CN106009813A - Transparent conductive film - Google Patents

Abstract

The invention provides a hard coating with excellent etching resistance, a laminate for forming a transparent conductive film and capable of stably enabling a pattern shape of a transparent conductive layer to be invisible and providing the transparent conductive film with excellent adhesion resistance, and a transparent conductive film using the laminate. The laminate is made from the hard coating, a substrate film and an optical adjustment layer through laminating in sequence. The hard coating is formed from a composition containing components of (A) 100 parts by weight of an active energy ray cured resin and (B) 15-100 parts by weight of silicon dioxide micro-particles through photo-curing.

Description

Transparent and electrically conductive film

Technical field

The present invention relates to transparency conducting layer formation lamilated body and transparent and electrically conductive film.

The elching resistant particularly relating to hard coat is excellent, can be stably by invisible for the pattern form of transparency conducting layer Change and transparency conducting layer formation lamilated body that the resistance to blocking of gained transparent and electrically conductive film is excellent and use this lamilated body Transparent and electrically conductive film.

Background technology

In the past, can input the contact panel of information by directly touching image displaying part is by the input equipment of light transmission It is configured on display.

As the representative form of such contact panel, there is following contact panel: by 2 transparent electrode substrates with Make the mode that respective transparent electrode layer is relative, while space is set, carries out the resistance membrane type contact panel configured； Or utilize the static capacitive contact panel of the change of the direct capacitance produced between ELD and finger.

Wherein, in static capacitive contact panel, as the sensor of the position of touch for detecting finger, substantially deposit At: the glass sensor that is laminated on glass baseplate by transparency conducting layer and transparency conducting layer is laminated at overlay Film sensors on base material.

Particularly in film sensors, mostly lead by 2 being possessed the transparent of transparency conducting layer being patterned as wire Electrically film configures so that respective pattern intersects, thus forms cancellate pattern.

But, in the case of so by pattern for transparent conductive layer, it was found that problems with: drafting department and non-drafting department Junction section become to be easily discernible, make the variation attractive in appearance of static capacitive contact panel.

Therefore, the technology (referring for example to patent documentation 1) for solving such problem is disclosed.

That is, Patent Document 1 discloses hard and be coated with cloth base material, it is to contain transparent base, easy adhesive linkage and folding successively The hard penetrating rate adjustment layer is coated with cloth base material, it is characterised in that and refractive index adjustment layer refractive index under 550nm wavelength is 1.60 ~ 1.90, the thickness of refractive index adjustment layer is 0.3 ~ 5 μm, and easy adhesive linkage refractive index under 550nm wavelength is 1.56 ~ 1.70.

Have it addition, describe the further lamination in opposition side in the side being formed with refractive index adjustment layer of transparent base The functional layer (can pay) containing filler of resistance to blocking.

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2013-202844 publication (claims).

Summary of the invention

Invent problem to be solved

But, the hard disclosed in patent documentation 1 is coated with cloth base material and is found that problems with: transparency conducting layer is being passed through etching When patterning, the functional layer containing filler is easily etched liquid and corrodes, and is thus difficult to stably by transparency conducting layer Pattern form invisibleization.

More specifically, in recent years, increase along with the production of smart phone etc., it is desirable to etch processes rapid, especially It is in the alkali of the photoresist for removing residual as the final operation of etch processes processes, such as, has use to be heated to be The situation of the sodium hydrate aqueous solution of 5 weight % of 40 DEG C.

In the case of the alkali carrying out such harshness processes, the hard disclosed in patent documentation 1 is coated with in cloth base material and sends out Having showed problems with: the filler in functional layer easily dissolves or comes off, it is as a result, it is difficult to stably by the figure of transparency conducting layer Case shape invisibleization.

Therefore, find when the present inventor etc. makes great efforts with keen determination in view of situation as above, formed as transparency conducting layer shape During the hard coat at the back side of one-tenth lamilated body, by using relative to active energy ray-curable resin with the model of regulation Enclose the hard coat formation compositions of mixing silicon dioxide microparticle, it is possible to resolve above-mentioned problem, thus complete this Bright.

That is, it is an object of the invention to: the elching resistant providing hard coat is excellent, can be stably by transparency conducting layer Transparency conducting layer formation lamilated body that the resistance to blocking of pattern form invisibleization and gained transparent and electrically conductive film is excellent and Use the transparent and electrically conductive film of this lamilated body.

For solving the means of problem

According to the present invention, it is provided that transparency conducting layer formation lamilated body, it is hard coat, base material film and optical adjustment layer to be depended on The secondary transparency conducting layer formation lamilated body carrying out lamination, it is characterised in that hard coat is by containing following (A) ~ (B) The hard coat formation compositions of composition carries out photocuring, thus can solve above-mentioned problem:

(A) active energy ray-curable resin 100 weight portion,

(B) silicon dioxide microparticle 15 ~ 100 weight portion.

If that is, the transparency conducting layer formation lamilated body of the present invention, due to formed as its back side hard be coated with The hard coat formation compositions used during layer contains with less scope relative to active energy ray-curable resin Silicon dioxide microparticle, even so carrying out the situation of the etch processes processed containing harsh alkali, it is possible to suppression is hard effectively Silicon dioxide microparticle in matter coating dissolves or comes off (following, to have the situation that such effect is referred to as " elching resistant ").

Its result, can suppress the film thickness of hard coat and refractive index to change, and then can suppress the light of hard coat Characteristic changes, therefore can be stably by pattern form invisibleization of transparency conducting layer.

Further, since can effectively suppress the silicon dioxide microparticle in hard coat dissolve or come off, so can be effectively It is maintained at the small concave-convex surface that the surface of hard coat is formed because of silicon dioxide microparticle.

Its result, when batching gained transparent and electrically conductive film into web-like, can suppress the film that directly contacts just effectively Reverse side sticks together (following, to have the situation that such effect is referred to as " resistance to blocking ").

It addition, when constituting the transparency conducting layer formation lamilated body of the present invention, preferably will be as the titanium dioxide of (B) composition The volume average particle size (D50) of silicon particle is set to the value in the range of 10 ~ 100nm.

By so constituting, the transparency of hard coat can not be reduced, and obtain the resistance to blocking of regulation.

It addition, when constituting the transparency conducting layer formation lamilated body of the present invention, preferably as the silicon dioxide of (B) composition Microgranule is solid silicon dioxide microparticle.

By so constituting, compared with hollow silica particles, can make particle diameter little, although being therefore mixed into terrible To the amount required for resistance to blocking, still can effectively keep the transparency of hard coat.

It addition, when constituting the transparency conducting layer formation lamilated body of the present invention, preferably as the silicon dioxide of (B) composition Microgranule is reactive silicon dioxide microgranule.

By so constituting, silicon dioxide microparticle can be firmly fixed on hard coat, therefore can be more effective Ground improves elching resistant.

It addition, when constituting the transparency conducting layer formation lamilated body of the present invention, preferably hard coat formation compositions Containing the fluorine class levelling agent as (C) composition, and, solid relative to the active energy beam as (A) composition of 100 weight portions The property changed resin, is set to the value in the range of 0.01 ~ 0.2 weight portion by the combined amount of this fluorine class levelling agent.

By so constituting, can more effectively protect the silicon dioxide microparticle in hard coat, therefore can be further It is effectively improved elching resistant.

It addition, when constituting the transparency conducting layer formation lamilated body of the present invention, preferably the film thickness of hard coat is set It it is the value in the range of 0.5 ~ 5 μm.

By so constituting, available enough elching resistants, and, when implementing annealing, can be effectively The generation of the curling of suppression transparency conducting layer formation lamilated body.

It should be noted that, " annealing " refers to improve the electrical conductivity of the transparency conducting layer in transparent and electrically conductive film, And the transparency conducting layer of the state being laminated on transparency conducting layer formation lamilated body is carried out crystallization by heat treated Process.

It addition, when constituting the transparency conducting layer formation lamilated body of the present invention, hard coat is being coated with as the 1st hard In the case of Ceng, preferably there is between base material film and optical adjustment layer the 2nd hard coat.

By so constituting, the oligomer composition because oozing out from base material film not only can be effectively suppressed to pollute optics Adjustment layer, and when implementing annealing, can effectively suppress the generation of the curling of transparency conducting layer formation lamilated body.

It addition, when constituting the transparency conducting layer formation lamilated body of the present invention, the preferably the 2nd hard coat is by with the 1st The hard coat formation compositions that hard coat is identical carries out photocuring, and, have identical with the 1st hard coat Film thickness.

By so constituting, the formation of the 1st and the 2nd hard coat becomes easy, and, implementing annealing Time, can more effectively suppress the generation of the curling of transparency conducting layer formation lamilated body.

