication that film is layered on base material；Patent documentation 1), But hard coat function (marresistance, film-strength etc.) is not enough.It addition, it is known that in display device etc. Base material on formed containing metal particle, the conductive cell envelope of electroconductive oxide microgranule and give anti-charging property Energy, scheme (the Japanese Patent Laid-Open 2003-105268 publication of electromagnetic shielding performance；Patent documentation 2). Now, disclose stannum oxide as electroconductive oxide microgranule, doped with the stannum oxide of F, Sb or P, oxygen Change indium, doped with the Indium sesquioxide. of Sn or F, stibium oxide, oxidation two titaniums etc..It addition, the applicant is also Disclose the hard painting blending Antimonic oxide microgranule in order to make hardcoat film self have charging preventive property Tunic (Japanese Patent Laid-Open 2004-50810 publication；Patent documentation 3).Also disclose blending chain five Transparent coating (the Japanese Patent Laid-Open 2005-139026 publication of stibium oxide microgranule；Patent documentation 4).

Additionally, it is known that by the coating solution containing low-refraction microgranules such as silicon dioxide microparticles at substrate surface And form antireflective coating film (Japanese Patent Laid-Open 7-133105 publication；Patent documentation 5).It addition, In order to have charging preventive property, electromagnetic shielding performance and also on base material formed containing metal particle, lead Electrically form antireflection film on the conductive cell envelope of oxide fine particle.Even if in order to have antireflection at this set Film, conductive cell envelope occasion under also be able to improve marresistance, also in base material and antireflection film and electric conductivity Hardcoat film is formed between at least one in tunicle.The applicant is in such as Japanese Patent Laid-Open 2007-321049 publication (patent documentation 6), Japanese Patent Laid-Open 2008-19358 publication (patent Document 7), Japanese Patent Laid-Open 2010-128309 publication (patent documentation 8) etc. discloses for Form the coating fluid of antireflection film.

Particularly under the occasion that base material is resin molding, it was on the film base material being stretched to specific thickness in the past Form transparent coating, but in recent years from the viewpoint of productivity, safety, environmental factors, seeking always Ask to be coated with on film before the stretching and form film, the most after the stretch for forming the coating fluid of transparent coating Solidify, or the film before stretching is carried out stretching while coating is for the coating forming transparent coating Liquid and form film, the method then carrying out solidifying.

But, under the occasion using conventional coating fluid, owing to producing speckle during stretching because of blend particles, Due to the unstability of coating fluid or inhomogeneities etc., to produce film uneven, thus forms that flatness is impaired, outward appearance Deterioration, the transparency, the stretched film with transparent coating of mist degree deficiency, need to improve these problems.

Prior art literature

Patent documentation

Patent documentation 1: Japanese Patent Laid-Open 2005-119909 publication

Patent documentation 2: Japanese Patent Laid-Open 2003-105268 publication

Patent documentation 3: Japanese Patent Laid-Open 2004-50810 publication

Patent documentation 4: Japanese Patent Laid-Open 2005-139026 publication

Patent documentation 5: Japanese Patent Laid-Open 7-133105 publication

Patent documentation 6: Japanese Patent Laid-Open 2007-321049 publication

Patent documentation 7: Japanese Patent Laid-Open 2008-19358 publication

Patent documentation 8: Japanese Patent Laid-Open 2010-128309 publication

Summary of the invention

The technical problem to be solved

So, speckle generation when it is an object of the invention to realize suppressing the resin molding after being coated with to stretch, Film inequality produce for forming the coating fluid of transparent coating and there is the manufacturer of base material of transparent coating Method.

Solve the technical scheme that technical problem is used

The inventors discovered that, inorganic oxide particle and resin emulsion are scattered in containing water if used and have The coating fluid in the disperse medium of at least one in machine solvent, then can suppress the resin molding stretching after coating Time the uneven generation of the generation of speckle, film.Now, all solids constituent concentration of coating fluid is 0.03～70 Weight %, the concentration (C of the inorganic oxide particle in coating fluid_P) it is calculated as 0.0009～56 with solid constituent Weight %, the concentration (C of resin emulsion_R) it is calculated as 0.006～68 weight % with solid constituent.It addition, nothing Alkali-metal solid component concentration total amount contained in machine oxide fine particle is with oxide (Me₂O, Me=Li, Na, K) count at below 1000ppm.

The coating fluid of the application of the invention, though on base material coating after again base material is stretched or Stretch base material while being coated, it is also possible to do not provide with not producing speckle or film uneven (island structure) What surface was smooth has the base material of transparent coating.

Here, it is preferred that utilize at least one in organo-silicon compound and polymeric dispersant to inorganic oxide Microgranule carries out surface process.Now, for organo-silicon compound, with R_n-SiX_(4-n)/2Relative to nothing during expression Machine oxide fine particle with solid component meter in the range of 1～100 weight %；For polymeric dispersant, Relative to inorganic oxide particle with solid component meter in the range of 1～300 weight %.

And, inorganic oxide particle be monodispersed inorganic oxide particle (A) and primary particle size 3～ 30 at least one connected in catenulate chain inorganic oxide particle (B), inorganic oxide particle (A) mean diameter (D_PA) at 3≤D_PAIn the range of≤100nm, inorganic oxide particle (B) Average primary particle diameter (D_PB) at 3≤D_PBIn the range of≤50nm.

The average diameter of resin emulsion preferably in the range of 10～500nm, described inorganic oxide particle Concentration (C_P) and the concentration (C of resin emulsion_R) concentration ratio (C_P/C_R) preferably 0.03～4 model In enclosing.

Detailed description of the invention

Below, the coating fluid that first present invention is used for being formed transparent coating is specifically described.

[for forming the coating fluid of transparent coating]

In the present invention for being formed in the coating fluid of transparent coating, inorganic oxide particle and resin emulsion divide Dissipate in containing in the disperse medium of at least one in water and organic solvent.Now, all solids of coating fluid Constituent concentration in the range of 0.03～70 weight %, the concentration (C of inorganic oxide particle_P) become with solid Divide and count in the range of 0.0009～56 weight %, the concentration (C of resin emulsion_R) exist with solid component meter In the range of 0.006～68 weight %.Now, inorganic oxide particle uses alkali-metal solid constituent dense Degree is with oxide (Me₂O) total amount meter is at the high-purity inorganic oxide particle of below 1000ppm.Nothing When alkali metal total amount in machine oxide fine particle is more than 1000ppm, inorganic oxide particle cannot be in coating In liquid dispersed, stability is not enough.Therefore, the intensity of transparent coating, marresistance decline, haze value Raise.

And then, inorganic oxide particle is preferably through using in organo-silicon compound and polymeric dispersant extremely Few a kind of surface carried out processes.Now, organo-silicon compound become with solid relative to inorganic oxide particle Divide conversion, as R_n-SiX_(4-n)/2It is 1～100 weight %.If the amount of organo-silicon compound is few, then with Resin emulsion in coating fluid described later or the affinity of disperse medium is low, stability is not enough and cannot be in coating Liquid is uniformly dispersed.Polymeric dispersant relative to inorganic oxide particle with solid component meter 1～300 Exist in the range of weight %.If the amount of polymeric dispersant is less than 1 weight %, then with described later for Form the resin emulsion in the coating fluid of transparent coating or the affinity of disperse medium is low, stability is not enough and nothing Method is uniformly dispersed in coating fluid.When the amount of polymeric dispersant is more than 300 weight %, dispersibility also without Method improves further.

Inorganic oxide particle uses monodispersed inorganic oxide particle (A) and primary particle size 3～ 30 at least one connected in catenulate chain inorganic oxide particle (B).Now, inorganic oxide Mean diameter (the D of thing microgranule (A)_PA) it is 3≤D_PA≤ 100nm, inorganic oxide particle (B) Average primary particle diameter (D_PB) it is 3≤D_PB≤50nm。

The state of the tunicle after coating changes according to the concentration of inorganic oxide particle in coating fluid, but in nothing Mean diameter (the D of machine oxide fine particle (A)_PA) less than 3nm time, inorganic oxide particle (A) Brokenly coagulation and arrange, make the haze value of transparent coating raise, film strength, marresistance, cut Intensity etc. become not enough.If mean diameter (D_PA) more than 100nm, then the transparency becomes not enough, by Make film strength also become not enough in the thickness of transparent coating.Putting down of chain inorganic oxide particle (B) All primary particle size (D_PB) less than 3nm time, be not connected to into chain but become agglutination particle.If it is average Primary particle size (D_PB) more than 50nm, then be difficult to obtain chain particle.

Below, the key element constituting coating fluid is described in detail.

Inorganic oxide particle

Inorganic oxide particle used in the present invention can be according to purposes from known inorganic oxide so far Microgranule selects.But, alkali-metal solid component concentration contained in inorganic oxide particle is with oxidation Thing (Me₂O) total amount meter must be at below 1000ppm.As Me, sodium (Na) or potassium can be illustrated Or lithium (Li) (K).

When alkali metal total amount in inorganic oxide particle is more than 1000ppm, it is likely to be due to common heteroion (day Literary composition: altogether イオ Application) increase, it is impossible to be uniformly dispersed in coating fluid, existence and stability become not enough, The situation of inorganic oxide particle coagulation.Accordingly, there exist intensity or marresistance reduction, the mist of transparent coating Angle value rising and the performance such as electric conductivity, reflectance become not enough situation.As reducing alkali-metal method, The known so far method of cleaning using ultrafilter membrane or ion exchange resin etc. can be illustrated.

As inorganic oxide particle, can illustrate selected from TiO₂、ZrO₂、SiO₂、Sb₂O₅、ZnO₂、SnO₂、 In₂O₃, antimony doped tin oxide (ATO), tin-doped indium oxide (ITO), mix F stannum oxide (FTO), mix The composite oxides of at least one or they in phosphorus oxidation stannum (PTO), Al-Doped ZnO (AZO) Or mixture.Suitably can select from above-mentioned inorganic oxide particle according to the purposes of transparent coating.Specifically For, under the occasion forming high refractive index film etc., TiO₂、ZrO₂、Sb₂O₅、ZnO₂、SnO₂、In₂O₃ Etc. being suitable.In the occasion forming hardcoat film, low refractive index film, easy adhesive film, anti-caking film etc. Under, SiO₂It is suitable.

Particularly in terms of in case being reflected into the low refractive index film of purpose, the Japanese Patent Laid-Open of the applicant Inside disclosed in 2001-233611 publication, Japanese Patent Laid-Open 2003-192994 publication has sky The hollow silica microgranule in hole is suitable.It is about this is because hollow silica microgranule is refractive index The microgranule of 1.10～1.40 the lowest colloid categories, the excellence such as its dispersibility.It addition, hollow silica Microgranule also is suitable as thermal isolation film.It addition, inside does not have the silicon dioxide microparticle in cavity (otherwise referred to as Silicon dioxide solid microspheres) in, the silicon dioxide microparticle of smaller particles (particle diameter is about at below 100nm) Making hardness increase, the silicon dioxide microparticle that particle diameter is bigger than it is then suitable to give anticaking capacity.

Under the occasion preventing interference fringe, form the TiO of high refractive index film₂It is suitable.It addition, Formed under the occasion of anti-charged membrane, Sb₂O₅、In₂O₃, antimony doped tin oxide (ATO), tin-doped indium oxide (ITO), Mix F stannum oxide (FTO), p-doped stannum oxide (PTO), Al-Doped ZnO (AZO) etc. owing to having Electric conductivity and be suitable for.

Inorganic oxide particle is preferably monodispersed inorganic oxide particle (A) and primary particle connects At least one in catenulate chain inorganic oxide particle (B).Here, so-called single dispersing, refer to Particle is non-agglutination state.

Mean diameter (the D of inorganic oxide particle (A)_PA) different according to the kind of transparent coating, but At 3≤D_PAIn the range of≤100nm, preferably at 5≤D_PAIn the range of≤80nm, further preferably At 8≤D_PAIn the range of≤80nm.

The state of the tunicle after coating changes according to the concentration of inorganic oxide particle in coating fluid, but Mean diameter (the D of inorganic oxide particle (A)_PA) less than under the occasion of 3nm, inorganic oxide is micro- Grain (A) coagulation brokenly and arrange, there is the situation that the haze value of transparent coating raises, and film be strong Degree, marresistance, cut intensity etc. become not enough situation.It addition, at above-mentioned hollow silica microgranule Occasion under, have that the empty ratio within silica-based hollow minute particle is little, refractive index cannot be 1.40 Following situation, and antireflection property becomes not enough situation.It addition, in crystallinity such as ATO or ITO Under the occasion of conducting particles, crystallinity can become insufficient, and electric conductivity can become not enough.If mean diameter (D_PA) more than 100nm, then the transparency can become not enough.There is also film strength also due to transparent quilt The thickness of film and become not enough situation.Be additionally, since the surface of transparent coating formed highdensity concavo-convex and There is the situation that haze value raises, and marresistance, cut intensity become not enough situation.

It addition, the average primary particle diameter (D of chain inorganic oxide particle (B)_PB) preferably at 3≤D_PB In the range of≤50nm, further preferably at 5≤D_PBIn the range of≤30nm, such primary particle The average number that connects preferably in the scope of 3～30, further preferably in the scope of 5～20.

The state of the tunicle after coating changes according to the concentration of chain inorganic oxide particle in coating fluid, but It is that chain inorganic oxide particle (B) is at mean diameter (D_PB) less than 3nm time be not connected to into chain and To become agglutination particle, exist transparent coating haze value raise situation, and film strength, marresistance, Cut intensity etc. becomes not enough situation.If average primary particle diameter (D_PB) more than 50nm, then be difficult to obtain Obtaining chain particle, even if obtaining chain particle, there is also the mist degree that chain particle is long-chain, transparent coating It is worth situation about raising, and film strength, marresistance, cut intensity etc. become not enough situation.

Concentration (the C of the inorganic oxide particle in the coating fluid forming transparent coating_P) with solid constituent Meter is preferably in the range of 0.0009～56 weight %, further preferably in the scope of 0.03～40 weight % In.Concentration (C_PIf) the lowest, then with the adaptation of base material, film-strength, surface, scratch resistance Property, cut intensity etc. can become not enough.And, exist cannot fully obtain desirable effect (electric conductivity, Antireflection property etc.) situation.Concentration (C_PIf) the highest, then too much due to particle, except adaptation, Outside film-strength, marresistance, cut intensity etc. become to be not enough to, the haze value that there is also transparent coating raises Situation.And, also can due to during stretching the stretching, extension of film do not chase after the stretching of base material and crack.

Coating fluid also can contain inorganic oxide particle (C).Additionally, it is possible to micro-containing inorganic oxide Grain (C) replaces at least one party in inorganic oxide particle (A) and chain inorganic oxide particle (B) A part.

Mean diameter (the D of inorganic oxide particle (C)_PC) at 100 ＜ D_PCIn the range of≤500nm, Preferably at 100 ＜ D_PCIn the range of≤400nm, further preferably at 100 ＜ D_PCThe scope of≤300nm In.By adding inorganic oxide particle (C), it is possible to form protuberance on transparent coating surface, therefore Available sufficient anticaking capacity.

The state of the tunicle after coating changes according to the concentration of inorganic oxide particle in coating fluid, but in nothing Mean diameter (the D of machine oxide fine particle (C)_PC) less than 100nm time, the thickness of transparent coating becomes Thinner, there is the situation that cannot form protuberance on transparent coating surface, utilize described hereinafter having The manufacture method of the base material of bright tunicle to for forming the coating fluid of transparent coating and be coated, being dried, so Batch under the occasion of the base material with transparent coating after rear solidification again, the surface of transparent coating with batch afterwards To the base material with transparent coating base material between closely sealed (otherwise referred to as caking), making after existing Situation about peeling off it is difficult in.If mean diameter (D_PC) more than 500nm, then except the transparency of film Can reduce, beyond film haze value can raise, absorbance can reduce, the concavo-convex meeting on surface become excessive cause resistance to The scratch resistance hardness waiting film reduces.

Concentration (the C of the inorganic oxide particle (C) in the coating fluid forming transparent coating_PC) with Solid component meter is preferably in the range of 0.000003～3 weight %, further preferably 0.000015～1.5 In the range of weight %.Concentration (C_PC) less than 0.000003 weight % time, be used for being formed transparent in use The coating fluid of tunicle and the density of protuberance that formed on the surface of film that obtains is too low, exist and cannot be filled The situation of the anticaking capacity divided.If concentration (C_PC) more than 3 weight %, then formed in film coated surface The density of protuberance is too high, there is the transparency, marresistance, antireflection property become not enough situation.

Here, inorganic oxide particle is preferably through using in organo-silicon compound and polymeric dispersant extremely Few a kind of surface carried out processes.Organo-silicon compound can improve inorganic oxide particle and resin emulsion it Between affinity.On the other hand, polymeric dispersant can not only equally improve affinity with above-mentioned, also Can suppress to produce between filler, binding agent due to stretching space, be particularly suitable for when stretching ratio height.

Use when surface processes under the occasion of water, be replaced as organic solvent the most after surface treatment, formed The dispersion in organic solvent of surface treated inorganic oxide particle.Take this, can improve in film inorganic Oxide fine particle dispersibility in resin.As organic solvent, it is preferably used with described hereinafter for shape Become the organic solvent that the coating fluid of transparent coating is identical.

Below, to using (i) organo-silicon compound, (ii) polymeric dispersant to come inorganic oxide micro- Grain carries out the occasion of surface process and illustrates.

(i) organo-silicon compound

The organo-silicon compound represented with following formula (1) can be used.

R_n-SiX_4-n (1)

(in formula, R is the non-substituted of carbon number 1～10 or substituted alkyl, may be the same or different each other.X: The alkoxyl of carbon number 1～4, silanol group, halogen, hydrogen, the integer of n:0～3)

In formula (1), under the occasion that n is 1～3, it is preferably used that have can be with the official of aftermentioned resin emulsion The organo-silicon compound of the organo-functional group reacted can be rolled into a ball.Such as, in use, there is epoxy radicals, methyl The resin of acryloyl group, acryloyl group, NCO etc. is as under the occasion of resin emulsion, as organic Silicon compound, be preferably used have glycidoxy, methacryloxy, propyl group acyloxy, vinyl, The organo-silicon compound of the functional groups such as NCO, urea groups, amino.If using and utilizing this organosilicon Compound carried out the inorganic oxide particle that surface processes, then can form film-strength, marresistance, draw The transparent coating that the aspects such as trace intensity are excellent.

The surface of inorganic oxide particle processes and can use known method so far, such as, to inorganic oxide The alcohol dispersion liquid of microgranule adds the organo-silicon compound of ormal weight, is added thereto to water, adds as required It is hydrolyzed as acid or the alkali of hydrolysis catalyst.Now, relative to inorganic oxide particle, organic Silicon compound presses solid constituent conversion, as R_n-SiX_(4-n)/2In the range of 1～100 weight %, preferably In the range of 2～80 weight %, further preferably in the range of 5～70 weight %.

If the amount of organo-silicon compound is few, then with the resin in the aftermentioned coating fluid for forming transparent coating Affinity between emulsion or disperse medium is low and stability is not enough, it is impossible to disperse in coating fluid equably, There is the situation of inorganic oxide particle coagulation according to occasion, and the intensity of transparent coating, marresistance reduce And the performance such as haze value rising, electric conductivity, reflectance becomes not enough situation.The amount of organo-silicon compound is i.e. Make too much, dispersibility can not be improved further, there is refractive index under the occasion of empty microgranule in silica Rising, antireflection property become not enough situation, there is charging preventive property and become under the occasion of electrically conductive microparticle Obtain not enough situation.

(ii) polymeric dispersant

As disperse medium used in the present invention, as long as resin emulsion can not dissolved and maintain emulsion, Can dissolve or disperse aftermentioned cross-linking agent or polymerization initiator and the dispersion of inorganic oxide particle can be disperseed Medium.

Specifically, the known polymer such as polyethylene, polyacrylic acid, polycarboxylic acids, polyurethane can be used to divide Powder.More specifically, as polyethylene polymer, can use polyvinyl alcohol, polyvinylpyrrolidone, Polyvinyl acetate, polyvinyl ester etc. and copolymer thereof；As acrylic acid polymer, polypropylene can be used Acid, sodium polyacrylate, ammonium polyacrylate etc. and copolymer thereof；As polycarboxylic acid polymer, poly-carboxylic can be used Acid, polycarboxylic acids sodium, polycarboxylic acids ammonium etc. and copolymer thereof；As polyether polyols with reduced unsaturation, polyurethane etc. can be used And copolymer etc.；It is also possible to use the copolymer etc. of these copolymers or sulfonic acid polymer.

If use polymeric dispersant, then can reduce the haze value after stretching.The amount of polymeric dispersant Be preferably 1～300 weight % relative to inorganic oxide particle with solid component meter, more preferably 1～ 100 weight %.If the amount of polymeric dispersant is less than 1 weight %, then with aftermentioned for forming transparent quilt The affinity between resin emulsion or disperse medium in the coating fluid of film is low and stability is not enough, it is impossible to uniformly Ground disperses in coating fluid, there is the situation of inorganic oxide particle coagulation according to occasion, and transparent coating The performances such as the reduction of intensity, marresistance and haze value rising, electric conductivity, reflectance become not enough situation. When the amount of polymeric dispersant is more than 300 weight %, dispersibility can not be improved further, at silicon dioxide Have under the occasion of hollow minute particle that refractive index rises, antireflection property becomes not enough situation, micro-in electric conductivity The situation that charging preventive property becomes not enough is there is under the occasion of grain.

It addition, the molecular weight of the polymeric dispersant of the present invention is preferably 1000～100000, the most excellent Elect 5000～50000 as.When molecular weight is less than 1000, owing to polymeric dispersant does not chases after stretching, therefore Can produce space after stretching when stretching ratio height, haze value raises.When molecular weight is more than 100000, nothing The meeting coagulation of machine oxide fine particle, the haze value of film can rise.

Resin emulsion

Resin emulsion is to be dispersed stably in dispersion by organic resin with the state of droplet, i.e. emulsion state to be situated between In matter, resin can be in thermoplastic resin, heat curing-type (including electronic beam solidified) resin Any one, both can be the resin breast being dispersed in the hydrophilic solvent such as water or alcohol by lipophilic resin Liquid, it is also possible to be to be dispersed in the liphophilic solvents that polarity is low by the hydrophilic resin with water with affinity The resin emulsion become.This means such resin emulsion have resin insoluble in disperse medium but shape Become the non-compatibility of emulsion.During it addition, the droplet state of emulsion maintains formation tunicle, in the present invention When also maintaining stretching.

Under the occasion of lipophile disperse medium, use and water have the hydrophilic resin (A) of affinity, Under the occasion of hydrophilic dispersion medium, use and water do not have the lipophilic resin (B) of affinity.

As having the resin (A) of affinity with water, can enumerate selected from epoxy resin, polyester resin, poly- Carbonate resin, polyamide, polyphenylene oxide resin, vinyl chloride resin, fluororesin, vinyl acetate tree Fat, organic siliconresin, polyurethane resin, melmac, butyral resin, phenolic resin, insatiable hunger With at least one in the two or more copolymer in polyester resin, these resins or modified body；As with Water does not have the resin (B) of affinity, can use selected from organic siliconresin, polyurethane resin, thermoplasticity At least one in acrylic resin, thermal-curable acrylic resin, ultraviolet hardening acrylic resin.

From the viewpoint of environmental pressure, use and not there is with water the resin (B) of affinity and hydrophilic divides The resin emulsion of dispersion media is advisable.

It addition, resin (B) is in order to form emulsion, himself can have carboxyl, sulfonyl, amino, The functional group of phosphoryl, hydroxyl and other derivant etc., it is possible to have be used between resin or resin Process organo-silicon compound with surface and carry out any functional group of cross-linking, such as epoxy radicals, carbodiimide, NCO, acryloyl group, vinyl etc..Wherein, polyurethane resin, PVA resin, acrylic acid tree Fat is transparent due to prepared film and these resins are thermoplastic resins, thus is preferably used.

Specifically, " ADEKA that ADEKA Corp. (ADEKA (strain)) manufacture is preferably used BONTIGHTER (アデカボ Application タイタ) " the serial, " BONDIC of Dainippon Ink Chemicals's manufacture (ボ Application ディッ Network) " serial, " HYDRAN (Ha イ De ラ Application) " series, Japanese polyurethane work " MIRACTRAN (the ミラ Network that industry Co., Ltd. (Japan's Port リウレタ Application work (strain)) manufactures トラ Application) " " IMPRANIL (the イ Application プラニ that manufactures of series, Bayer AG (バイエ Le society) Le) " " Soflanate that manufactures of Soflan Co., Ltd. serial, Japanese (Japan ソ Off ラ Application (strain)) (ソ Off ラネト) " series, Kao Corp's (flower king (strain)) manufacture " POIZ " series, " SANPRENE (the サ Application プ that Sanyo Chemical Industries, Ltd. (Sanyo's chemical conversion work (strain)) manufactures レ Application) " series, " the Aizerax that manufactures of Baotugu Chemical Industrial Co., Ltd's (hodogaya chemical work (strain)) (アイゼラッ Network ス) " serial, Di-ichi Kogyo Seiyaku Co., Ltd.'s (the first work (strain)) " SUPERFLEX (the スパ Off レッ Network ス) " manufactured is serial, " ELASTRON (エラストロ Application) " series, the " NeoRez (ネ that manufactures of Zeneca Co., Ltd. (ゼネカ (strain)) オレッ Star) " the serial ester-polyurethane resin emulsion waited with water as disperse medium.