It addition, the other mode of the present invention is transparent and electrically conductive film, it is by hard coat, base material film, pH effect Layer and transparency conducting layer carry out the transparent and electrically conductive film of lamination successively, it is characterised in that hard coat is by containing following (A) ~ (B) the hard coat formation compositions of composition carries out photocuring:

(A) active energy ray-curable resin 100 weight portion,

(B) silicon dioxide microparticle 15 ~ 100 weight portion.

If that is, the transparent and electrically conductive film of the present invention, owing to using the transparency conducting layer formation lamilated body of regulation, so The elching resistant of hard coat is excellent, can be stably by pattern form invisibleization of transparency conducting layer and available excellent Resistance to blocking.

It addition, when constituting the transparent and electrically conductive film of the present invention, preferably make pattern for transparent conductive layer by etching.

Even if being performed such the situation of composition, owing to the elching resistant of hard coat is excellent, thus also can stably by Pattern form invisibleization of transparency conducting layer.

Accompanying drawing explanation

[Fig. 1] Fig. 1 (a) ~ (b) illustrates that the composition of the transparency conducting layer formation lamilated body of the present invention provides Figure.

[Fig. 2] Fig. 2 illustrates that the combined amount of silicon dioxide microparticle and the elching resistant of hard coat and resistance to blocking Relation and the figure that provides.

[Fig. 3] Fig. 3 illustrates that the composition of the transparent and electrically conductive film of the present invention and the figure that provides.

Detailed description of the invention

[the 1st embodiment]

1st embodiment of the present invention is transparency conducting layer formation lamilated body 10, and as shown in Fig. 1 (a), it is by hard coat 3a, base material film 4 and optical adjustment layer 2 carry out the transparency conducting layer formation lamilated body 10 of lamination successively, it is characterised in that Hard coat 3a is that the hard coat formation compositions containing following (A) ~ (B) composition carries out photocuring:

(A) active energy ray-curable resin 100 weight portion,

(B) silicon dioxide microparticle 15 ~ 100 weight portion.

It should be noted that, in Fig. 1 (a), saturating in the way of the two sides at base material film 4 has hard coat 3 (3a, 3b) Bright conductive layer formation lamilated body 10 is that an example is indicated, but the hard coat between base material film 4 and optical adjustment layer 2 3b can omit.

It addition, for optical adjustment layer 2, also in the way of being made up of high refractive index layer 2b and low-index layer 2a these 2 layers It is that an example is indicated, but may also be by 1 layer of mode constituted or by the optical adjustment layer 2 of more than the 3 layers modes constituted.

It addition, in Fig. 1 (a), the particle in each layer represents silicon dioxide microparticle or metal oxide particle.

Hereinafter, the most referring to the drawings, the 1st embodiment of the present invention is specifically described.

1. base material film

(1) kind

As the kind of base material film, without particular restriction, the known base material film as optical substrate can be used.

For instance, it may be preferable to list: polyethylene terephthalate (PET), polybutylene terephthalate (PBT), poly-naphthalene The polyester films such as naphthalate (PEN), polyethylene film, polypropylene screen, cellophane, cellulose diacetate film, three acetic acid are fine Dimension element film, acetylbutyrylcellulose film, polychloroethylene film, polyvinylidene chlorida film, polyvinyl alcohol film, ethene-vinyl acetate copolymerization Thing film, polystyrene film, polycarbonate membrane, polymethylpentene film, polysulfone membrane, polyether-ether-ketone film, poly (ether sulfone) film, Polyetherimide Film, polyimide film, fluororesin film, polyamide membrane, acrylic resin film, norbornene resin film, cycloolefin resin film etc. Plastic foil.

It addition, among them, from the viewpoint of thermostability, more preferably polyester film, polycarbonate membrane, polyimides Film, norbornene resin film, cycloolefin resin film.

It addition, from the transparency and film-strength and flexibility and from the viewpoint of depositing, particularly preferably PET film.

(2) film thickness

Additionally, it is preferred that the film thickness of base material film is set to the value in the range of 20 ~ 200 μm.

Its reason is: if the film thickness of base material film is the value less than 20 μm, then reduce due to base material film strength, with or without Method suppresses the change during annealing of the existence part of the transparency conducting layer in optical adjustment layer and non-existence part effectively The situation of the generation of shape.On the other hand, its reason is: if the film thickness of base material film is the value more than 200 μm, then have base material film The optical characteristics such as transparency situation about being deteriorated.

Therefore, more preferably the film thickness of base material film is set to the value in the range of 30 ~ 180 μm, further preferably it is set to 50 ~ Value in the range of 150 μm.

It should be noted that, " annealing " refers to improve the electrical conductivity of the transparency conducting layer in transparent and electrically conductive film, And the transparency conducting layer of the state being laminated on transparency conducting layer formation lamilated body is carried out crystallization by heat treated Process.

2. hard coat

As shown in Fig. 1 (a), constitute the present invention transparency conducting layer formation with lamilated body 10 time, it is characterised in that at least with Lamination in base material film 4 has the face of the opposition side of the side of optical adjustment layer 2 to arrange hard coat 3a.

Its reason is: by arranging such hard coat, at the preparation section of transparency conducting layer formation lamilated body In, marresistance can be given to base material film, and prevent optical characteristics from reducing, in addition, base material film batched as web-like In the case of can suppress the phenomenon that base material film is adhering to each other produce (following, have the feelings that such effect is referred to as " resistance to blocking " Condition).

It addition, as shown in Fig. 1 (a), using hard coat 3a as in the case of the 1st hard coat, preferably at base material film 4 And there is between optical adjustment layer 2 the 2nd hard coat 3b.

Its reason is: by having such 2nd hard coat, not only can effectively suppress because oozing out from base material film Oligomer composition and pollute optical adjustment layer, and can effectively suppress the product of the curling of transparency conducting layer formation lamilated body Raw.

Additionally, it is preferred that the 2nd hard coat is that the hard coat formation compositions identical with the 1st hard coat is carried out light Solidification, and, there is the film thickness identical with the 1st hard coat.

Its reason is: by so constituting the 2nd hard coat, the formation of the 1st and the 2nd hard coat becomes easy, and And, can effectively suppress the generation of the curling of transparency conducting layer formation lamilated body in the case of implementing annealing.

Therefore, the following description is the 1st hard coat and the content of the 2nd this two square tube of hard coat.

(1) raw material

It addition, the hard coat of the present invention is characterised by: be that the hard containing following (A) ~ (B) composition as raw material is coated with Layer formation compositions carries out photocuring:

(A) active energy ray-curable resin 100 weight portion,

(B) silicon dioxide microparticle 15 ~ 100 weight portion.

Its reason is: relative to active-energy in the hard coat formation compositions used when forming hard coat Ray-curable resin contains silicon dioxide microparticle with less scope, even thus carrying out the erosion processed containing harsh alkali The situation that quarter processes, it is possible to the silicon dioxide microparticle in suppression hard coat dissolves or comes off effectively.

More specifically, as shown in Fig. 1 (a), the situation that the combined amount of the silicon dioxide microparticle in hard coat 3a is few Under, the existence ratio of the base portion being made up of resin becomes many, even the situation that the alkali therefore carrying out harshness processes, titanium dioxide Silicon particle is still protected effectively at base portion, can effectively suppress to dissolve or come off.

Its result, can suppress the film thickness of hard coat and refractive index to change, and then can suppress the light of hard coat Characteristic changes.

On the other hand, as shown in Fig. 1 (b), the situation that the combined amount of the silicon dioxide microparticle in hard coat 3a ' is many Under, the existence ratio of the base portion being made up of resin tails off, therefore in the case of the alkali carrying out harshness processes, and silicon dioxide Microgranule is not protected fully by base portion, becomes easily to dissolve or come off.

Therefore, as shown in Fig. 1 (a), if the few present invention of the combined amount of the silicon dioxide microparticle in hard coat 3a Transparency conducting layer is formed uses lamilated body 10, then can be stably by the pattern shape of the transparency conducting layer of formation in optical adjustment layer 2 Shape invisibleization.

Further, since can effectively suppress the silicon dioxide microparticle in hard coat dissolve or come off, so can be effectively It is maintained at the small concave-convex surface that the surface of hard coat is formed because of silicon dioxide microparticle.

Therefore, when gained transparent and electrically conductive film is batched as web-like, the film that can effectively suppress directly to contact positive and negative Face sticks together.

Hereinafter, every kind of composition is illustrated.

(1)-1 (A) composition: active energy ray-curable resin

(A) composition is active energy ray-curable resin.

Active energy ray-curable resin as such (A) composition refers to by electromagnetic wave or charge-particle beam Middle irradiation has the ray (i.e. ultraviolet or electron beam etc.) of the quanta of energy and carries out the polymerizable compound cross-linking, solidifying, example As listed: photopolymerizing prepolymers or photopolymerization monomer.

It addition, in above-mentioned photopolymerizing prepolymers, have radical polymerization mould assembly and cationic polymerization type, as radical polymerization The photopolymerizing prepolymers of mould assembly, can list: polyester acrylic esters, Epoxy Acrylates, urethane acrylates Esters, polyalcohol acrylate class etc..

It addition, as polyester acrylic esters prepolymer, include, for example out the compound obtained by the following method: use The polyester oligomer at double ends with hydroxyl that condensation by polybasic carboxylic acid and polyhydric alcohol is obtained by (methyl) acrylic acid Hydroxyl be esterified, or the hydroxyl of the end of oligomer oxyalkylene and polybasic carboxylic acid addition obtained with (methyl) acrylic acid Base is esterified.

It addition, as Epoxy Acrylates prepolymer, include, for example out the compound obtained by the following method: right In bisphenol-type epoxy resin or the oxirane ring of phenol aldehyde type epoxy resin of lower molecular weight, carry out ester with (methyl) acrylic acid Change.

It addition, as urethane acrylate class prepolymer, include, for example out the change obtained by the following method Compound: the poly-ammonia reaction by polyether polyol or PEPA and polyisocyanate obtained with (methyl) acrylic acid Carbamate oligomer is esterified.

Additionally, as polyalcohol acrylate class prepolymer, can list: by with (methyl) acrylic acid by polyether polyols The compound that the hydroxyl of alcohol carries out being esterified and obtains.

It should be noted that, these polymerizing prepolymer may be used alone or in combination of two or more kinds.

On the other hand, as the photopolymerizing prepolymers of cationic polymerization type, generally use epoxylite.

As such epoxy resin, include, for example out: polynary to bisphenol resin or phenolic resin etc. with chloropropylene oxide etc. Compound that phenols carries out epoxidation and obtains, with peroxide etc., straight-chain olefin(e) compound or cyclic alkene compound are entered The compound etc. that row aoxidizes and obtains.

It addition, as photopolymerization monomer, include, for example out: two (methyl) acrylic acid-BDO ester, two (first Base) acrylic acid-1,6-HD ester, two (methyl) acrylic acid DOPCP, two (methyl) polyalkylene glycol acrylate ester, new penta Glycol adipic acid two (methyl) acrylate, 3-hydroxypivalic acid neopentyl glycol two (methyl) acrylate, two (methyl) acrylic acid Dicyclopentenyl ester, caprolactone modification two (methyl) acrylic acid dicyclopentenyl ester, ethylene oxide denatured di(2-ethylhexyl)phosphate (methyl) third Olefin(e) acid ester, allylation two (methyl) cyclohexyl acrylate, isocyanuric acid two (methyl) acrylate, propanoic acid modified two seasons penta 4 Alcohol three (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, propylene oxide modification trimethylolpropane tris (methyl) Acrylate, three (acryloyl-oxyethyl) chlorinated isocyanurates, propanoic acid modification dipentaerythritol five (methyl) acrylate, two seasons The polyfunctional acrylic esters such as penta tetrol six (methyl) acrylate, caprolactone modification dipentaerythritol six (methyl) acrylate.

It should be noted that, these photopolymerization monomers may be used alone or in combination of two or more kinds.

(1)-2 (B) composition: silicon dioxide microparticle

(B) composition is silicon dioxide microparticle.

As the kind of such silicon dioxide microparticle, without particular restriction, but solid silicon dioxide microparticle is preferably used.

Its reason is: if solid silicon dioxide microparticle, then with the hollow dioxy that volume average particle size is more than 20nm SiClx microgranule is compared, can make particle diameter little, although being therefore mixed into the amount obtained required for resistance to blocking, still can effectively keep The transparency of hard coat.

It addition, compared with the hollow silica particles of high price, the most favourable.

It should be noted that, " solid silicon dioxide microparticle " refers to that the silicon dioxide in the inside of particle without cavity is micro- Grain.

Additionally, it is preferred that silicon dioxide microparticle is reactive silicon dioxide microgranule.

Its reason is: if reactive silicon dioxide microgranule, then silicon dioxide microparticle can be firmly fixed at hard In coating, therefore can more effectively improve elching resistant.

It should be noted that, " reactive silicon dioxide microgranule " refers to be bonded with the organic compound containing polymerism unsaturated group Silicon dioxide microparticle, can be by making the silanol of the organic compound containing polymerism unsaturated group and silica particle surface Base reacts and obtains, and the described organic compound containing polymerism unsaturated group has the sense can reacted with this silanol group Group.

It addition, as above-mentioned polymerism unsaturated group, include, for example out: free-radical polymerised acryloyl group or methyl Acryloyl group etc..

Additionally, it is preferred that the volume average particle size (D50) of silicon dioxide microparticle is set to the value in the range of 10 ~ 100nm.

Its reason is: by the volume average particle size of silicon dioxide microparticle (D50) is set to the value in such scope, The transparency of hard coat can not be reduced, and obtain the resistance to blocking of regulation.

That is, its reason is: if the volume average particle size of silicon dioxide microparticle (D50) is the value less than 10nm, then hard The concave-convex surface of coating surface exceedingly diminishes, thus has the situation being difficult to effectively present resistance to blocking.On the other hand, it is former Because being: if the volume average particle size of silicon dioxide microparticle (D50) is the value more than 100nm, the most easily produce scattering of light, from And have the situation that the transparency of hard coat is easily reduced.

Therefore, more preferably the volume average particle size (D50) of silicon dioxide microparticle is set to the value in the range of 12 ~ 60nm, Further preferably it is set to the value in the range of 14 ~ 30nm.

It should be noted that, the volume average particle size (D50) of silicon dioxide microparticle such as can be come by Zeta potential algoscopy Try to achieve, in addition, it is possible to use laser diffraction and scattering formula particle size distribution device is tried to achieve, and is also based on SEM image in addition Try to achieve.

Additionally, it is characterised in that relative to the active energy ray-curable resin as (A) composition of 100 weight portions, The combined amount of silicon dioxide microparticle is set to the value in the range of 15 ~ 100 weight portions.

Its reason is: if the combined amount of silicon dioxide microparticle is the value less than 15 weight portions, then the hardness of hard coat Become not enough, or be difficult to be formed on hard coat surface enough concave-convex surfaces, thus have and be difficult to obtain resistance to blocking or right Situation in the adhesiveness of adhesive layer etc..On the other hand, its reason is: if the combined amount of silicon dioxide microparticle is for exceeding The value of 100 weight portions, then, in the case of carrying out the etch processes processed containing harsh alkali, have the titanium dioxide in hard coat The situation that silicon particle easily dissolves or comes off.

Therefore, more preferably relative to the active energy ray-curable resin as (A) composition of 100 weight portions, by two The combined amount of silicon oxide particle is set to the value in the range of 20 ~ 70 weight portions, is further preferably set to the scope of 30 ~ 50 weight portions Interior value.

Then, use Fig. 2, the combined amount of silicon dioxide microparticle and the elching resistant of hard coat and resistance to blocking be describeds Relation.

That is, figure 2 illustrates transverse axis and use the combined amount (weight portion) of silicon dioxide microparticle, and the left longitudinal axis uses transparent leading Characteristic curve A and the right longitudinal axis of the reflectance variable quantity (%) before and after the alkali process of electric layer formation lamilated body use resistance to blocking The characteristic curve B of (relative value).

It should be noted that, the reflectance variable quantity and anti-stick before and after the alkali of transparency conducting layer formation lamilated body is processed Even the concrete assay method of property, records in an embodiment.

It addition, the film thickness of hard coat or refractive index or this two side change because alkali processes, thus hard coat Reflectance change, therefore transparency conducting layer formation lamilated body alkali process before and after reflectance variable quantity (%) be hard The index of the elching resistant of matter coating, reflectance variable quantity is the least, represents that elching resistant is the most excellent, if 0.5% value below, Then can determine whether the elching resistant in actual use with excellence.

It addition, the relative value of resistance to blocking is for anti-stick by be evaluated as described in embodiment according to following standard The value that even property obtains relative to value.

4: layer surface is the most nonadherent

1: layer surface is adhering to each other and does not moves

First, as understood according to characteristic curve A, reflectance variable quantity has along with the combined amount of silicon dioxide microparticle increases And the trend sharply increased.