Such resin emulsion is in the most spherical, but its diameter is preferably in the range of 10～500nm, enters One step is preferably in the range of 20～300nm.The footpath of the resin emulsion emulsion less than 10nm is difficult to obtain, Even if obtaining, contraction during hardening is also big, can crack.The footpath of if tree fat liquor is more than 500 Nm, then inorganic oxide particle becomes to be difficult to dispersed, internal reflection rate in face can produce film uneven, outward appearance Can be deteriorated.

The footpath (diameter) of resin emulsion measure in use dynamic scattering particle size determination device (FPAR-1000, Big Electronics Co., Ltd (great Zi She) manufactures).

Concentration (the C of the resin emulsion in the coating fluid forming transparent coating_R) preferred with solid component meter In the range of 0.006～68 weight %, further preferably in the range of 0.2～49 weight %.If Concentration (C with solid component meter_R) low, then owing to resin is few, inorganic oxide particle is too much, there is film Intensity, marresistance, cut intensity etc. become not enough situation.The stretching, extension of transparent coating when there is also stretching Uneven and situation about cracking.Concentration (C_R) the highest, except with the adaptation of base material, film-strength, table Outside face flatness, marresistance, cut intensity etc. become to be not enough to, due also to inorganic oxide particle tails off And there is the situation that cannot obtain sufficient electric conductivity, antireflection property etc..

Concentration (the C of inorganic oxide particle in coating fluid_P) and resin emulsion concentration (C_R) concentration ratio (C_P/C_R) different according to the purposes usage of transparent coating, but preferably in the range of 0.03～4.It addition, As the purposes of transparent coating, hard coat, anti-charged, easy-adhesion, antireflection, agglomeration resistance can be enumerated Property, thermal insulation etc., set the most preferably scope according to these purposes.

Specifically, under the occasion of hardcoat film, (C_P/C_R) preferably in the range of 0.1～4, Further preferably in the range of 0.25～2.4.If within the range, then can be formed with base material is close The transparent hard that the aspect such as conjunction property, film-strength, surface, marresistance, cut intensity is excellent is coated with Tunic.

Under the occasion of anti-charged membrane, (C_P/C_R) preferably in the range of 0.03～2.4, further preferably In the range of 0.05～1.If within the range, then can be formed the adaptation with base material, film-strength, The aspects such as anti-charging property (electric conductivity) aspect excellence and surface, marresistance, cut intensity are excellent The anti-charged membrane of the transparency.

Under the occasion of easy-adhesion layer, (C_P/C_R) preferably in the range of 0.03～1, the most excellent It is selected in the range of 0.05～0.25.If within the range, then can not damage be arranged at base material and on Under conditions of the function of other functional membrane on layer, formed the most bonding with the adaptation aspect of base material excellence Property layer.

It addition, under the occasion of easy-adhesion layer, it is also possible to contain inorganic oxide particle (C) further. Additionally, it is also possible to inorganic oxide particle (C) replaces inorganic oxide particle (A) and chain is inorganic The part of at least one party in oxide fine particle (B).By using inorganic oxide particle (C), energy Enough form the easy-adhesion layer that anticaking capacity aspect is excellent.

It addition, as inorganic oxide particle, if it being carried out surface at unused above-mentioned organo-silicon compound Use under conditions of process, then inorganic oxide particle presents the state of aggregation of appropriateness, it is possible to by light Scatter and suppress interference fringe.Or, it is possible to by the particle as inorganic oxide particle is selected So that the obtained refractive index of easy-adhesion layer connects with the refractive index of base material recently suppresses interference fringe.

Under the occasion of antireflection film, (C_P/C_R) preferably in the range of 0.1～4, further preferably exist In the range of 0.25～2.4.If within the range, then can be formed the adaptation with base material, film-strength, The transparent antireflection film that antireflection property aspect is excellent.

Under the occasion of anticaking capacity film, it is also possible to contain inorganic oxide particle (C) further.It addition, Also inorganic oxide particle (A) and chain inorganic oxide can be replaced with inorganic oxide particle (C) The part of at least one party in microgranule (B).By using inorganic oxide particle (C), it is possible to formed Easy-adhesion layer.In these situations, if (C_P/C_R) 0.03～1, further 0.05～0.25 In the range of, then can form the transparent anticaking capacity film that the aspects such as the adaptation with base material, film-strength are excellent.

Under the occasion of thermal isolation film, (C_P/C_R) preferably in the range of 0.1～4, further preferably exist In the range of 0.25～2.4.If within the range, then can be formed the adaptation with base material, film-strength, The transparent thermal isolation film that the aspects such as surface, marresistance, cut intensity are excellent.

Disperse medium

As disperse medium, it is necessary to be not dissolve resin emulsion and it can be made scattered molten with emulsion state Agent.Such as, water or organic solvent can be used.As long as it addition, can dissolve or disperse crosslinking described hereinafter Agent or polymerization initiator and can disperse inorganic oxide particle, the most particularly limit.

Specifically, can enumerate: water, methanol, ethanol, propanol, 2-propanol (IPA), butanol, two The alcohols such as pyruvic alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, hexanediol, Isopropanediol, methyl acetate, second The esters such as acetoacetic ester, butyl acetate, diethyl ether, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol list The ethers such as butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, acetone, first and second The ketones such as ketone, methyl iso-butyl ketone (MIBK), acetylacetone,2,4-pentanedione, pyruvate, methyl cellosolve, ethyl cellosolve, Butyl cellosolve, toluene, Ketohexamethylene, isophorone, DMF etc..Wherein, water and Alcohols is suitable.

Cross-linking agent

Coating fluid can be added as needed on cross-linking agent.Cross-linking agent is thermoplastic resin at the resin of resin emulsion Occasion under use.As cross-linking agent, occur anti-as long as have the active group being had with resin emulsion The compound of the functional group answered just is not particularly limited, and can carry out from known cross-linking agent so far according to resin Suitably select and use, the epoxide with water as disperse medium, amino-compound, Carbimide. can be used Ester compounds, carbodiimide compound etc..

The addition of cross-linking agent is not particularly limited, the addition of cross-linking agent according to the kind of resin emulsion and Different, but relative to being calculated as the resin emulsion of 100 weight % with solid constituent, cross-linking agent is excellent with solid component meter It is selected in below 200 weight %, further preferably in the range of 10～100 weight %.If cross-linking agent Addition is few, then according to the kind of resin emulsion, the solidification of transparent coating can become insufficient.If crosslinking The addition of agent is too much, then the stability that there is coating fluid becomes the situation of deficiency, and obtained transparent quilt Situation about cracking on film.

Polymerization initiator

Coating fluid can be added as needed under the occasion of gel-type resin polymerization initiator.Draw as polymerization Send out agent, as long as resin emulsion polymerization, solidification can be made, the most particularly limit, can carry out according to resin Suitably select.

Such as, azo-compound, benzoyl peroxide or the peroxidating first such as azonitrile or azo amide can be enumerated The organic peroxides such as ethyl ketone.

The addition of polymerization initiator is different according to the kind of resin emulsion, but is calculated as relative to solid constituent The resin emulsion of 100 weight %, polymerization initiator, enters with solid component meter preferably below 200 weight % One step is preferably in the range of 10～100 weight %.If the usage amount of polymerization initiator is few, the most transparent quilt The solidification of film can become insufficient.If the addition of polymerization initiator is too much, then there is stablizing of coating fluid Property become not enough situation, and situation about cracking on obtained transparent coating.

For forming all solids constituent concentration of the coating fluid of transparent coating preferably in 0.03～70 weight % In the range of, further preferably in the range of 1～50 weight %.

If the solid component concentration of coating fluid is too low, then it is difficult to adjust thickness, and easily the most in the dry state Produce inequality.It is difficult to obtain required film it addition, exist under the occasion of the after-drawing base material film of coating solution Thick situation, and situation about producing with crackle.If the solid of the coating fluid for forming transparent coating becomes Divide excessive concentration, then reduce due to stability reduction, coating, there is obtained transparent coating and base material Adaptation, film-strength, marresistance, cut intensity etc. become not enough situation.Especially because coating The viscosity of liquid raises, exist be difficult to catch up with base material stretching even spread, be difficult to stretching after coating Time situation that film is evenly stretched, and produce speckle or film uneven (island structure), produce and split The situation of stricture of vagina.

Below, the method using above-mentioned coating fluid to manufacture the base material with film is illustrated.

[there is the manufacture method of the base material of transparent coating]

The manufacture method of the base material with transparent coating of the present invention includes operation and the stretching of applied coating solution The operation of base material film.Specifically, as long as (1) film after by coating solution to base material is done The method and (2) that before dry stretch the base material with film stretch base material while being coated with painting The method of cloth liquid, does not makees special provision to the application frequency of coating fluid or the direction of stretching or number of times.Enter one Walk specifically simplified method, following four form can be enumerated.

·First form

In first form, after painting process, carry out biaxial stretch-formed operation.

Carry out following operation i.e., successively:

A () be the operation of applied coating solution on resin molding base material；

B () carries out the operation that twin shaft (vertical and horizontal) stretches to the resin molding with film；

C () removes the operation of disperse medium contained in (being dried) film；

D () carries out the operation solidified.

Operation (a)

Resin molding base material is coated with above-mentioned coating fluid.Here, the base material before stretching is used.Base before stretching The thickness of material is generally in the range of 400～5000 μm.Specifically, can enumerate: poly terephthalic acid The polyester base material such as glycol ester, PEN, polyethylene film, polypropylene screen, cyclic polyolefin Polyolefin base material, the polyamide substrate such as nylon-6, nylon-66, and polypropylene sorrel, the poly-ammonia such as hydrocarbon film Ester film, polycarbonate membrane, polyester film, poly (ether sulfone) film, polystyrene film, polymethylpentene film, polyether-ketone The base material such as film, acrylonitril membrane.Particularly polyester base material or polypropylene sorrel are owing to thermostability aspect is excellent and thoroughly Bright property is high and preferably uses.

The coating process of coating fluid can use nebulization, spin-coating method, rolling method, stick coating method, slot coated to print The known method such as brush method, woodburytype, micro-woodburytype.Recommend in the present invention rolling method, Slot coated print process, woodburytype, micro-woodburytype.

Coating weight now is that the thickness of the transparent coating after being applied to stretching reaches desired thickness.Such as, exist Easily under the occasion of adhesive linkage or anticaking capacity film, it is applied to average film thickness (T_F) reach 10～2000nm, Preferably 20～800nm preferably.Under the occasion of antireflection film, it is applied to average film thickness (T_F) reach 80～ 400nm, preferably 90～300nm are preferably.Under the occasion of hardcoat film, it is applied to average film thickness (T_F) Reach 0.5～30 μm, preferably 1～10 μm preferably.Under the occasion of anti-charged membrane, it is applied to average film Thick (T_F) reach 1～20 μm, preferably 3～15 μm preferably.Under the occasion of thermal isolation film, it is applied to put down All thickness (T_F) reach 1～300 μm, preferably 5～100 μm preferably.

Operation (b)

The resin molding with film is stretched.Drawing process can use biaxial stretching process.Now, stretching After the thickness of base material generally preferably in the range of 20～200 μm.Here, so-called biaxial stretch-formed, be Refer to the base material with film is stretched along the direction batching (roller) (longitudinal axis stretching), go back edge simultaneously Direction normal thereto to carry out stretching (transverse axis stretching).

Operation (c)

As drying means, as long as the disperse medium that can remove coating fluid is just not particularly limited.Such as, Can air-dry, but be possible with heating and the resin molding being formed with film is dried.Heating-up temperature is about 50～200 DEG C, the time is about 1 second～1 hour.

Operation (d)

The method making curing of coating is different according to the kind of resin emulsion used in coating fluid, but is using heat It is heating and curing under the occasion of curable type resin, under the occasion using ultraviolet curing resin, carries out ultraviolet Line irradiates, and heating can be used as required to wait known method so far.Pass through under the occasion of thermoplastic resin Cooling after heating solidifies.

·Second form

In second form, after the base material stretched through the longitudinal axis is coated operation, carry out transverse axis stretching work Sequence.

Carry out following operation i.e., successively:

(a ') operation of applied coating solution on the resin molding base material stretched through the longitudinal axis；

(b ') carries out the operation of transverse axis stretching to the resin molding with film；

D () carries out the operation solidified.

Operation (a ')

The resin molding base material stretched through the longitudinal axis is coated with the above-mentioned coating fluid for forming transparent coating.Warp The thickness of the base material of overstretching is generally in the range of 40～500 μm.Base material uses described in the first form Base material, the coating process of coating fluid also uses identical method.Coating weight now is to be applied to final obtaining Average film thickness (the T of the transparent coating arrived_F) reach above-mentioned scope preferably.

Operation (b ')

The resin molding with film is carried out transverse axis stretching.Now, the thickness of the base material after being stretched to stretching reaches Scope to usual 20～200 μm.