More specifically, it will be appreciated that: if the scope that the combined amount of silicon dioxide microparticle is below 100 weight portions, then can be steady Surely making reflectance variable quantity is 0.5% value below, if but the combined amount of silicon dioxide microparticle is more than 100 weight portions, then reflects Rate variable quantity increases sharp, can be more than 0.5%.

Can speculate: the increase of this reflectance variable quantity drastically comes from the surface of hard coat or layer itself and processes because of alkali And damage.

It addition, as understood according to characteristic curve B, the value of resistance to blocking has the combined amount along with silicon dioxide microparticle The trend increased and sharply increase.

More specifically, it will be appreciated that: if the combined amount of silicon dioxide microparticle is the scope less than 15 weight portions, then tissue adhesion Property value low, if but more than 15 weight portions, then can obtain the resistance to blocking of in actual use required regulation, if 40 More than weight portion, then can stably obtain the resistance to blocking of excellence.

Therefore, it is appreciated that to make elching resistant and resistance to blocking and depositing according to characteristic curve A and B, should be by silicon dioxide The combined amount of microgranule is set to the value in the range of 15 ~ 100 weight portions.

(1)-3 (C) composition: fluorine class levelling agent

Preferably further contain fluorine class levelling agent as (C) composition.

Its reason is: by containing fluorine class levelling agent, can more effectively protect the silicon dioxide microparticle in hard coat, Therefore elching resistant can more effectively be improved.

More specifically, its reason is: the water proofing property being had due to fluorine class levelling agent, can effectively protect hard to be coated with The alkali component damage that silicon dioxide microparticle in Ceng uses in not processed by alkali.

It should be noted that, as the kind of fluorine class levelling agent, known material can be used, but due to the fluorine with straight chain Class levelling agent is compared, and volatility is low and excellent heat stability, it is advantageous to the upright and outspoken molecular structure containing side chain and double bond Fluorine class levelling agent, as such fluorine class levelling agent, include, for example out: Neos (strain) system, Ftergent 7602A etc..

Additionally, it is preferred that relative to the active energy ray-curable resin as (A) composition of 100 weight portions, by fluorine class The combined amount of levelling agent is set to the value in the range of 0.01 ~ 0.2 weight portion.

Its reason is: if the combined amount of fluorine class levelling agent is the value less than 0.01 weight portion, then be difficult to effectively protect Silicon dioxide microparticle in hard coat, and then have the situation being difficult to improve elching resistant.On the other hand, its reason is: if The combined amount of fluorine class levelling agent is the value more than 0.2 weight portion, then the surface free energy of hard coat can become too low value, has Be difficult to obtain required by hard coat for the regulation adhesiveness of adhesive layer etc. in the case of.

Therefore, more preferably relative to the active energy ray-curable resin as (A) composition of 100 weight portions, by fluorine The combined amount of class levelling agent is set to the value in the range of 0.03 ~ 0.18 weight portion, is further preferably set to 0.05 ~ 0.15 weight portion In the range of value.

(1)-4 (D) composition: Photoepolymerizationinitiater initiater

Further, since can be by active energy beam, particularly ultraviolet effectively by active energy ray-curable resin Solidification, so it is also preferred that as required and be used as the Photoepolymerizationinitiater initiater of (D) composition.

As such Photoepolymerizationinitiater initiater, for photopolymerizing prepolymers or the optical polymerism list of radical polymerization mould assembly Body, include, for example out: Benzoinum, Benzoinum methyl ether, Benzoinum ethylether, benzoin isobutyl propyl group ether, Benzoinum normal-butyl Ether, benzoin isobutyl butyl ether, 1-Phenylethanone., dimethylamino benzoylformaldoxime, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethyl Epoxide-2-phenyl acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid- [4-(methyl mercapto) phenyl]-2-morpholino-propane-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-2 (hydroxyl-2-propyl group) ketone, two Benzophenone, to phenyl benzophenone, 4,4 '-diethylamino benzophenone, dichloro benzophenone, 2-methylanthraquinone, 2-ethyl Anthraquinone, 2-tert-butyl group anthraquinone, 2-amino anthraquinones, 2-methyl thiaxanthone, 2-ethyl thiaxanthone, CTX, 2,4-dimethyl Thiaxanthone, 2,4-diethyl thioxanthone, benzyl dimethyl ketal, 1-Phenylethanone. dimethyl ketal, to dimethyl amine benzoate etc..

It addition, as the Photoepolymerizationinitiater initiater of the photopolymerizing prepolymers for cationic polymerization type, include, for example out: By aromatic sulfonium ion, aromatics oxo sulfonium cation, aromatics iodide ion etc. and tetrafluoroborate, hexafluoro-phosphate radical, hexafluoro-antimonic acid The compound etc. that the aniones such as root, hexafluoroarsenate root are constituted.

It should be noted that, they may be used alone or in combination of two or more kinds.

It addition, as the combined amount of Photoepolymerizationinitiater initiater, relative to the activity as above-mentioned (A) composition of 100 weight portions Energy ray-curable resin, is preferably set to the value in the range of 0.2 ~ 10 weight portion, is more preferably set to the scope of 1 ~ 5 weight portion Interior value.

(2) hard coat formation compositions

It addition, the preferred previously prepared hard coat formation compositions of hard coat, as described by being coated, being dried also Solidification is formed.

Said composition can be prepared by the following method: as required, respectively with the ratio of regulation in suitable solvent Add active energy ray-curable resin, Photoepolymerizationinitiater initiater, silicon dioxide microparticle and the various interpolations used as required Composition, carries out dissolving or disperseing.

It should be noted that, as various adding ingredients, include, for example out: antioxidant, UV absorbent, (closely) are red Ultraviolet absorbers, silane coupling agent, light stabilizer, levelling agent, antistatic additive, defoamer etc..

It addition, as the solvent used, include, for example out: the aliphatic hydrocarbon such as hexane, heptane, the virtue such as toluene, dimethylbenzene Race's hydrocarbon, the halogenated hydrocarbons such as dichloromethane, dichloroethanes, the alcohol such as methanol, ethanol, propanol, butanol, acetone, butanone, 2 pentanone, different The ketone such as phorone, Ketohexamethylene, the ester such as ethyl acetate, butyl acetate, the cellosolve type solvents etc. such as ethyl cellosolve.

As the concentration of hard coat formation compositions being prepared, viscosity, if for the concentration that can be coated, Viscosity, without particular determination, can the most suitably select.

Therefore, generally from the sight of the scope that easily film thickness of gained hard coat formation compositions is adjusted to regulation Point sets out, and is preferably diluted so that solid component concentration is 0.05 ~ 30 weight %, is more preferably diluted so that solid constituent Concentration is 0.1 ~ 25 weight %.

(3) film thickness

Additionally, it is preferred that the film thickness of hard coat is set to the value in the range of 0.5 ~ 5 μm.

Its reason is: if the film thickness of hard coat is the value less than 0.5 μm, then be not only due to the curable fall of resin Low and be difficult to obtain enough elching resistants, and the holding function of the thermal contraction of base material film for causing because of annealing Also become not enough, have the situation of the generation that cannot suppress curling.On the other hand, its reason is: if the film thickness of hard coat For the value more than 5 μm, then there is the situation becoming easily to produce aerofluxus from hard coat because of annealing.

Therefore, more preferably the film thickness of hard coat is set to the value in the range of 0.8 ~ 4 μm, further preferably it is set to 1 ~ Value in the range of 3 μm.

3. optical adjustment layer

As shown in Fig. 1 (a), optical adjustment layer 2 is preferably high refractive index layer 2b relatively high for refractive index and folding from base material film 4 side The relatively low low-index layer 2a of rate of penetrating carries out lamination successively.

Its reason is: by optical adjustment layer is set to such laminate structures, can effectively suppress because of electrically conducting transparent The specific refractivity of refractive index and the base material film 4 of layer and become to be easily discernible the pattern form of transparency conducting layer.

(1) high refractive index layer

(1)-1 refractive index

Preferably the refractive index of high refractive index layer is set to the value of more than 1.6.

Its reason is: if the refractive index of high refractive index layer is the value less than 1.6, then cannot obtain and low-index layer Significantly refractivity, has the situation of the pattern form becoming to be easily discernible transparency conducting layer.On the other hand, its reason is: If the refractive index of high refractive index layer is excessive value, then there is the situation that the film of high refractive index layer becomes fragile.

Therefore, more preferably the refractive index of high refractive index layer is set to the value in the range of 1.61 ~ 2, is further preferably set to Value in the range of 1.63 ~ 1.8.

(1)-2 raw material

It addition, high refractive index layer is preferably by containing the metal oxide microparticle as raw material and active energy ray-curable resin Compositions solidfied material constitute.

Its reason is: by containing metal oxide microparticle and active energy ray-curable resin, making high index of refraction The adjustment of the refractive index of layer becomes easy.

It addition, the kind of metal-oxide preferably lists: tantalum oxide, zinc oxide, Indium sesquioxide., hafnium oxide, cerium oxide, Stannum oxide, niobium oxide, indium tin oxide (ITO), antimony tin oxide (ATO) etc..

It addition, never reduce the transparency and from the viewpoint of realizing high index of refraction, particularly preferably selected from titanium oxide and Zirconic at least one.

It should be noted that, these metal-oxides can be used alone a kind or be two kinds or more.

It addition, the volume average particle size of metal oxide microparticle (D50) is preferably set in the range of 0.005 μm ~ 1 μm Value.

It should be noted that, the volume average particle size (D50) of metal oxide microparticle such as can be surveyed by using Zeta potential The algoscopy determining method is tried to achieve, in addition, it is possible to use laser diffraction and scattering formula particle size distribution device is tried to achieve, additionally Can try to achieve based on SEM image.

It addition, as the active energy ray-curable resin used in high refractive index layer and Photoepolymerizationinitiater initiater, can fit Preferably use the compound enumerated in the explanation of hard coat.

It addition, as the combined amount of metal oxide microparticle, relative to the active energy ray-curable tree of 100 weight portions Fat, preferably 20 ~ 2000 weight portions, more preferably 80 ~ 1000 weight portion, more preferably 150 ~ 400 weight portions.

(1)-3 high refractive index layer formation compositions

It addition, the compositions that the preferred previously prepared high refractive index layer of high refractive index layer is formed, as described by being coated, It is dried and solidifies to be formed.

Said composition can be prepared by the following method: as required, respectively with the ratio of regulation in suitable solvent Add active energy ray-curable resin, Photoepolymerizationinitiater initiater, metal oxide microparticle and various adding of using as required Add composition, carry out dissolving or disperseing.

It should be noted that, for various adding ingredients, solvent, the concentration of compositions of high refractive index layer formation, viscosity Deng, identical with the content in the explanation of hard coat.

(1)-4 film thickness

Additionally, it is preferred that the film thickness of high refractive index layer is set to 20 ~ 130nm.

Its reason is: if the film thickness of high refractive index layer is the value less than 20nm, then the film of high refractive index layer becomes fragile, and has It is unable to maintain that the situation of the shape of layer.On the other hand, its reason is: if the film thickness of high refractive index layer is more than 130nm's Value, then have the situation of the pattern form becoming to be easily discernible transparency conducting layer.

Therefore, more preferably the film thickness of high refractive index layer is set to 23 ~ 120nm, is further preferably set to 30 ~ 110nm.

(2) low-index layer

(2)-1 refractive indexs

Preferably the refractive index of low-index layer is set to 1.45 value below.

Its reason is: if the refractive index of low-index layer is the value more than 1.45, then cannot obtain and high refractive index layer Significant refractivity, have the situation of the pattern form being easily discernible transparency conducting layer.On the other hand, its reason is: if The refractive index of low-index layer is too small value, then have the situation that the film of low-index layer becomes fragile.

Therefore, more preferably the refractive index of low-index layer is set to the value in the range of 1.3 ~ 1.44, further preferably sets It it is the value in the range of 1.35 ~ 1.43.

(2)-2 raw materials

It addition, the low-index layer of the present invention is preferably using the low-index layer containing following (a) ~ (b) composition as raw material Formation compositions carries out photocuring:

(a) active energy ray-curable resin 100 weight portion,

(b) silicon dioxide microparticle 2 ~ 120 weight portion.

Its reason is: by formed low-index layer time use low-index layer formation compositions in relative to Active energy ray-curable resin contains silicon dioxide microparticle with less scope, even carrying out processing containing harsh alkali The situation of etch processes, it is possible to the silicon dioxide microparticle in suppression low-index layer dissolves or comes off effectively.

It addition, active energy ray-curable resin constitutes the base portion in low-index layer by solidification, can be more Silicon dioxide microparticle in protection low-index layer effectively, thus can effectively further improve elching resistant.

Hereinafter, every kind of composition is illustrated.

(i) (a) composition: active energy ray-curable resin

A () composition is active energy ray-curable resin.

Active energy ray-curable resin as such (a) composition can suitably use in the explanation of hard coat The photopolymerizing prepolymers enumerated or photopolymerization monomer.

It addition, active energy ray-curable resin preferably comprises waterproof resin.

Its reason is: by containing waterproof resin, can effectively further protect the titanium dioxide in low-index layer Silicon particle, therefore can more effectively improve elching resistant.

It addition, its reason is: if waterproof resin, then with as main active energy ray-curable resin (methyl) acrylic compounds uv curing resin is compared, and refractive index is low, therefore can be more easily by the refraction of low-index layer Rate is reduced to the scope of regulation.

It addition, as such waterproof resin, if having the resin of water proofing property, then without particular restriction, can use with Toward known waterproof resin.

More specifically, if the model that surface free energy is 10 ~ 30mN/m of resin molding formed with waterproof resin monomer Enclose interior value, then can be suitable as the waterproof resin of the present invention.

It addition, as the instantiation of waterproof resin, include, for example out: silicone resin or such as Kynoar, The fluororesin such as fluorine class acrylic resin and polyvinyl fluoride.

It addition, fluororesin is wherein preferably used, particularly preferred reactive perfluoroalkyl acrylate resin.

Its reason is: if fluororesin, then can more effectively protect the silicon dioxide microparticle in low-index layer, therefore Can effectively further improve elching resistant.

Additionally, it is preferred that in the case of (a) composition entirety is set to 100 weight %, the content of waterproof resin is set to 50 Value in the range of ~ 90 weight %.

Its reason is: if the content of waterproof resin is the value less than 50 weight %, then be difficult to effectively protect low refraction Silicon dioxide microparticle in rate layer, and then have the situation being difficult to improve elching resistant.It addition, its reason is: have and be difficult to low The refractive index of index layer is set to the situation of of a sufficiently low value.On the other hand, its reason is: if the content of waterproof resin is More than the value of 90 weight %, then the surface free energy of low-index layer can become too low value, has and is difficult to obtain index layer and is wanted Ask for the regulation adhesiveness of transparency conducting layer etc. in the case of.

Therefore, more preferably in the case of (a) composition entirety is set to 100 weight %, the content of waterproof resin is set to Value in the range of 60 ~ 85 weight %, is further preferably set to the value in the range of 70 ~ 80 weight %.

(ii) (b) composition: silicon dioxide microparticle

B () composition is silicon dioxide microparticle.

As the kind of such silicon dioxide microparticle, without particular restriction, but hollow silica particles is preferably used.

Its reason is: if hollow silica particles, then contains air at internal hollow space, therefore makes conduct The refractive index of silicon dioxide microparticle entirety reduces further, even few combined amount, it is possible to more effectively by low-index layer Refractive index be adjusted to the refractive index of regulation.

It should be noted that, " hollow silica particles " refers to the silicon dioxide microparticle in the inside of particle with cavity.

It addition, silicon dioxide microparticle is preferably reactive silicon dioxide microgranule.

Its reason is: if reactive silicon dioxide microgranule, then silicon dioxide microparticle can be firmly fixed at low folding Penetrate on rate layer, therefore can more effectively improve elching resistant.

It should be noted that, " reactive silicon dioxide microgranule " refers to be bonded with the organic compound containing polymerism unsaturated group Silicon dioxide microparticle, can be by making the silanol of the organic compound containing polymerism unsaturated group and silica particle surface Base reacts and obtains, and the described organic compound containing polymerism unsaturated group has the sense can reacted with this silanol group Group.

It addition, as above-mentioned polymerism unsaturated group, include, for example out: free-radical polymerised acryloyl group or methyl Acryloyl group etc..

Additionally, it is preferred that the volume average particle size (D50) of silicon dioxide microparticle is set to the value in the range of 20 ~ 70nm.

Its reason is: by the volume average particle size of silicon dioxide microparticle (D50) is set to the value in such scope, The transparency of low-index layer can not be reduced, and obtain the refractive index of regulation.

That is, its reason is: if the volume average particle size of silicon dioxide microparticle (D50) is the value less than 20nm, the most especially It is in the case of hollow silica particles, its structure is difficult to substantially ensure that the blank part of inside particles, makes low folding The effect of the refractive index reduction penetrating rate layer becomes not enough situation.On the other hand, its reason is: if the body of silicon dioxide microparticle Long-pending mean diameter (D50) is the value more than 70nm, then become easily to produce scattering of light, have the transparency of low-index layer to become Situation about being easily reduced.