Operation (c) and operation (d) and the first homomorphosis.

·3rd form

In 3rd form, it is coated operation and longitudinal axis stretching process simultaneously.

Carry out following operation i.e., successively:

(a ") carry out longitudinal axis stretching base material while on resin molding base material the operation of applied coating solution；

(b ") carries out the operation of transverse axis stretching to the resin molding with film；

D () carries out the operation solidified.

Operation (a ")

Carry out longitudinal axis stretching base material while being coated with above-mentioned coating fluid on resin molding base material.

The drawing process of base material and the longitudinal axis drawing process of the second form are identical.Base material uses institute in the first form The base material stated, the coating process of coating fluid also uses identical method.Coating weight now is to be applied to finally Average film thickness (the T of the transparent coating obtained_F) reach above-mentioned scope preferably.

Operation (b ")

Operation (c) and operation (d) and the first and second homomorphosis.

·4th form

In 4th form, it is coated operation and biaxial stretch-formed operation simultaneously.

Carry out following operation i.e., successively:

(a " ') while base material being carried out twin shaft (longitudinal axis and transverse axis) stretching while being coated with on base material The operation of coating fluid；

D () makes the operation of curing of coating.

Operation (a " ')

While base material being carried out biaxial stretch-formed while being coated with above-mentioned coating fluid on resin molding base material.Drawing process Use biaxial stretching process.Now, the thickness of the base material after stretching is in the range of usual 20～200 μm Good.Base material uses the base material described in the first form, and the coating process of coating fluid also uses identical method. Coating weight now is the average film thickness (T of transparent coating being applied to finally give_F) reach above-mentioned scope and be Good.

Operation (c) and operation (d) and first～the 3rd homomorphosis.

Take this, the base material with transparent coating of the present invention can be manufactured.

Average film thickness (the T of obtained transparent coating_F) different according to the kind of transparent coating, preferably upper In the range of stating.Such as, under there is the occasion of base material of antireflection film, the average film thickness (T of antireflection film_F) less than 80nm time, there is antireflection film strength, marresistance becomes not enough situation, also can nothing Method obtains required reflectance.If average film thickness (T_F) more than 400nm, then easily produce on antireflection film Raw crackle, and therefore there is the situation that antireflection film strength becomes not enough, and the antireflection owing to film is the thickest Performance becomes not enough situation.If the average film thickness (T of antireflection film_F) within the above range, then can Obtain that reflectance (bottom reflection rate, visual reflection rate) is low and antireflection film that the aspect such as film-strength is excellent.

In the present invention, the average film thickness (T of transparent coating_F) can be by utilizing transmission electron microscope (TEM) The cross section of transparent coating is shot and measures.

In transparent coating, the content of inorganic oxide particle is preferably in the range of 3～80 weight %, further Preferably in the range of 5～70 weight %.In transparent coating, the content of inorganic oxide particle is less than 3 weight During %, except becoming with the adaptation of base material, film-strength, surface, marresistance, cut intensity etc. Outside must being not enough to, the reduction that there is also refractive index under the occasion of antireflection film is insufficient, antireflection property becomes Obtain not enough situation.If the content of inorganic oxide particle is more than 80 weight % in transparent coating, then remove Due to particle too many and outside making film-strength, marresistance, the cut intensity etc. become to be not enough to, at antireflection The situation that haze value raises is there is also under the occasion of film.Also can due to stretching time transparent coating stretching, extension do not chase after The stretching of base material and crack.

In transparent coating, the content of the resin of resin emulsion is preferably in the range of 20～97 weight %, Further preferably in the range of 30～95 weight %.Inventors believe that, its reason be resin emulsion extremely In film, droplet shape is maintained till the most before it is dried, therefore, even if base material is pullled when stretching, It also is able to move in film correspondingly or deformation.Then, dry by afterwards of this droplet shape Dry, cured and melt, solidify, thus overall film forming.

If low from the content of the resin of resin emulsion in transparent coating with solid component meter, then resin Few, in addition to film-strength, marresistance, cut intensity etc. become to be not enough to, due also to particle is many and exist The situation that the haze value of transparent coating raises.Also can due to stretching time transparent coating stretching, extension do not chase after base material Stretch and crack.Too much if from the content of the resin of resin emulsion in transparent coating, then particle is few, Except becoming not enough with the adaptation of base material, film-strength, surface, marresistance, cut intensity etc. In addition, there is also that inorganic oxide particle is few and the function of transparent coating becomes not enough situation.

Below, by embodiment, the present invention will be described, but the invention is not limited in these embodiments.

[embodiment 1]

For forming the preparation of the coating fluid (H-1P) of hardcoat film

Use ultrafilter membrane by Ludox (RiHui catalyst synthesis Co., Ltd's (day catalyst chemical conversion (strain)) system Make: Cataloid-SN (カタロイ De-SN), mean diameter is 12nm, SiO₂Concentration is 20 Weight %, disperse medium is water) in replacing dispersion medium be ethanol, being configured to solid component concentration is 20 The alcohol dispersion liquid of the silicon dioxide microparticle (H-1V) of weight %.

Alcohol dispersion liquid to the silicon dioxide microparticle (H-1V) that 100g solid component concentration is 20 weight % Middle addition 4g silane coupler (MTMS, KCC of SHIN-ETSU HANTOTAI (SHIN-ETSU HANTOTAI's chemistry (strain)) Manufacture: KBM-13), carrying out heat treated at 50 DEG C, being configured to solid component concentration is 20 weight % The alcohol dispersion liquid of surface treated silica microgranule (H-1VS).Use rotary evaporator by disperse medium It is replaced into water, is configured to the surface treated silica microgranule that solid component concentration is 40.5 weight % (H-1VS) aqueous dispersions.Now alkali concn is 200ppm.

Then, in the aqueous dispersions of 10.0g surface treated silica microgranule (H-1VS), mix 11.4 (Di-ichi Kogyo Seiyaku Co., Ltd.: SUPERFLEX 210, resin concentration is g ester-polyurethane resin emulsion 35 weight %, emulsion diameter: 50nm, disperse medium: water), 5.3g isopropanol and be configured to solid Point concentration is the coating fluid (H-1P) for forming hardcoat film of 30.0 weight %.

There is the manufacture of the stretched film base material (H-1F) of hardcoat film

Relative to the dimethyl terephthalate (DMT) of 100 weight %, add the ethylene glycol and 0.01 of 70 weight % The calcium acetate as ester exchange catalyst of weight %, three oxidations as polycondensation catalyst of 0.03 weight % Antimony, is warming up to 220 DEG C, evaporates theoretic methanol, completes ester exchange reaction.Then, add in system Add the trimethyl phosphate of 0.04 weight %.Reduce pressure in system, under the decompression of 1mmHg, in The temperature of 290 DEG C carries out the polycondensation reaction of 4 hours, prepares polyester resin.

Utilize extruder by obtained polyester resin slabbing at 295 DEG C, prepare base material polyester tree Adipose membrane (1).The thickness of polyester resin film (1) is 1125 μm.This polyester resin film (1) is carried out After longitudinal axis stretching (140 DEG C, 2.5 times of stretchings), stick coating method (rod #60) coating is utilized to be used for being formed firmly The coating fluid (H-1P) of matter coated film, after carrying out 120 seconds be dried, carries out transverse axis and draws at 140 DEG C Stretch (140 DEG C, 4.5 times of stretchings), prepare the stretched film base material (H-1F) with hardcoat film.Now, The thickness of film base material is 100 μm, and the thickness of hardcoat film is 5 μm.

Obtained had total light transmittance of stretched film base material (H-1F) of hardcoat film, mist degree Value, adaptation, pencil hardness, speckle, film uneven (island structure), have flawless, film surface flat Smooth property and marresistance are measured, and result is shown in table.Utilize haze meter (testing machine strain formula meeting must be congratulated Society's (スガ (strain)) manufactures) measure total light transmittance and mist degree.

It addition, only base material polyester resin film (1) to be stretched in an identical manner the thickness of 100 μm, Total light transmittance is 93.14%, and haze value is 0.27%.

Pencil hardness

Pencil hardness utilizes pencil hardness test device to measure according to JISK 5400.That is, with relative to hard Coated film surface is that the angle of 45 degree arranges pencil, applies the load of regulation, pulls with fixed speed, Observation has not damaged.

Adaptation

11 are gone out by cutter interval scribing with 1mm anyhow on the base material (H-1F) have hardcoat film The parallel scar of bar, to form 100 grids, is pasted cellophane tape thereon, then, will be peeled off glass During paper self-adhesive tape, tunicle is unstripped and that remain grid number is divided into following Three Estate, thereby carries out adaptation Evaluate.Result is shown in table.

Residual grid number is more than 90: ◎

Residual grid number is between 85～89: zero

Residual grid number is below 84: △

Film is uneven (island structure)

By visually surface being observed, it is evaluated according to following benchmark.

The open defect of uneven shape on surface cannot be confirmed.: ◎

Almost cannot confirm the open defect of uneven shape on surface.: zero

Slightly observe the open defect of uneven shape on surface.: △

Substantially observe the open defect of uneven shape on surface.: ×

Crackle

Utilize ultramicroscope that surface is observed, be evaluated according to following benchmark.

Entirely without observing crackle.: ◎

Slightly observe blind crack.: zero

Substantially observe blind crack.: △

Observe blind crack and big crackle.: ×

The flatness on film surface

Surface (Ra) utilizes high-tech Co., Ltd. of Hitachi ((strain) Hitachi Ha イテ Network サイエ Application ス society) atomic force microscope (AFM) that manufactures measures, is evaluated according to following benchmark.

Ra value is less than 10nm: ◎

Ra value at 10nm less than 20nm: zero

Ra value at 20nm less than 50nm: △

Ra value is at more than 50nm: ×

The mensuration of marresistance

Use #0000 steel wool with 500g/cm²Loaded journal 50 times, the surface of film is visually seen Examining, be evaluated according to following benchmark, result is shown in table.

Have no lines scar: ◎

Slightly see lines scar: zero

See a large amount of lines scar: △

Surface is by overall scraping: ×

[embodiment 2]

For forming the preparation of the coating fluid (H-2P) of hardcoat film

At the surface treated silica microgranule that 5.9g is configured to according to the same manner as in Example 1 (H-1VS) aqueous dispersions is mixed into 16.0g ester-polyurethane resin emulsion (Di-ichi Kogyo Seiyaku Co., Ltd.: SUPERFLEX 210, resin concentration is 35 weight %, emulsion diameter: 50nm, disperse medium: water), 4.7g isopropanol, is configured to the painting for forming hardcoat film that solid component concentration is 30.0 weight % Cloth liquid (H-2P).

There is the manufacture of the stretched film base material (H-2F) of hardcoat film

Except substitute with (H-2P) (H-1P) as being used for forming the coating fluid of hardcoat film in addition to, Prepare the stretched film base material (H-2F) with hardcoat film according to the same manner as in Example 1.Now, The thickness of film base material is 100 μm, and the thickness of hardcoat film is 4.8 μm.

Obtained had total light transmittance of stretched film base material (H-2F) of hardcoat film, mist degree Value, adaptation, pencil hardness, speckle, film uneven (island structure), have flawless, film surface flat Smooth property and marresistance are measured, and result is shown in table.

[embodiment 3]

For forming the preparation of the coating fluid (H-3P) of hardcoat film

At the surface treated silica microgranule that 13.8g is configured to according to the same manner as in Example 1 (H-1VS) aqueous dispersions is mixed into 6.9g ester-polyurethane resin emulsion (Di-ichi Kogyo Seiyaku Co., Ltd.: SUPERFLEX 210, resin concentration is 35 weight %, emulsion diameter: 50nm, disperse medium: water), 6.0g isopropanol, is configured to the painting for forming hardcoat film that solid component concentration is 30.0 weight % Cloth liquid (H-3P).

There is the manufacture of the stretched film base material (H-3F) of hardcoat film

Except substituting (H-1P) as forming hardcoat film with (H-3P) in embodiment 1 Beyond coating fluid, prepare the stretched film base material (H-3F) with hardcoat film in the same fashion.This Time, the thickness of film base material is 100 μm, and the thickness of hardcoat film is 5.4 μm.

Obtained had total light transmittance of stretched film base material (H-3F) of hardcoat film, mist degree Value, adaptation, pencil hardness, speckle, film uneven (island structure), have flawless, film surface flat Smooth property and marresistance are measured, and result is shown in table.

[embodiment 4]

For forming the preparation of the coating fluid (H-4P) of hardcoat film

At the surface treated silica microgranule that 10.0g is configured to according to the same manner as in Example 1 (H-1VS) aqueous dispersions is mixed into 11.4g ester-polyurethane resin emulsion (Di-ichi Kogyo Seiyaku Co., Ltd.: SUPERFLEX 210, resin concentration is 35 weight %, emulsion diameter: 50nm, disperse medium: water), The pure water of 10.6g, 8.0g isopropanol, being configured to solid component concentration is the hard for being formed of 20.0 weight % The coating fluid (H-4P) of matter coated film.