Therefore, more preferably the volume average particle size (D50) of silicon dioxide microparticle is set to the value in the range of 30 ~ 60nm, Further preferably it is set to the value in the range of 40 ~ 50nm.

It should be noted that, the volume average particle size (D50) of silicon dioxide microparticle such as can be come by Zeta potential algoscopy Try to achieve, in addition, laser diffraction and scattering formula particle size distribution device can be used to try to achieve, be also based on SEM image in addition and ask ?.

Additionally, it is preferred that it is solid relative to the active energy beam containing waterproof resin as (a) composition of 100 weight portions The property changed resin, is set to the value in the range of 2 ~ 120 weight portions by the combined amount of silicon dioxide microparticle.

Its reason is: if the combined amount of silicon dioxide microparticle is the value less than 2 weight portions, then be difficult to make low-index layer Refractive index fully reduce, or be difficult to be formed enough concave-convex surfaces on low-index layer surface, thus have be difficult to obtain for The situation of the regulation adhesiveness of transparency conducting layer etc..On the other hand, its reason is: if the combined amount of silicon dioxide microparticle is super Cross the value of 120 weight portions, then, in the case of carrying out the etch processes processed containing harsh alkali, have two in low-index layer Silicon oxide particle becomes the situation easily dissolved or come off.

Therefore, more preferably relative to the active energy beam containing waterproof resin as (a) composition of 100 weight portions Curable resin, is set to the value in the range of 30 ~ 110 weight portions by the combined amount of silicon dioxide microparticle, is further preferably set to Value in the range of 50 ~ 100 weight portions.

(2)-3 low-index layer formation compositionss

It addition, low-index layer previously prepared low-index layer formation compositions, as described by being coated, being dried also Solidification is formed.

Said composition can be prepared by the following method: as required, respectively with the ratio of regulation in suitable solvent Add the active energy ray-curable resin as above-mentioned (a) composition and the silicon dioxide microparticle as (b) composition, Yi Jiguang The various adding ingredient such as polymerization initiator, carries out dissolving or disperseing.

It should be noted that, for various adding ingredients, solvent, the concentration of low-index layer formation compositions, viscosity etc., Identical with the content in the explanation of hard coat.

(2)-4 film thicknesses

Additionally, it is preferred that the film thickness of low-index layer is set to the value in the range of 20 ~ 150nm.

Its reason is: by the value being set in such scope by the film thickness of low-index layer, can more stably by Pattern form invisibleization of transparency conducting layer, and, available enough elching resistants.

That is, its reason is: if the film thickness of low-index layer is the value less than 20nm, then the film of low-index layer becomes Crisp, there is elching resistant to become the situation of deficiency.On the other hand, its reason is: if the film thickness of low-index layer is for exceeding The value of 150nm, then have the pattern form of transparency conducting layer to become situation about being easily discernible.

Therefore, more preferably the film thickness of low-index layer is set to the value in the range of 25 ~ 120nm, further preferably sets It it is the value in the range of 30 ~ 100nm.

4. the preparation method of transparency conducting layer formation lamilated body

The transparency conducting layer formation lamilated body of the present invention such as can be obtained by the preparation method containing following procedures (a) ~ (b) Arrive:

A () forms the operation of hard coat on the two sides of base material film,

B () forms the operation of optical adjustment layer on the hard coat of side.

Hereinafter, omit the part repeated with content before this, describe different parts the most in detail.

It should be noted that, although the transparency conducting layer formation lamilated body of the present invention on the two sides of base material film not by hard Coating is as required constitutive requirements, but the two sides being set forth in base material film in the following description forms the situation of hard coat for real Example illustrates.

(1) operation (a): form the operation of hard coat

On the two sides of base material film, it is coated with above-mentioned hard coat formation compositions by known method and forms film After, it is dried, to its irradiation active energy beam so that curing of coating, is consequently formed hard coat.

It addition, as the coating process of hard coat formation compositions, include, for example out: scraper rubbing method, scraper Rubbing method, rolling method, scraper plate rubbing method, die coating methods, gravure coating process etc..

It addition, as drying condition, preferably carry out at 60 ~ 150 DEG C 10 seconds ~ about 10 minutes.

Additionally, as active energy beam, include, for example out ultraviolet or electron beam etc..

It addition, as the light source of ultraviolet, can list: high voltage mercury lamp, electrodeless lamp, metal halide lamp, xenon lamp etc., Its irradiation dose is generally preferably set to 100 ~ 500mJ/cm²。

On the other hand, as the light source of electron beam, can list electron-beam accelerator etc., its irradiation dose is generally preferably set to 150~350kV。

It addition, when irradiating active energy beam, carry out the most under nitrogen atmosphere.

Its reason is: by carrying out under nitrogen atmosphere, can effectively carry out the curing reaction on hard coat surface, can enter One step is effectively improved the elching resistant of hard coat.

(2) operation (b): form the operation of optical adjustment layer

Then, the hard coat formed forms (in the case of not forming hard coat directly on base material film) height refraction Rate layer.

That is, high refractive index layer can be formed by the following method: identically with forming hard coat on base material film by upper State high refractive index layer formation compositions to be coated, be dried, and, irradiate active energy beam so that it solidifies.

Then, the high refractive index layer formed forms low-index layer further.

That is, low-index layer can be formed by the following method: identically with forming hard coat on base material film by upper State low-index layer formation compositions to be coated, be dried, and, irradiate active energy beam so that it solidifies.

It addition, when irradiating active energy beam, carry out the most under nitrogen atmosphere.

Its reason is: by carrying out under nitrogen atmosphere, can effectively carry out the curing reaction on optical adjustment layer surface, can Effectively further improve optical adjustment layer, the elching resistant of low-index layer especially as most surface layer.

[the 2nd embodiment]

2nd embodiment of the present invention is transparent and electrically conductive film, as it is shown on figure 3, it is hard coat, base material film, optics to be adjusted Flood and transparency conducting layer carry out the transparent and electrically conductive film of lamination successively, it is characterised in that hard coat be will contain under The hard coat formation compositions of row (A) ~ (B) composition carries out photocuring:

(A) active energy ray-curable resin 100 weight portion,

(B) silicon dioxide microparticle 15 ~ 100 weight portion.

Hereinafter, the 2nd embodiment of the present invention being omitted the part repeated with content before this, narration is not the most in detail Same part.

1. transparency conducting layer

(1) raw material

In the transparent and electrically conductive film of the present invention, as the raw material of transparency conducting layer, if having the former of the transparency and electric conductivity concurrently Material, then without particular restriction, include, for example out: Indium sesquioxide., zinc oxide, stannum oxide, indium tin oxide (ITO), tin-antimony oxide, Zinc-aluminium, indium-zinc oxide etc..

It addition, particularly preferably use ITO as raw material.

Its reason is: if ITO, then by using suitable membrance casting condition, can form the transparency and excellent electric conductivity Transparency conducting layer.

(2) pattern form

It addition, transparency conducting layer is preferably formed such as wire or cancellate pattern form by etching.

It addition, the live width of the existence part of above-mentioned pattern form preferably clear conductive layer and the non-existent portion of transparency conducting layer The live width approximately equal divided.

Additionally, this live width is usually 0.1 ~ 10mm, preferably 0.2 ~ 5mm, particularly preferably 0.5 ~ 2mm.

It should be noted that, above-mentioned wire or cancellate live width are not limited to as constant situation, such as can be freely Select the live width etc. being connected with the shape required by the contact panel of static capacitive.

Specifically, can list: the pattern form etc. that rhombus part is connected repeatedly with line portion, such pattern form is also It is included in the category of " wire ".

It should be noted that, in the case of so forming transparency conducting layer, being made annealing treatment by enforcement, normally transparent conducts electricity The pattern form of layer becomes the most noticeable, as it is shown on figure 3, in the case of the both sides of base material film arrange hard coat, if For the transparent and electrically conductive film of the present invention, then can be by pattern form invisibleization of transparency conducting layer.

(3) film thickness

It addition, the thickness of transparency conducting layer is preferably 5 ~ 500nm.

Its reason is: if the thickness of transparency conducting layer is the value less than 5nm, the most not only transparency conducting layer becomes fragile, and There is the situation that cannot obtain enough electric conductivity.On the other hand, its reason is: if the thickness of transparency conducting layer is for exceeding The value of 500nm, then the tone deriving from transparency conducting layer becomes strong, has pattern form to become situation about easily identifying.

Therefore, the thickness of transparency conducting layer is more preferably 15 ~ 250nm, more preferably 20 ~ 100nm.

2. the preparation method of transparent and electrically conductive film

For the optical adjustment layer obtained in the operation (b) in the preparation method of above-mentioned transparency conducting layer formation lamilated body, By the known method such as vacuum vapour deposition, sputtering method, CVD, ion plating method, nebulization, sol-gel process, formed thoroughly Bright conductive layer, thus can get transparent and electrically conductive film.

It addition, as sputtering method, can list: use the common sputtering method of compound or use the reactivity of metallic target Sputtering method etc..

Now, it is also preferred that importing oxygen, nitrogen, steam etc. are as reactant gas, or add ozone or and assist with ion Deng.

It addition, transparency conducting layer can form the pattern etc. of wire after film forming executed as described above by the following method: passing through After the photoresistive mask of the pattern that photoetching process forms regulation, implement etch processes by known method.

It should be noted that, as etching solution, preferably list: the aqueous acids etc. such as hydrochloric acid, sulphuric acid, nitric acid, phosphoric acid.

It addition, from etch processes rapid from the viewpoint of, as the final operation of etch processes be used for remove residual The alkali of photoresist process in the solution that uses be preferably used liquid temperature be 10 ~ 50 DEG C, concentration be that 1 ~ 10 weight %, pH are The strong alkali aqueous solution of 13.4 ~ 14.4.

It addition, as the highly basic being suitable for, can list: Lithium hydrate, sodium hydroxide, potassium hydroxide, rubidium hydroxide, hydrogen-oxygen Change caesium, tetramethylammonium hydroxide, tetraethylammonium hydroxide, calcium hydroxide, Strontium hydrate., barium hydroxide, europium hydroxide (II), hydroxide Thallium (I), guanidine etc..

It addition, for the crystallinity improving transparency conducting layer, and reduce resistivity, it is preferably provided with annealing operation and specifies Annealing.

I.e., preferably gained transparent and electrically conductive film is exposed 0.5 ~ 2 hour under the temperature conditions of 130 ~ 180 DEG C.

Embodiment

Hereinafter, with reference to embodiment, the transparency conducting layer formation lamilated body etc. of the present invention is illustrated in greater detail.

[embodiment 1]

1. the preparation of hard coat formation compositions

House as the active energy ray-curable resin of (A) composition, as the two of (B) composition using following composition in container Silicon oxide particle, as the levelling agent of (C) composition and the Photoepolymerizationinitiater initiater as (D) composition after, add solvent equably Mix, be prepared for the hard coat formation compositions that solid component concentration is 22 weight %.

It should be noted that, shown in following composition and table 1, the combined amount of composition represents the pure component eliminating retarder thinner.

(A) composition: dipentaerythritol acrylate 100 weight portion

(B) composition: reactive solid silicon dioxide microparticle 43.2 weight portion

(volume average particle size (D50) 15nm)

(C) composition: fluorine class levelling agent 0.05 weight portion

(Neos (strain) makes, Ftergent 7602A)

(D) composition: Photoepolymerizationinitiater initiater 3 weight portion

(BASF Japan (strain) makes, Irgacure 184)

It should be noted that, the volume average particle size (D50) of above-mentioned (B) composition is filled by laser diffraction and scattering formula particle size distribution Put and be determined.

Have the situation of the light trigger referred to as " Irgacure 184 " as above-mentioned (D) composition it addition, following.

2. the preparation of high refractive index layer formation compositions

Uv curing resin (industry (strain) of refining big day system, the Seika-Beam of 100 weight portions is housed in container EXF-01L (NS)) (expression eliminates the pure component of retarder thinner.The most identical.), the Zirconium oxide dispersion liquid of 200 weight portions (CIK Nanotech (strain) makes, ZRMIBK15WT%-F85), acrylic compounds levelling agent (the BYK Chemie of 0.05 weight portion Japan (strain) makes, BYK-355) and the Photoepolymerizationinitiater initiater (BASF Japan (strain) makes, Irgacure 907) of 3 weight portions After, add solvent and mix equably, being prepared for the high refractive index layer formation combination that solid component concentration is 1 weight % Thing.

3. the preparation of low-index layer formation compositions

The active energy ray-curable tree containing waterproof resin as (a) composition is housed using following composition in container Fat, the silicon dioxide microparticle as (b) composition, the levelling agent as (c) composition and the Photoepolymerizationinitiater initiater as (d) composition After, add solvent and mix equably, being prepared for the low-index layer formation combination that solid component concentration is 1 weight % Thing.

It should be noted that, shown in following composition, the combined amount of composition represents the pure component eliminating retarder thinner.

(a) composition: ultra-violet solidified acrylic resin 100 weight portion containing fluororesin

(kind of fluororesin: reactive F acrylic resin, the content of fluororesin: 80 weight %, the solidification tree of fluororesin monomer The surface free energy of fat film: 25mN/m)

(b) composition: reactive hollow silica particles 100 weight portion

(volume average particle size (D50) is 45nm)

(c) composition: acrylic compounds levelling agent 0.05 weight portion

(BYK Chemie Japan (strain) makes, BYK-355)

(d) composition: Photoepolymerizationinitiater initiater 5 weight portion

(BASF Japan (strain) makes, Irgacure 184)

It should be noted that, the volume average particle size (D50) of above-mentioned (b) composition is filled by laser diffraction and scattering formula particle size distribution Put and be determined.

4. the formation of hard coat

As base material film, prepare (Teijin DuPont (strain) of the polyester film with easy adhesive linkage that film thickness is 125 μm System, PET125KEL86W).

Then, surface bar #8 at the base material film prepared is coated with hard coat formation compositions.

Then, after being dried 1 minute in 70 DEG C, ultraviolet lamp (GS Yuasa is used under nitrogen atmosphere Corporation (strain) makes) with following condition irradiation ultraviolet radiation, define the hard that film thickness is 2 μm on the surface of base material film Coating.

It addition, be also identically formed hard coat in the face of the opposition side of base material film.

Light source: high voltage mercury lamp

Illumination: 150mW/cm²

Light quantity: 150mJ/cm²

5. the formation of high refractive index layer

Then, the hard coat of the side formed is coated with high index of refraction formation compositions by bar #4.

Then, after being dried 1 minute at 50 DEG C, ultraviolet lamp (GS Yuasa is used under nitrogen atmosphere Corporation (strain) makes) with the irradiation condition irradiation ultraviolet radiation identical with hard coat, hard coat defines film Thickness is 35nm, refractive index is n_DThe high refractive index layer of=1.65.

6. the formation of low-index layer

Then, the high refractive index layer formed is coated with, by bar #4, the compositions that low-index layer is formed.

Then, after being dried 1 minute at 50 DEG C, ultraviolet lamp (GS Yuasa is used under nitrogen atmosphere Corporation (strain) makes) with the irradiation condition irradiation ultraviolet radiation identical with hard coat, high refractive index layer forms film Thickness is 50nm, refractive index is n_DThe low-index layer of=1.37, has obtained the transparency conducting layer formation layer as shown in Fig. 1 (a) Fit.

7. evaluate

(1) evaluation of elching resistant

Have rated the elching resistant of gained transparency conducting layer formation lamilated body.

That is, (Shimadzu Seisakusho Ltd.'s (strain) makes, UV-to use UV, visible light near-infrared (UV-vis-NIR) spectrophotometer 3600), with reflection angle: 8 °, Sampling Distance: 1nm, mode determination: single condition determine gained transparency conducting layer formed With the reflectance (%) (low-index layer side) of lamilated body.

Then, transparency conducting layer formation lamilated body is soaked in being heated to be the sodium hydrate aqueous solution of 5 weight % of 40 DEG C Then stain determines reflectance (%) with the condition identical with above-mentioned condition to carry out alkali process in 5 minutes.

Then, from alkali reflectance before treatment (%), deduct the reflectance (%) after alkali processes, calculated reflectance change Amount (%).Acquired results is shown in Table 1.

It should be noted that, if reflectance variable quantity is 0.5% value below, then can determine whether as having in actual use excellent Different elching resistant.

It addition, can be by the reason of reflectance variable quantity (%) evaluation elching resistant: if being coated with by etch processes hard The film thickness of layer or refractive index or this two side change, then the reflectance of hard coat changes.

(2) evaluation of pattern recognition

For the surface of the low-index layer of gained transparency conducting layer formation lamilated body, form the transparency conducting layer of patterning, Have rated its identification.

That is, after gained transparency conducting layer formation lamilated body being cut into long 90mm × wide 90mm, ITO target (10 weights are used The amount stannum oxide of %, the Indium sesquioxide. of 90 weight %) sputter, the central part on low-index layer defines long 60mm × wide The square of 60mm, film thickness are the transparency conducting layer of 30nm.