There is the manufacture of the stretched film base material (H-4F) of hardcoat film

Except substituting (H-1P) as forming hardcoat film with (H-4P) in embodiment 1 Beyond coating fluid, prepare the stretched film base material with hardcoat film according to the same manner as in Example 1 (H-4F).Now, the thickness of film base material is 100 μm, and the thickness of hardcoat film is 3.2 μm.

Obtained had total light transmittance of stretched film base material (H-4F) of hardcoat film, mist degree Value, adaptation, pencil hardness, speckle, film uneven (island structure), have flawless, film surface flat Smooth property and marresistance are measured, and result is shown in table.

[embodiment 5]

For forming the preparation of the coating fluid (H-5P) of hardcoat film

At the surface treated silica microgranule that 10.0g is configured to according to the same manner as in Example 1 (H-1VS) aqueous dispersions is mixed into 13.5g ester-polyurethane resin emulsion (Di-ichi Kogyo Seiyaku Co., Ltd.: SUPERFLEX 150, resin concentration is 30 weight %, emulsion diameter: 70nm, disperse medium: water), 3.5g isopropanol, is configured to the painting for forming hardcoat film that solid component concentration is 30.0 weight % Cloth liquid (H-5).

There is the manufacture of the stretched film base material (H-5F) of hardcoat film

Except substituting (H-1P) as forming hardcoat film with (H-5P) in embodiment 1 Beyond coating fluid, prepare the stretched film base material with hardcoat film according to the same manner as in Example 1 (H-5F).Now, the thickness of film base material is 100 μm, and the thickness of hardcoat film is 4.9 μm.

Obtained had total light transmittance of stretched film base material (H-5F) of hardcoat film, mist degree Value, adaptation, pencil hardness, speckle, film uneven (island structure), have flawless, film surface flat Smooth property and marresistance are measured, and result is shown in table.

[embodiment 6]

For forming the preparation of the coating fluid (H-6P) of hardcoat film

The solid component concentration by embodiment 1 at 10.0g is adjusted to the surface of 60 weight % and processes two Silicon oxide particle (H-6VS) is mixed into 17.1g ester-polyurethane resin emulsion (Di-ichi Kogyo Seiyaku Co., Ltd.: SUPERFLEX 210, resin concentration is 35 weight %, emulsion diameter: 50nm, disperse medium: water), 6.8g isopropanol, is configured to the painting for forming hardcoat film that solid component concentration is 35.3 weight % Cloth liquid (H-6P).

There is the manufacture of the stretched film base material (H-6F) of hardcoat film

Utilize stick coating method (rod #72) in the base material polyester tree prepared according to the same manner as in Example 1 The upper coating of adipose membrane (1), for forming the coating fluid (H-6P) of hardcoat film, then, adds at 140 DEG C Temperature lower so that reach 2.5 times on y direction, the condition that reaches 4.5 times in X direction stretches, so After, at 140 DEG C, carry out 120 seconds be dried, prepare and there is the stretched film base material (H-6F) of hardcoat film. Now, the thickness of base material is 100 μm, and the thickness of hardcoat film is 2 μm.

Obtained had total light transmittance of stretched film base material (H-6F) of hardcoat film, mist degree Value, adaptation, pencil hardness, speckle, film uneven (island structure), have flawless, film surface flat Smooth property and marresistance are measured, and result is shown in table.

[embodiment 7]

There is the manufacture of the stretched film base material (H-7F) of hardcoat film

While at 140 DEG C of lower base material polyester resin to preparing according to the same manner as in Example 1 of heating Film (1), so that reaching the condition of 2.5 times on y direction and stretching, utilizes stick coating method (rod #60) The coating fluid for forming hardcoat film that coating is configured to according to the same manner as in Example 1 (H-1P), then, heat lower so that reaching the condition of 4.5 times in X direction and stretching at 140 DEG C, Then, at 140 DEG C, carry out 120 seconds be dried, prepare and there is the stretched film base material of hardcoat film (H-7F).Now, the thickness of base material is 100 μm, and the thickness of antireflection film is 5.1 μm.

Obtained had total light transmittance of stretched film base material (H-7F) of hardcoat film, mist degree Value, adaptation, pencil hardness, speckle, film uneven (island structure), have flawless, film surface flat Smooth property and marresistance are measured, and result is shown in table.

[embodiment 8]

There is the manufacture of the stretched film base material (H-8F) of hardcoat film

While at 140 DEG C of lower base material polyester resin to preparing according to the same manner as in Example 1 of heating Film (1) so that reach 2.5 times on y direction, the condition that reaches 4.5 times in X direction stretches, While utilize that stick coating method (rod #16) coating is configured to according to the same manner as in Example 1 for being formed The coating fluid (H-1P) of hardcoat film, then, carry out at 140 DEG C 120 seconds be dried, prepare tool There is the stretched film base material (H-8F) of hardcoat film.Now, the thickness of film base material is 100 μm, counnter attack The thickness penetrating film is 5 μm.

Obtained had total light transmittance of stretched film base material (H-8F) of hardcoat film, mist degree Value, adaptation, pencil hardness, speckle, film uneven (island structure), have flawless, film surface flat Smooth property and marresistance are measured, and result is shown in table.

[embodiment 9]

For forming the preparation of the coating fluid (H-9P) of hardcoat film

The solid component concentration obtained in 100g embodiment 1 is the silicon dioxide microparticle of 20 weight % (H-1V) (Toagosei Co., Ltd (closes to add 2g polyacrylic acid dispersant in alcohol dispersion liquid Become (strain)) manufacture: Aron SD-10), carrying out heat treated at 50 DEG C, reusing ultrafilter membrane will Replacing dispersion medium becomes ethanol to be configured to the silicon dioxide microparticle that solid component concentration is 20 weight % (H-9VS) alcohol dispersion liquid.Using rotary evaporator is water by replacing dispersion medium, is configured to solid Point concentration is the aqueous dispersions of the surface treated silica microgranule (H-9VS) of 40.5 weight %.Now alkali The concentration of metal is 200ppm.

Then, in the aqueous dispersions of 10.0g surface treated silica microgranule (H-9VS), mix 11.4 (Di-ichi Kogyo Seiyaku Co., Ltd.: SUPERFLEX 210, resin concentration is g ester-polyurethane resin emulsion 35 weight %, emulsion diameter: 50nm, disperse medium: water), 5.3g isopropanol, be configured to solid Point concentration is the coating fluid (H-9P) for forming hardcoat film of 30.0 weight %.

There is the manufacture of the stretched film base material (H-9F) of hardcoat film

At 140 DEG C of lower base material polyester resin films to preparing according to the same manner as in Example 1 of heating (1) stick coating method (rod #60) so that reaching the condition of 2.5 times on y direction and stretching, then, is utilized Coating is for forming the coating fluid (H-9P) of hardcoat film, after being dried 120 seconds, irradiates at 80 DEG C 600mJ/cm²Ultraviolet make it solidify, heat at 140 DEG C afterwards lower so that reaching 4.5 in X direction Times condition stretch, then, carry out at 140 DEG C 120 seconds be dried, prepare there is hard coat The stretched film base material (H-9F) of film.Now, the thickness of base material is 101 μm, and the thickness of antireflection film is 5 μm。

Obtained had total light transmittance of stretched film base material (H-9F) of hardcoat film, mist degree Value, adaptation, pencil hardness, speckle, film uneven (island structure), have flawless, film surface flat Smooth property and marresistance are measured, and result is shown in table.

[comparative example 1]

For forming the preparation of the coating fluid (RH-1P) of hardcoat film

By 53g dipentaerythritol acrylate (Kyoeisha Chemical Co., Ltd. (society's chemistry (strain) altogether) LIGHT ACRYLATE DPE-6A), the 1,6 hexanediol diacrylate of 5.9g (Japan manufacture: KAYARAD KS-HDDA), 0.4g strand chemical medicine Co., Ltd. (Japanization (strain)) manufactures: Terminal methyl acrylic acid organic silicone oil (Chemical Co., Ltd of SHIN-ETSU HANTOTAI (SHIN-ETSU HANTOTAI's chemistry work (strain)) manufactures: X-22-174DX), 75.5g propylene glycol monomethyl ether and 3.5g Photoepolymerizationinitiater initiater 2,4,6-trimethylbenzene first Acyl diphenyl phosphine oxide (BAS Amada Co., Ltd. (PVC-エエスジャパ Application (strain)) manufactures: Lucirin TPO) mix, it is configured to the substrate forming component that solid component concentration is 44 weight % molten Liquid (1).

Then, by substrate forming component solution (1) that 30.0g solid component concentration is 44 weight % and 30.0g The solid component concentration being configured to according to the same manner as in Example 1 is that the silicon dioxide of 40 weight % is micro- The alcohol dispersion liquid of grain (H-1VS) and the mixing of 22.6g isopropanol, being configured to solid component concentration is 30 weights The coating fluid (RH-1P) for forming transparent coating of amount %.

There is the manufacture of the stretched film base material (RH-1F) of hardcoat film

At 140 DEG C of lower base material polyester resin films to preparing according to the same manner as in Example 1 of heating (1) stick coating method (rod #60) so that reaching the condition of 2.5 times on y direction and stretching, then, is utilized Coating is for forming the coating fluid (RH-1P) of hardcoat film, after being dried 120 seconds, irradiates at 80 DEG C 600mJ/cm²Ultraviolet make it solidify, heat at 140 DEG C afterwards lower so that reaching 4.5 in X direction Times condition stretch, then, carry out at 140 DEG C 120 seconds be dried, prepare there is hard coat The stretched film base material (RH-1F) of film.Now, the thickness of base material is 100 μm, and the thickness of antireflection film is 5μm。

Obtained had total light transmittance of stretched film base material (RH-1F) of hardcoat film, mist Angle value, adaptation, pencil hardness, speckle, film uneven (island structure), there are flawless, film surface Flatness and marresistance are measured, and result is shown in table.

[comparative example 2]

For forming the preparation of the coating fluid (RH-2P) of hardcoat film

By 3.8g ester-polyurethane resin emulsion, (the first Industrial Co., Ltd manufactures: SUPERFLEX 210, tree Lipid concentration is 35 weight %, particle diameter: 50nm, disperse medium: water), 17.4g isopropanol, 1.8g first Base isobutyl ketone and 1.7g Isopropanediol mix, and are modulated into emulsus diluent.

Emulsus diluent is observed, result be visually under transparent, further, since particle diameter cannot be recorded, Therefore speculate that resin emulsion disappears.

Then, the surface treated silica that 3.28g is configured to according to the same manner as in Example 1 is added The aqueous dispersions of microgranule (H-1VS), being configured to solid component concentration is the hard for being formed of 9.5 weight % The coating fluid (RH-2P) of matter coated film.

There is the manufacture of the stretched film base material (RH-2F) of hardcoat film

At 140 DEG C of lower base material polyester resin films to preparing according to the same manner as in Example 1 of heating (1) so that reaching on y direction after the condition of 2.5 times stretches, to utilize stick coating method (rod #50) to be coated with Cloth, for forming the coating fluid (RH-2P) of hardcoat film, then, is carried out 120 seconds at 140 DEG C After drying, heat lower so that reaching the condition of 4.5 times in X direction and stretching at 140 DEG C, prepare tool There is the stretched film base material (RH-2F) of hardcoat film.Now, the thickness of base material is 100 μm, and hard is coated with The thickness of tunic is 5 μm.

Obtained had total light transmittance of stretched film base material (RH-2F) of hardcoat film, mist Angle value, adaptation, pencil hardness, speckle, film uneven (island structure), there are flawless, film surface Flatness and marresistance are measured, and result is shown in table.

[comparative example 3]

There is the manufacture of the stretched film base material (RH-3F) of hardcoat film

The base material polyester resin film (1) prepared according to the same manner as in Example 1 is carried out twin shaft draw Stretching, prepared thickness is the polyester resin film base material of 100 μm.

Then, utilize stick coating method (rod #18) coating according to consolidating that the mode identical with comparative example 1 is configured to Body constituent concentration is the coating fluid (RH-1P) for forming hardcoat film of 30.0 weight %, then, Carry out at 80 DEG C 120 seconds be dried, irradiate 600mJ/cm afterwards²Ultraviolet make it solidify, prepare There is the stretched film base material (RH-3F) of hardcoat film.Now, the thickness of base material is 100 μm, hard The thickness of coated film is 5 μm.

Obtained had total light transmittance of stretched film base material (RH-3F) of hardcoat film, mist Angle value, adaptation, pencil hardness, speckle, film uneven (island structure), there are flawless, film surface Flatness and marresistance are measured, and result is shown in table.

[embodiment 10]

For forming the preparation of the coating fluid (P-10P) of easy adhesive linkage

The aqueous dispersions of the silicon dioxide microparticle (H-1VS) obtained in 33.2g embodiment 1 is mixed into 1.4 (RiHui catalyst synthesis Co., Ltd manufactures g silicon dioxide organosol: ELCOM V-8901, average particle Footpath is 120nm, SiO₂Concentration is 20 weight %, disperse medium: methanol), 88.5g polyurethane resin (the first Industrial Co., Ltd manufactures emulsion: SUPERFLEX 210, and resin concentration is 35 weight %, breast Liquid diameter: 50nm, disperse medium: water), 89.1g isopropanol, 233.2g pure water, be configured to solid Constituent concentration is the coating fluid (P-10P) for forming easy adhesive linkage of 10.0 weight %.

There is the preparation of the stretched film base material (P-10F) of easy adhesive linkage

The base material polyester resin film (1) prepared according to the same manner as in Example 1 is carried out the longitudinal axis draw After stretching (140 DEG C, 2.5 times of stretchings), utilize stick coating method (rod #4) coating for forming easy adhesive linkage Coating fluid (P-10P), after carrying out 120 seconds be dried at 140 DEG C, carry out transverse axis stretching (140 DEG C, 4.5 times of stretchings), prepare the stretched film base material (P-10F) with easy adhesive linkage.Now, the thickness of film base material Degree is 100 μm, and the thickness of easy adhesive linkage is 0.1 μm.

Obtained had total light transmittance of stretched film base material (P-10F) of easy adhesive linkage, mist degree Value, adaptation, pencil hardness, speckle, film uneven (island structure), have flawless, film surface flat Smooth property, marresistance, anticaking capacity and cementability are measured, and also observe interference fringe, knot Fruit is shown in table.It addition, utilize following methods that anticaking capacity, cementability and interference fringe are evaluated.

Anticaking capacity

A part with the stretched film base material (P-10F) of easy adhesive linkage is cut into two pieces, wherein One piece of stretched film base material (base material+easy adhesive linkage) upper another block overlapping with easy adhesive linkage has the most bonding The stretched film base material (base material+easy adhesive linkage) of layer, according to every 1cm²The load of upper 10kg applies to bear a heavy burden, The complexity of the stripping after placing 24 hours is evaluated according to following benchmark.

It is very easy to peel off: ◎

Can be easily peeled off: zero

Somewhat it is difficult to peel off: △

Cannot peel off or be difficult to peel off: ×

Interference fringe

When being black when making the background with the stretched film base material (P-10F) of easy adhesive linkage, make glimmering The light of light modulation reflects on the surface of transparent coating, the rainbow figure that visualization is formed due to interference of light Case, is evaluated according to following benchmark.

Have no rainbow pattern: ◎ completely

Slightly see rainbow pattern: zero

Obvious rainbow pattern: △

See distinct rainbow pattern: ×

The evaluation of cementability

Stick coating method (rod #12) is utilized to be coated with hard on the stretched film base material (P-10F) have easy adhesive linkage (RiHui catalyst synthesis Co., Ltd manufactures coated coating: ELCOM HP-1004), is dried at 80 DEG C After 1 minute, utilize ultraviolet lamp (the Japanese battery strain being equipped with high voltage mercury lamp (120W/cm) Formula commercial firm (Japan pond) manufactures: UV irradiation unit CS30L21-3) it is carried out 600mJ/cm²'s Irradiation makes it solidify, and prepares the base material with hardcoat film easy-adhesion layer.Hardcoat film now Thickness be 5 μm, total film thickness is 5.6 μm.

Utilize said method that the adaptation of obtained hard coating film is measured, cementability is commented Valency.

[comparative example 4]

For forming the preparation of the coating fluid (RP-10P) of easy adhesive linkage

By 38.0g ester-polyurethane resin emulsion (first Industrial Co., Ltd manufacture: SUPERFLEX 210, Resin concentration is 35 weight %, particle diameter: 50nm, disperse medium: water), 170.4g isopropanol, 18.0 G methyl iso-butyl ketone (MIBK) and 17.0g Isopropanediol mix, and are modulated into emulsus diluent.

Then, the silicon dioxide microparticle that 33.2g is configured to according to the same manner as in Example 1 is added (H-1VS) aqueous dispersions and 0.6g silicon dioxide organosol (RiHui catalyst synthesis Co., Ltd Manufacture: ELCOM V-8901, mean diameter is 120nm, SiO₂Concentration is 20 weight %, and dispersion is situated between Matter: methanol), it is configured to the coating fluid for forming easy adhesive linkage that solid component concentration is 7.4 weight % (RP-4P)。

There is the preparation of the stretched film base material (RP-1) of easy adhesive linkage

The base material polyester resin film (1) prepared according to the same manner as in Example 1 is carried out the longitudinal axis draw After stretching (140 DEG C, 2.5 times of stretchings), utilize stick coating method (rod #6) coating for forming easy adhesive linkage Coating fluid (RP-4P), after carrying out 120 seconds be dried at 140 DEG C, carry out transverse axis stretching (140 DEG C, 4.5 times of stretchings), prepare the stretched film base material (RP-4F) with easy adhesive linkage.Now, the thickness of film base material Degree is 100 μm, and the thickness of easy adhesive linkage is 0.1 μm.

Obtained had total light transmittance of stretched film base material (RP-4F) of easy adhesive linkage, mist degree Value, adaptation, pencil hardness, speckle, film uneven (island structure), have flawless, film surface flat Smooth property, marresistance and anticaking capacity are measured, and result is shown in table.Also by according to embodiment 9 identical modes form hardcoat film and are evaluated cementability.

[embodiment 11]

For forming the preparation of the coating fluid (AS-11P) of anti-charged membrane

(RiHui catalyst synthesis Co., Ltd manufactures: ELCOM to make 60g mix Sb stannum oxide (ATO) microgranule TL-30HK, Sb₂O₅Content is 16 weight %, and mean diameter is 8nm) to be scattered in 140g concentration be 4.3 In the potassium hydroxide aqueous solution of weight %, this dispersion liquid is incubated at 30 DEG C, while carrying out with sand mill The pulverizing of 3 hours is to be configured to colloidal sol.

Then, utilize ion exchange resin that this colloidal sol is carried out dealkalize metal ion treatment until pH is 3.0, Be subsequently adding pure water and be configured to solid component concentration be 20 weight % mix Sb tin oxide particles dispersion liquid (AS-11V).The pH of this ATO particle dispersion liquid is 3.3.It addition, mean diameter is 8nm.

Then, ATO particle dispersion liquid (AS-11V) that 100g concentration is 20 weight % is adjusted to 25 DEG C, added 1.0g silane coupler (MTMS) (SHIN-ETSU HANTOTAI's chemistry strain with 3 minutes Formula commercial firm manufactures: KBM-13), carry out the stirring of 30 minutes afterwards.Then 100 were added with 1 minute G ethanol, was warming up to 50 DEG C with 30 minutes, carried out the Overheating Treatment of 15 hours.Solid constituent now is dense Degree is 10 weight %.

Then, utilize ultrafilter membrane that from the mixed solvent of water, ethanol, disperse medium is replaced as water, be configured to solid Body constituent concentration is that the surface treated ATO microparticle aqueous of 30 weight % dissipates liquid (AS-11VS). The most alkali-metal concentration is 100ppm.

Then, dissipate in liquid (AS-11VS) at 5.0g surface treated ATO microparticle aqueous and be mixed into 38.6g ester-polyurethane resin emulsion (Di-ichi Kogyo Seiyaku Co., Ltd.: SUPERFLEX 210, resin concentration Be 35 weight %, particle diameter: 50nm, disperse medium: water), 6.4g isopropanol, be configured to solid constituent Concentration is the coating fluid (AS-11P) for forming anti-charged membrane of 30.0 weight %.

There is the manufacture of the stretched film base material (AS-11F) of anti-charged membrane

The polyester resin film (1) prepared according to the same manner as in Example 1 is carried out longitudinal axis stretching (140 DEG C, 2.5 times of stretchings) after, utilize stick coating method (rod #42) coating for forming the coating fluid of anti-charged membrane (AS-11P), after carrying out 120 seconds be dried at 140 DEG C, carry out transverse axis stretching (140 DEG C, 4.5 Stretching again), prepare the stretched film base material (AS-11F) with anti-charged membrane.Now, the thickness of film base material Being 100 μm, the thickness of anti-charged membrane is 3 μm.

Obtained had total light transmittance of stretched film base material (AS-11F) of anti-charged membrane, mist Angle value, adaptation, pencil hardness, speckle, film uneven (island structure), there are flawless, film surface Flatness, marresistance and sheet resistance value are measured, and result is shown in table.Also utilize sheet resistance (Mitsubishi chemical Co., Ltd's (Mitsubishi Chemical (strain)) manufactures meter: Hiresta) measure sheet resistance value.

[comparative example 5]

For forming the preparation of the coating fluid (RAS-5P) of anti-charged membrane

Then, the solid component concentration that interpolation 4.9g is configured to according to the same manner as in Example 10 is The surface treated ATO microparticle aqueous of 30 weight % dissipates liquid (AS-11VS), is configured to solid Point concentration is the coating fluid (RAS-5P) for forming anti-charged membrane of 5.9 weight %.

B has the manufacture of the stretched film base material (RAS-5F) of anti-charged membrane

The polyester resin film (1) prepared according to the same manner as in Example 1 is carried out longitudinal axis stretching (140 DEG C, 2.5 times of stretchings) after, utilize stick coating method (rod #48) coating for forming the coating fluid of anti-charged membrane (RAS-5P), after carrying out 120 seconds be dried at 140 DEG C, carry out transverse axis stretching (140 DEG C, 4.5 Stretching again), prepare the stretched film base material (RAS-5F) with anti-charged membrane.Now, the thickness of film base material Degree is 100 μm, and the thickness of anti-charged membrane is 3.1 μm.

Obtained had total light transmittance of stretched film base material (RAS-5F) of anti-charged membrane, mist Angle value, adaptation, pencil hardness, speckle, film uneven (island structure), there are flawless, film surface Flatness, marresistance and sheet resistance are measured, and result is shown in table.

[embodiment 12]

For forming the preparation of the coating fluid (HI-12P) of thermal isolation film

At 98.0g hollow silica organosol, (RiHui catalyst synthesis Co., Ltd manufactures: ス Le リア 4110, solid component concentration: 20.5%, mean diameter is 60nm, disperse medium: isopropanol) in (the first Industrial Co., Ltd manufactures: SUPERFLEX 210, tree to be mixed into 24.0g ester-polyurethane resin emulsion Lipid concentration is 35 weight %, particle diameter: 50nm, disperse medium: water), then utilize rotary evaporator to remove Remove solvent, be configured to the coating fluid for forming thermal isolation film that solid component concentration is 50.0 weight % (HI-12P).The most alkali-metal concentration is 5ppm.

There is the manufacture of the stretched film base material (HI-12F) of thermal isolation film

The polyester resin film (1) prepared according to the same manner as in Example 1 is carried out longitudinal axis stretching (140 DEG C, 2.5 times of stretchings) after, utilize nebulization to be coated with 45 μm for forming the coating fluid of thermal isolation film (HI-12P), after carrying out 120 seconds be dried at 140 DEG C, carry out transverse axis stretching (140 DEG C, 1.5 Stretching again), prepare the stretched film base material (HI-12F) with thermal isolation film.Now, the thickness of film base material is 300 μm, the thickness of thermal isolation film is 30 μm.

To obtained have total light transmittance of stretched film base material (HI-12F) of thermal isolation film, haze value, Adaptation, pencil hardness, speckle, film uneven (island structure), have flawless, the flatness on film surface, Marresistance and thermal conductivity are measured, and result is shown in table.It addition, measure heat by the following method Conductance.

The mensuration of thermal conductivity

Use hot wire probe formula measuring thermal conductivity device (capital of a country Electronics Co., Ltd (capital of a country) manufactures: QTM-500) thermal conductivity of the stretched film base material (HI-12F) with thermal isolation film is measured.

[comparative example 6]

For forming the preparation of the coating fluid (RHI-6P) of thermal isolation film

By 38.0g ester-polyurethane resin emulsion (first Industrial Co., Ltd manufacture: SUPERFLEX 210, Resin concentration is 35 weight %, particle diameter: 50nm, disperse medium: water), 50.2g isopropanol, 18.0g Methyl iso-butyl ketone (MIBK) and 17.0g Isopropanediol mix, and are modulated into emulsus diluent.

Then, add 151.2g hollow silica organosol (RiHui catalyst synthesis Co., Ltd manufacture: ス Le リア 4110, solid component concentration: 20.5%, mean diameter is 60nm, disperse medium: different Propanol), it is configured to the coating fluid (RHI-6P) for forming thermal isolation film.