Then, the surface of gained transparency conducting layer defines it is patterned as cancellate photoresist film.

Then, at room temperature, within 1 minute, it is etched processing, by electrically conducting transparent by dipping in the hydrochloric acid of 10 weight % Pattern layers is clathrate.

Then, in being heated to be the sodium hydrate aqueous solution of 5 weight % of 40 DEG C, dipping removes for 5 minutes to carry out alkali process Photoresist film on transparency conducting layer, has obtained the transparent and electrically conductive film of the transparency conducting layer with patterning.

This transparent and electrically conductive film has the transparency conducting layer of 30nm, and described transparency conducting layer has by being 2mm by live width ITO constitute line portion and be cancellate pattern form by the foursquare spaces separate that 1 limit is 2mm.

Then, gained transparent and electrically conductive film is arranged at the position away from white fluorescent lamp 1m, so that white fluorescent lamp is mirrored The state of transparent and electrically conductive film, from the position of the transparent and electrically conductive film 30cm away from the side identical with arranging white fluorescent lamp, logical Cross the pattern form of visualization transparency conducting layer, evaluated according to following standard.Acquired results is shown in Table 1.

Zero: cannot the pattern form of identification transparency conducting layer

×: can the pattern form of identification transparency conducting layer

(3) evaluation of resistance to blocking

Have rated the resistance to blocking of gained transparency conducting layer formation lamilated body.

That is, on smooth glass plate, not by binding agent etc., make hard coat placed transparency conducting layer upward and formed Use lamilated body.

Then, on the transparency conducting layer formation lamilated body placed, overlap placed other transparency conducting layer shape After one-tenth lamilated body, press with hands, by these 2 transparency conducting layer formation lamilated bodies that rub, carry out hard coat that The phase mutual friction of this phase mutual friction and hard coat and low-index layer, the resistance to blocking according to following standard evaluation.By institute Obtain result to be shown in Table 1.

Zero: layer surface is the most nonadherent

×: layer surface is adhering to each other and does not moves

[embodiment 2]

In example 2, when preparing hard coat formation compositions, it is set to following composition, in addition, with embodiment 1 Prepare transparency conducting layer formation lamilated body in the same manner and evaluated.Acquired results is shown in Table 1.

It should be noted that, shown in following composition and table 1, the combined amount of composition represents the pure component eliminating retarder thinner.

(A1) composition: dipentaerythritol acrylate 99.5 weight portion

(A2) composition: crosslink propylene acids copolymer resins 0.5 weight portion

(hydrops finished industrial (strain) is made, Tech Polymer XX-27LA)

(B) composition: reactive solid silicon dioxide microparticle 100 weight portion

(volume average particle size (D50) is 15nm)

(C) composition: fluorine class levelling agent 0.13 weight portion

(Neos (strain) makes, Ftergent 7602A)

(D) composition: Photoepolymerizationinitiater initiater 6.7 weight portion

(BASF Japan (strain) makes, Irgacure 184)

It should be noted that, the volume average particle size (D50) of above-mentioned (B) composition is filled by laser diffraction and scattering formula particle size distribution Put and be determined.

Have crosslink propylene acid copolymer resin referred to as " the Tech Polymer as (A2) composition it addition, following XX-27LA " situation.

[comparative example 1]

In comparative example 1, when preparing hard coat formation compositions, it is set to following composition, in addition, with embodiment 1 Prepare transparency conducting layer formation lamilated body in the same manner and evaluated.Acquired results is shown in Table 1.

It should be noted that, shown in following composition and table 1, the combined amount of composition represents the pure component eliminating retarder thinner.

(A) composition: dipentaerythritol acrylate 100 weight portion

(B) composition: reactive solid silicon dioxide microparticle 150 weight portion

(volume average particle size (D50) is 15nm)

(C) composition: fluorine class levelling agent 0.05 weight portion

(Neos (strain) makes, Ftergent 7602A)

(D) composition: Photoepolymerizationinitiater initiater 5 weight portion

(BASF Japan (strain) makes, Irgacure 184)

It should be noted that, the volume average particle size (D50) of above-mentioned (B) composition is filled by laser diffraction and scattering formula particle size distribution Put and be determined.

[comparative example 2]

In comparative example 2, when preparing hard coat formation compositions, it is set to following composition, in addition, with embodiment 1 Prepare transparency conducting layer formation lamilated body in the same manner and evaluated.Acquired results is shown in Table 1.

It should be noted that, shown in following composition and table 1, the combined amount of composition represents the pure component eliminating retarder thinner.

(A) composition: dipentaerythritol acrylate 100 weight portion

(C) composition: fluorine class levelling agent 0.05 weight portion

(Neos (strain) makes, Ftergent 7602A)

(D) composition: Photoepolymerizationinitiater initiater 5 weight portion

(BASF Japan (strain) makes, Irgacure 184)

Industrial applicability

As narration in detail above, according to the present invention, forming the back side as transparency conducting layer formation lamilated body Hard coat time, use relative to active energy ray-curable resin with regulation scope mixing silicon dioxide microparticle form Hard coat formation compositions, it is possible to obtain the transparency conducting layer formation layer that the elching resistant of hard coat is excellent Fit.

It is as a result, it is possible to obtain can be stably by pattern form invisibleization of transparency conducting layer, and gained is transparent leads The transparency conducting layer formation lamilated body that electrically resistance to blocking of film is excellent.

Therefore, the transparency conducting layer formation lamilated body expecting the present invention and the transparent and electrically conductive film using this lamilated body show Write ground and contribute to the high-quality of contact panel.

Symbol description

1: transparency conducting layer, 2: optical adjustment layer, 2a: low-index layer, 2b: high refractive index layer, 3: hard coat, 3a: the 1 is hard Matter coating, the 3b: the 2 hard coat, 4: base material film, 10: transparency conducting layer formation lamilated body, 100: transparent and electrically conductive film.

Claims (10)

1. transparency conducting layer formation lamilated body, its be that hard coat, base material film and optical adjustment layer are carried out successively lamination and The transparency conducting layer formation lamilated body become, it is characterised in that

Above-mentioned hard coat is the hard coat formation compositions containing following (A) ~ (B) composition to be carried out photocuring form :

(A) active energy ray-curable resin 100 weight portion,

(B) silicon dioxide microparticle 15 ~ 100 weight portion.

2. the transparency conducting layer formation lamilated body described in claim 1, it is characterised in that will be as the two of above-mentioned (B) composition The volume average particle size of silicon oxide particle i.e. D50 is set to the value in the range of 10 ~ 100nm.

3. the transparency conducting layer formation lamilated body described in claim 1, it is characterised in that as the dioxy of above-mentioned (B) composition SiClx microgranule is solid silicon dioxide microparticle.

4. the transparency conducting layer formation lamilated body described in claim 1, it is characterised in that as the dioxy of above-mentioned (B) composition SiClx microgranule is reactive silicon dioxide microgranule.

5. the transparency conducting layer formation lamilated body described in claim 1, it is characterised in that above-mentioned hard coat formation is combined Thing contains the fluorine class levelling agent as (C) composition, and, relative to the active energy beam as above-mentioned (A) of 100 weight portions Curable resin, is set to the value in the range of 0.01 ~ 0.2 weight portion by the combined amount of this fluorine class levelling agent.

6. the transparency conducting layer formation lamilated body described in claim 1, it is characterised in that by the film thickness of above-mentioned hard coat It is set to the value in the range of 0.5 ~ 5 μm.

7. the transparency conducting layer formation lamilated body described in claim 1, it is characterised in that using above-mentioned hard coat as In the case of 1 hard coat, there is between above-mentioned base material film and above-mentioned optical adjustment layer the 2nd hard coat.

8. the transparency conducting layer formation lamilated body described in claim 7, it is characterised in that above-mentioned 2nd hard coat be by with The hard coat formation compositions that above-mentioned 1st hard coat is identical carries out photocuring, and, have and the above-mentioned 1st The film thickness that hard coat is identical.

9. transparent and electrically conductive film, its be that hard coat, base material film, optical adjustment layer and transparency conducting layer are carried out successively lamination and The transparent and electrically conductive film become, it is characterised in that

Above-mentioned hard coat is the hard coat formation compositions containing following (A) ~ (B) composition to be carried out photocuring form :

(A) active energy ray-curable resin 100 weight portion,

(B) silicon dioxide microparticle 15 ~ 100 weight portion.

10. the transparent and electrically conductive film described in claim 9, it is characterised in that make above-mentioned pattern for transparent conductive layer by etching.