There is the manufacture of the stretched film base material (RHI-6F) of thermal isolation film

The polyester resin film (1) prepared according to the same manner as in Example 1 is carried out longitudinal axis stretching (140 DEG C, 2.5 times of stretchings) after, utilize nebulization to be coated with 45 μm for forming the coating fluid of thermal isolation film (RHI-6P), after carrying out 120 seconds be dried at 140 DEG C, carry out transverse axis stretching (140 DEG C, 1.5 Stretching again), prepare the stretched film base material (RHI-6F) with thermal isolation film.Now, the thickness of film base material is 300 μm, the thickness of thermal isolation film is 30 μm.

To obtained have total light transmittance of stretched film base material (RHI-6F) of thermal isolation film, haze value, Adaptation, pencil hardness, speckle, film uneven (island structure), have flawless, the flatness on film surface, Marresistance and thermal conductivity are measured, and result is shown in table.

[embodiment 13]

The preparation of hollow silica microgranule (AR-13VS) dispersion liquid

To 100g silica alumina sol (RiHui catalyst synthesis Co., Ltd manufacture: USBB-120, Mean diameter is 25nm, SiO₂·Al₂O₃Concentration is 20 weight %, Al in solid constituent₂O₃Content It being 27 weight %) the middle 3900g pure water post-heating that adds is to 98 DEG C, while keeping this temperature, with 6 Hour add 1750g with SiO₂Meter the sodium silicate aqueous solution that concentration is 1.5 weight % and 1750g with Al₂O₃The sodium aluminate aqueous solution that concentration is 0.5 weight % of meter, obtains SiO₂·Al₂O₃Primary particle disperses Liquid.Now the pH of reactant liquor is 11.8, and solid component concentration is 0.7%.It addition, mean diameter is 40nm. Then, 1530g was added with SiO with 6 hours₂Meter the sodium silicate aqueous solution that concentration is 1.5 weight % and 500g is with Al₂O₃The sodium aluminate aqueous solution that concentration is 0.5 weight % of meter, obtains 9500g solid constituent dense Degree is that the silica alumina of 0.8 weight % is coated to composite oxide particle dispersion liquid.It addition, it is average Particle diameter is 60nm.

Then, to 500g utilize ultrafilter membrane clean the titanium dioxide silica that solid component concentration is 13 weight % Change aluminum and be coated in the dispersion liquid of composite oxide particle (1) addition 1125g pure water, then it is (dense to drip concentrated hydrochloric acid Degree is 35.5 weight %) to make pH be 1.0, carries out dealumination treatment.Then, adding 10L pH is 3 Aqueous hydrochloric acid solution and 5L pure water, to utilize ultrafilter membrane lysed aluminium salt is carried out separate clean, Obtain the aqueous dispersions of the silicon dioxide granule (1) that solid component concentration is 20 weight %.

Then, the aqueous dispersions of 150g silicon dioxide microparticle (1), 500g pure water, 1750g will be comprised After the mixed liquor of ethanol and ammonia that 626g concentration is 28 weight % is heated to 35 DEG C, add 80g silicic acid Ethyl ester (SiO₂Concentration is 28 weight %) to form silica-coated layer, add 5L pure water Clean with ultrafilter membrane, obtain being formed with the two of the silica-coated layer that solid component concentration is 20 weight % The aqueous dispersions of silica type hollow minute particle.

Then, in the hollow silica particle dispersion liquid be formed with silica-coated layer add ammonia and By the pH regulator of dispersion liquid to 10.5, then, at 150 DEG C after maturation 1 hour, it is cooled to room temperature, (Mitsubishi chemical Co., Ltd's (Mitsubishi Chemical (strain)) manufactures: DIAION to use 400g cation exchange resin SK1B) carry out the ion exchange of 3 hours, then, use 200g anion exchange resin (Mitsubishi Chemical Co., Ltd. manufactures: DIAION SA20A) carries out the ion exchange of 3 hours, then uses 200g cation (Mitsubishi chemical Co., Ltd manufactures exchanger resin: DIAION SK1B) carry out at 80 DEG C 3 hours Ion exchange afterwash, obtains hollow silica microgranule (13T) that solid component concentration is 20 weight % Aqueous dispersions.

Then, again at 150 DEG C, hollow silica microgranule (13T) dispersion liquid is carried out 11 hours After hydrothermal treatment consists, it is cooled to room temperature, uses 400g cation exchange resin (Mitsubishi chemical Co., Ltd's system Make: DIAION SK1B) carry out 3 hours ion exchange, then, use 200g anion exchange tree (Mitsubishi chemical Co., Ltd manufactures fat: DIAION SA20A) carries out the ion exchange of 3 hours, then uses (Mitsubishi chemical Co., Ltd manufactures 200g cation exchange resin: DIAION SK1B) enter at 80 DEG C The row ion of 3 hours exchange afterwash, obtains the hollow silica that solid component concentration is 20 weight % The aqueous dispersions of microgranule (AR-13V).

Using ultrafilter membrane that replacing dispersion medium is become ethanol, being configured to solid component concentration is 20 weight % The alcohol dispersion liquid of hollow silica microgranule (AR-13V).

Alcohol to hollow silica microgranule (AR-13V) that 100g solid component concentration is 20 weight % Dispersion liquid adds 2g methyl-monosilane coupling agent (MTMS, KCC of SHIN-ETSU HANTOTAI system Make: KBM-13), at 50 DEG C, carry out heat treated, being configured to solid component concentration is 20 weight % The alcohol dispersion liquid of surface treated silica class hollow minute particle (AR-13VS).Rotary evaporator is used to divide Dispersion media is replaced into water, is configured to the surface treated silica hollow that solid component concentration is 20 weight % The aqueous dispersions of microgranule (AR-13VS).The most alkali-metal concentration is 5ppm.

For forming the preparation of the coating fluid (AR-13P) of antireflection film

In the surface treated silica hollow minute particle that 10.0g solid component concentration is 20 weight % (AR-13VS) aqueous dispersions is mixed into (the first industrial pharmaceutical strain formula meeting of 3.8g ester-polyurethane resin emulsion Society: SUPERFLEX 210, resin concentration is 35 weight %, particle diameter: 50nm, disperse medium: water), 18g pure water, 1.53g isopropanol, be configured to solid component concentration be 10.0 weight % for forming counnter attack Penetrate the coating fluid (AR-13P) of film.

There is the manufacture of the stretched film base material (AR-1) of antireflection film

The polyester resin film (1) prepared according to the same manner as in Example 1 is carried out longitudinal axis stretching (140 DEG C, 2.5 times of stretchings) after, utilize stick coating method (rod #4) coating for forming the coating fluid of antireflection film (AR-13P), after carrying out 120 seconds be dried at 140 DEG C, carry out transverse axis stretching (140 DEG C, 4.5 Stretching again), prepare the stretched film base material (AR-13F) with antireflection film.Now, the thickness of film base material Being 100 μm, the thickness of antireflection film is 100 μm.

Obtained had total light transmittance of stretched film base material (AR-13F) of antireflection film, mist Angle value, reflectance, the refractive index of film, adaptation, pencil hardness, speckle, film uneven (island structure), Having flawless, the flatness on film surface and marresistance to be measured, result is shown in table.

[comparative example 7]

For forming the preparation of the coating fluid (RAR-7P) of antireflection film

Then, add 10.0g according to the mode identical with embodiment 13 be configured to surface treated The aqueous dispersions of hollow silica microgranule (AR-13VS), is configured to the coating for forming antireflection film Liquid (RAR-7P).

There is the manufacture of the stretched film base material (RAR-7F) of antireflection film

At 140 DEG C of lower base material polyester resin films to preparing according to the same manner as in Example 1 of heating (1) so that reaching on y direction after the condition of 2.5 times stretches, to utilize stick coating method (rod #18) to be coated with Cloth is for forming the coating fluid (RAR-1P) of antireflection film, then, carries out 120 seconds dry at 140 DEG C After dry, heat lower so that reaching the condition of 4.5 times in X direction and stretching at 140 DEG C, prepare and have The stretched film base material (RAR-1F) of antireflection film.Now, the thickness of base material is 100 μm, antireflection film Thickness be 100nm.

Obtained had total light transmittance of stretched film base material (RAR-1F) of antireflection film, mist Angle value, reflectance, the refractive index of film, adaptation, pencil hardness, speckle, film uneven (island structure), Having flawless, the flatness on film surface and marresistance to be measured, result is shown in table.

[embodiment 14] (use of the polymeric dispersant of hollow silica)

The hollow silica that solid component concentration be 20 weight % identical with embodiment 13 to 100g is micro- Grain (AR-13V) alcohol dispersion liquid in add 2g polyacrylic acid dispersant (Toagosei Co., Ltd manufacture: Aron SD-10), at 50 DEG C, carry out heat treated, being configured to solid component concentration is 20 weight % The alcohol dispersion liquid of hollow silica microgranule (AR-2).Using rotary evaporator is water by replacing dispersion medium, It is configured to surface treated silica hollow minute particle (AR-14VS) that solid component concentration is 20 weight % Aqueous dispersions.Now, pH is 9.0.The most alkali-metal concentration is 5ppm.

For forming the preparation of the coating fluid (AR-14P) of antireflection film

In the surface treated silica hollow minute particle that 10.0g solid component concentration is 20 weight % (AR-14VS) aqueous dispersions is mixed into (the first industrial pharmaceutical strain formula meeting of 3.8g ester-polyurethane resin emulsion Society: SUPERFLEX 210, resin concentration is 35 weight %, particle diameter: 50nm, disperse medium: water), 18g pure water, 1.53g isopropanol, be configured to solid component concentration be 10.0 weight % for forming counnter attack Penetrate the coating fluid (AR-14P) of film.

There is the manufacture of the stretched film base material (AR-14F) of antireflection film

The polyester resin film (1) prepared according to the same manner as in Example 1 is carried out longitudinal axis stretching (140 DEG C, 2.5 times of stretchings) after, utilize stick coating method (rod #4) coating for forming the coating fluid of antireflection film (AR-14P), after carrying out 120 seconds be dried at 140 DEG C, carry out transverse axis stretching (140 DEG C, 4.5 Stretching again), prepare the stretched film base material (AR-14F) with antireflection film.Now, the thickness of film base material Being 100 μm, the thickness of antireflection film is 100nm.

Obtained had total light transmittance of stretched film base material (AR-14F) of antireflection film, mist Angle value, reflectance, the refractive index of film, adaptation, pencil hardness, speckle, film uneven (island structure), Having flawless, the flatness on film surface and marresistance to be measured, result is shown in table.

[comparative example 8] polymeric dispersant is too much

For forming the preparation of the coating fluid (RAR-8P) of antireflection film

Except adding in addition to 80g polyacrylic acid dispersant in embodiment 14, according to embodiment 14 phase Same mode is configured to the aqueous dispersions of surface treated silica hollow minute particle (RAR-8VS), adds The aqueous dispersions of this hollow silica microgranule (RAR-8VS) of 10.0g, is configured to for forming antireflection The coating fluid (RAR-8P) of film.

There is the manufacture of the stretched film base material (RAR-8F) of antireflection film

At 140 DEG C of lower base material polyester resin films to preparing according to the same manner as in Example 1 of heating (1) so that reaching on y direction after the condition of 2.5 times stretches, to utilize stick coating method (rod #18) to be coated with Cloth is for forming the coating fluid (RAR-8P) of antireflection film, then, carries out 120 seconds dry at 140 DEG C After dry, heat lower so that reaching the condition of 4.5 times in X direction and stretching at 140 DEG C, prepare and have The stretched film base material (RAR-8F) of antireflection film.Now, the thickness of base material is 100 μm, antireflection film Thickness be 100nm.

Obtained had total light transmittance of stretched film base material (RAR-8F) of antireflection film, mist Angle value, reflectance, the refractive index of film, adaptation, pencil hardness, speckle, film uneven (island structure), Having flawless, the flatness on film surface and marresistance to be measured, result is shown in table.

[comparative example 9] polymeric dispersant is very few

For forming the preparation of the coating fluid (RAR-9P) of antireflection film

Except adding in addition to 0.1g polyacrylic acid dispersant in embodiment 14, according to embodiment 14 phase Same mode is configured to the aqueous dispersions of surface treated silica hollow minute particle (RAR-9VS), adds The aqueous dispersions of this hollow silica microgranule (RAR-9VS) of 10.0g, is configured to for forming antireflection The coating fluid (RAR-9P) of film.

There is the manufacture of the stretched film base material (RAR-9F) of antireflection film

At 140 DEG C of lower base material polyester resin films to preparing according to the same manner as in Example 1 of heating (1) so that reaching on y direction after the condition of 2.5 times stretches, to utilize stick coating method (rod #18) to be coated with Cloth is for forming the coating fluid (RAR-9P) of antireflection film, then, carries out 120 seconds dry at 140 DEG C After dry, heat lower so that reaching the condition of 4.5 times in X direction and stretching at 140 DEG C, prepare and have The stretched film base material (RAR-9F) of antireflection film.Now, the thickness of base material is 100 μm, antireflection film Thickness be 100nm.

Obtained had total light transmittance of stretched film base material (RAR-9F) of antireflection film, mist Angle value, reflectance, the refractive index of film, adaptation, pencil hardness, speckle, film uneven (island structure), Having flawless, the flatness on film surface and marresistance to be measured, result is shown in table.

[embodiment 15]

The preparation of titanium dioxide fine particles (T-15VS) dispersion liquid

To 100.0g titanium dioxide organosol, (RiHui catalyst synthesis Co., Ltd manufactures: オプトレイ Network 1130Z (S-25 A8), solid component concentration: 30%, mean diameter is 20nm, disperse medium: Methanol) middle interpolation 3g methyl-monosilane coupling agent (MTMS) (KCC of SHIN-ETSU HANTOTAI Manufacturing: KBM-13), carry out heat treated at 50 DEG C, replacing dispersion medium is become by recycling ultrafilter membrane Ethanol, is configured to the surface that solid component concentration is 20 weight % and processes the alcohol dispersion liquid of titanium dioxide fine particles. Using after replacing dispersion medium is water by rotary evaporator, spent ion exchange resin carry out dealkalize metal from Son processes until pH is 3.0, is subsequently adding pure water and is configured to the table that solid component concentration is 20 weight % Face processes the aqueous dispersions of titanium dioxide fine particles (T-15VS).The most alkali-metal concentration is 50ppm.

For forming the preparation of the coating fluid (T-15P) of easy adhesive linkage

1.4g silicon dioxide organosol (RiHui catalyst synthesis Co., Ltd manufacture: ELCOM V-8901, Mean diameter is 120nm, SiO₂Concentration is 20 weight %, disperse medium: methanol) in be mixed into 33.2g Surface processes titanium dioxide fine particles (T-15VS), (the first industry strain formula meeting of 88.5g ester-polyurethane resin emulsion Society manufactures: SUPERFLEX 210, and resin concentration is 35 weight %, emulsion diameter: 50nm, and dispersion is situated between Matter: water), 10.1g isopropanol, being configured to solid component concentration is the most bonding for being formed of 10 weight % The coating fluid (T-15P) of layer.

There is the preparation of the stretched film base material (T-15F) of easy adhesive linkage

The base material polyester resin film (1) prepared according to the same manner as in Example 1 is carried out the longitudinal axis draw After stretching (140 DEG C, 2.5 times of stretchings), utilize stick coating method (rod #6) coating for forming easy adhesive linkage Coating fluid (T-15P), after carrying out 120 seconds be dried at 140 DEG C, carry out transverse axis stretching (140 DEG C, 4.5 times of stretchings), prepare the stretched film base material (T-15F) with easy adhesive linkage.Now, the thickness of film base material Degree is 100 μm, and the thickness of easy adhesive linkage is 0.6 μm.

Obtained had total light transmittance of stretched film base material (T-15F) of easy adhesive linkage, mist degree Value, adaptation, pencil hardness, speckle, film uneven (island structure), have flawless, film surface flat Smooth property, marresistance, anticaking capacity and cementability are measured, and also observe interference fringe, knot Fruit is shown in table.

[comparative example 10]

For forming the preparation of the coating fluid (RT-10P) of easy adhesive linkage

Then, (RiHui catalyst synthesis Co., Ltd manufactures: ELCOM to add 0.6g silicon dioxide organosol V-8901, mean diameter is 120nm, SiO₂Concentration is 20 weight %, disperse medium: methanol), 14.3 G surface processes titanium dioxide fine particles (T-15VS), is configured to the use that solid component concentration is 7.4 weight % In the coating fluid (RT-10P) forming easy adhesive linkage.

There is the manufacture of the stretched film base material (RT-10F) of easy adhesive linkage

The base material polyester resin film (1) prepared according to the same manner as in Example 1 is carried out the longitudinal axis draw After stretching (140 DEG C, 2.5 times of stretchings), stick coating method (rod #40) coating is utilized to be used for forming easy adhesive linkage Coating fluid (RT-10P), after carrying out 120 seconds be dried at 140 DEG C, carry out transverse axis stretching (140 DEG C, 4.5 times of stretchings), prepare the stretched film base material (RT-10F) with easy adhesive linkage.Now, film base The thickness of material is 100 μm, and the thickness of easy adhesive linkage is 0.6 μm.

Obtained had total light transmittance of stretched film base material (RT-10F) of easy adhesive linkage, mist Angle value, adaptation, pencil hardness, speckle, film uneven (island structure), there are flawless, film surface Flatness, marresistance, anticaking capacity and cementability are measured, and also observe interference fringe, Result is shown in table.

[comparative example 11]

The preparation of titanium dioxide fine particles (RT-11VS) dispersion liquid

In addition in embodiment 15 without ion exchange resin, according to the side identical with embodiment 15 Method is configured to surface and processes the aqueous dispersions of titanium dioxide fine particles (RT-11VS).The most alkali-metal concentration For 1500ppm.

For forming the preparation of the coating fluid (RT-11P) of easy adhesive linkage

Add 10.0g surface process titanium dioxide fine particles (RT-11VS) aqueous dispersions, be configured to for Form the coating fluid (RT-11P) of antireflection film.

There is the manufacture of the stretched film base material (RT-11F) of easy adhesive linkage

At 140 DEG C of lower base material polyester resin films to preparing according to the same manner as in Example 1 of heating (1) so that reaching on y direction after the condition of 2.5 times stretches, to utilize stick coating method (rod #18) to be coated with Cloth is for forming the coating fluid (RT-11P) of antireflection film, then, carries out 120 seconds dry at 140 DEG C After dry, heat lower so that reaching the condition of 4.5 times in X direction and stretching at 140 DEG C, prepare and have The stretched film base material (RA-11F) of antireflection film.Now, the thickness of base material is 100 μm, antireflection film Thickness be 100nm.

Obtained had total light transmittance of stretched film base material (RT-11F) of antireflection film, mist Angle value, reflectance, the refractive index of film, adaptation, pencil hardness, speckle, film uneven (island structure), Having flawless, the flatness on film surface and marresistance to be measured, result is shown in table.

In above-described embodiment or comparative example, methyl three can be used with the organo-silicon compound that formula (1) represents Methoxy silane, other also can enumerate tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four Butoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, MTES, different Butyl trimethoxy silane, butyl trimethoxy silane, butyl triethoxysilane, isobutyl group triethoxy Silane, hexyl triethoxysilane, octyltri-ethoxysilane, decyl triethoxysilane, hexyl front three TMOS, octyl group trimethoxy silane, decyl trimethoxy silane, vinyltrimethoxy silane, second Thiazolinyl triethoxysilane, vinyl three (β methoxy ethoxy) silane, 3,3,3-trifluoro propyl trimethoxy Silane, methyl-3,3,3-trifluoro propyl dimethoxysilane, β-(3,4-expoxycyclohexyl) ethyl trimethoxy Silane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, two Diethylamino phenyl TMOS, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxypropyl Dimethoxysilane, γ-glycidoxypropyl group triethoxysilane, γ-glycidoxypropyl diethyl TMOS, γ-(beta epoxide propoxyl group ethyoxyl) propyl trimethoxy silicane, γ-(methyl) acryloxy first Base trimethoxy silane, γ-(methyl) acryloyloxymethyl triethoxysilane, γ-(methyl) acryloxy Ethyl trimethoxy silane, γ-(methyl) acryloyl-oxyethyl triethoxysilane, γ-(methyl) acryloyl-oxy Base propyl trimethoxy silicane, γ-(methyl) acryloxypropyl triethoxysilane, γ-urea groups isopropyl third Ethyl triethoxy silicane alkane, perfluorooctylethyl group trimethoxy silane, perfluorooctylethyl group triethoxysilane, Perfluorooctylethyl group three isopropoxy silane, trifluoro propyl trimethoxy silane, N-β (amino-ethyl) gamma-amino Hydroxypropyl methyl dimethoxysilane, N-β (amino-ethyl) gamma-amino propyl trimethoxy silicane, N-phenyl-γ- TSL 8330, γ mercaptopropyitrimethoxy silane, trimethyl silicane alkanol, methyl trichlorine Silane, γ-isocyanates propyl-triethoxysilicane, γ-ureidopropyltriethoxysilane etc..

[table 1-1]

[table 1-2]

[table 1-3]

Claims

1., for forming a coating fluid for transparent coating, this coating fluid is inorganic oxide particle and resin Emulsion dispersion in containing the coating fluid in the disperse medium of at least one in water and organic solvent,

The all solids constituent concentration of described coating fluid is 0.03～70 weight %, described inorganic oxide particle Concentration (C_P) with solid component meter in the range of 0.0009～56 weight %, described resin emulsion dense Degree (C_R) with solid component meter in the range of 0.006～68 weight %,

Alkali-metal solid component concentration total amount contained in described inorganic oxide particle is with oxide (Me₂O, Me=Li, Na, K) count at below 1000ppm.

2. the coating fluid for forming transparent coating as claimed in claim 1, it is characterised in that described Inorganic oxide particle is carried out through using at least one in organo-silicon compound and polymeric dispersant Surface processes,

Described organo-silicon compound relative to described inorganic oxide particle using solid component meter, as R_n-SiX_(4-n)/2Exist in the range of 1～100 weight %,

Described polymeric dispersant relative to described inorganic oxide particle with solid component meter at 1～300 weights Exist in the range of amount %.

3. the coating fluid for forming transparent coating as claimed in claim 1 or 2, it is characterised in that Described inorganic oxide particle is monodispersed inorganic oxide particle (A) and primary particle 3～30 Connect at least one in catenulate chain inorganic oxide particle (B),

Mean diameter (the D of described inorganic oxide particle (A)_PA) at 3≤D_PAThe scope of≤100nm In,

Average primary particle diameter (the D of described inorganic oxide particle (B)_PB) at 3≤D_PB≤ 50nm's In the range of.

4. the coating fluid for forming transparent coating as claimed in claim 3, it is characterised in that also contain There is mean diameter (D_PC) it is 100 ＜ D_PCThe inorganic oxide particle (C) of≤500nm, described inorganic Concentration (the C of oxide fine particle (C)_PC) with solid component meter in the range of 0.000003～5 weight %.

5. the coating fluid for forming transparent coating as according to any one of Claims 1 to 4, its feature Being, described inorganic oxide particle is selected from TiO₂、ZrO₂、SiO₂、Sb₂O₅、ZnO₂、SnO₂、In₂O₃、 Antimony doped tin oxide (ATO), tin-doped indium oxide (ITO), mix F stannum oxide (FTO), p-doped oxidation The composite oxides of at least one or they in stannum (PTO), Al-Doped ZnO (AZO) or mixing Thing.

6. the coating fluid for forming transparent coating as according to any one of Claims 1 to 5, its feature Being, the resin of described resin emulsion is selected from epoxy resin, polyester resin, polycarbonate resin, polyamide Resin, polyphenylene oxide resin, vinyl chloride resin, fluororesin, vinyl acetate resin, organic siliconresin, poly- Urethane resin, melmac, butyral resin, phenolic resin, unsaturated polyester resin, acrylic acid At least one in resin or the two or more copolymer of these resins or modified body.

7. the coating fluid for forming transparent coating as according to any one of claim 1～6, its feature Being, the average diameter of described resin emulsion is in the range of 10～500nm.

8. the coating fluid for forming transparent coating as according to any one of claim 1～7, its feature It is, the concentration (C of described inorganic oxide particle_P) and the concentration (C of resin emulsion_R) ratio (C_P/C_R) In the range of 0.03～4.

9. having a manufacture method for the base material of transparent coating, this manufacture method carries out following operation successively (a)～(d):

A () is coated with the painting for forming transparent coating according to any one of claim 1～8 on base material The operation of cloth liquid；

B () carries out the operation that twin shaft (longitudinal axis and transverse axis) stretches to the base material with film；

C () removes the operation of disperse medium contained in (being dried) described film；

D () makes the operation of described curing of coating.

10. having a manufacture method for the base material of transparent coating, this manufacture method carries out following operation successively (a ')～(d):

(a ') on the base material that the longitudinal axis stretches, it is being coated with being used for according to any one of claim 1～8 Form the operation of the coating fluid of transparent coating；

(b ') carries out the operation of transverse axis stretching to the base material with film；

D () makes the operation of described curing of coating.

The manufacture method of 11. 1 kinds of base materials with transparent coating, this manufacture method carries out following operation successively (a ")～(d):

(a ") while base material is carried out longitudinal axis stretching, base material is coated with in claim 1～8 The operation of the coating fluid for forming transparent coating described in any one；

(b ") carries out the operation of transverse axis stretching to the base material with film；

D () makes the operation of described curing of coating.

The manufacture method of 12. 1 kinds of base materials with transparent coating, this manufacture method carries out following operation successively (a " ')～(d):

(a " ') while base material to be carried out twin shaft (longitudinal axis and transverse axis) stretching, base material is coated with The operation of the coating fluid for forming transparent coating according to any one of cloth claim 1～8；

D () makes the operation of described curing of coating.