CN1894601A

CN1894601A - Antireflection film, electromagnetic wave shielding light transmitting window material, gas discharge type light emitting panel, flat display panel, show window material and solar cell module

Info

Publication number: CN1894601A
Application number: CN 200480037553
Authority: CN
Inventors: 吉川雅人; 西田三博
Original assignee: Bridgestone Corp
Current assignee: Bridgestone Corp
Priority date: 2003-12-17
Filing date: 2004-12-14
Publication date: 2007-01-10
Anticipated expiration: 2024-12-14
Also published as: CN100417954C; JP2005181543A

Abstract

An antireflection film comprising transparent base film 1 and, sequentially superimposed thereon, hard coat layer (2), high refractive index layer 3 and low refractive index layer 4. Alternatively, there is provided an antireflection film comprising a transparent base film and, sequentially superimposed thereon, a conductive high refractive index hard coat layer and a low refractive index layer. The low refractive index layer is obtained through irradiating of a coating film comprising hollow silica microparticles, a polyfunctional (meth)acrylic compound and a photopolymerization initiator with ultraviolet rays in an atmosphere of 0 to 10,000 ppm oxygen concentration so as to harden the same.

Description

Antireflection film, electromagnetic wave shielding transmitance window material, gas discharge type luminescent panel, panel display board, show window material and solar module

Technical field

I. first aspect relates to various displays such as being suitable for word processor, computer, CRT, plasm TV, LCD, organic EL, and the application type antireflection film of automobile, buildings, the glass pane of electric car and the picture glass of drawing etc.

II. second aspect relates to the application type light absorption type antireflection film of the display surface of various displays such as being suitable for word processor, computer, CRT, plasm TV, LCD, organic EL etc.

III. the 3rd aspect relates to various displays such as being suitable for word processor, computer, CRT, plasm TV, LCD, organic EL, and the application type antireflection film of automobile, buildings, the glass pane of electric car and the picture glass of drawing etc.

IV. the 4th aspect relates to electromagnetic wave shielding transmitance window material and gas discharge type luminescent panel, particularly formed the electromagnetic wave shielding transmitance window material and the gas discharge type luminescent panel of the good application type anti-reflection layer of antireflection property at outermost surface.

V. the 5th aspect relates to flat-panel monitor and show window material, particularly formed the flat-panel monitor and the show window material of the good application type anti-reflection layer of antireflection property on the surface.

VI. the 6th aspect relates to solar module, particularly low the thereby sunshine impingement rate height of external light reflection rate, solar module that luminescence efficiency is good.

Background technology

I. at various displays such as word processor, computer, CRT, plasm TV, LCD, organic EL, and in automobile, buildings, the glass pane of electric car and the picture glass of drawing etc., in order to prevent that reflection of light from guaranteeing higher transmitance, generally use antireflection film.

Up to now, as the antireflection film that is used for this purposes, provide the antireflection film that is provided with high refractive index layer and low-index layer on the surface of transparent base film.This antireflection film utilizes the difference of the refractive index of high refractive index layer and low-index layer to obtain anti-reflective function.

In existing antireflection film, provide in a large number and come stacked SiO by evaporation or sputter ₂, MgF ₂Deng low-index layer and TiO ₂, high refractive index layer such as ITO the dry type antireflection film that becomes embrane method to form, but dry process is very time-consuming and cost is very high when film forming.

On the other hand, if utilize the film build method of damp process such as nick version rubbing method, then can make antireflection film with lower cost.As the application type antireflection film, main use as shown in Figure 1 on the surface of the formed transparent base film 1 of synthetic resin, stack gradually hard conating 2, high refractive index layer 3 and low-index layer 4 formed antireflection films from lower floor's one side.Also have in addition on base film, to form the electric conductivity high index of refraction hard conating that has high refractive index layer and hard conating simultaneously, on it, form the formed antireflection film of low-index layer then.

But in damp process, the high index of refractionization of the low-refractionization of low-refraction composition and high index of refraction composition is difficult, is difficult to obtain good antireflection property.Particularly the low-refractionization of low-index layer is very difficult, up to now, has carried out various researchs at the low-refractionization of low-index layer.

Usually, as the low-refraction layer material of application type antireflection film, the fluororesin (for example Japanese patent laid-open 9-203801 communique) that uses the part hydrogen atom of alkyl to be replaced mostly by fluorine atom.

Although used the refractive index of low-index layer of fluororesin low, but in order to reduce refractive index, the chain length of the alkyl chain that the just necessary fluorine that increases fluororesin replaces, on the other hand, if increase the chain length of alkyl chain, then there is the problem of the film strength reduction of formed low-index layer.For example, if use plastic eraser to wipe the low-index layer that the existing fluororesin of wiping forms, then be very easy to produce film and peel off.In the low-index layer of the disclosed use fluororesin of Japanese patent laid-open 9-203801 communique, according to the inventor's test, with mar proof specification (4.9 * 10 ⁴N/m ²) pressure use plastic eraser to wipe to carry out wiping, about 10 times, will produce breaking of film.

As the application type low-index layer, also proposed by bond fixedly particle diameter be the method for particulate of the low-refraction (n) of 1～100nm.Wherein, by the acrylic compounds bond fixedly silicon dioxide microparticle (n=1.47) though layer film strength height, but the refractive index of silicon dioxide microparticle higher (1.47), thereby when using conventional bond, can not make the refractive index of formed low-index layer reach 1.49 or below it.

In addition, passing through fixedly MgF of acrylic compounds bond ₂In the layer of particulate (n=1.38), though the refractive index decrease to some degree (n=1.46) of low-index layer, MgF ₂Poor with the compatibility of acrylic acid bond, the film strength non-constant that becomes.

Therefore, as particulate good with the compatibility of bond, low-refraction, when having proposed in use empty silicon dioxide microparticle (hollow silica), the silicone composition that uses the fluorinated alkyl as bond with the improvement that realizes film strength and the technical scheme (the Jap.P. spy opens the 2003-202406 communique, the Jap.P. spy opens the 2003-202960 communique) of low-refractionization.

But in antireflection film, normally used base film is polyethylene terephthalate (PET) film or tri acetyl cellulose film, in the PET film, considers from the thermotolerance aspect, can not carry out the heating more than 130 ℃.In utilizing the one-tenth embrane method of damp process, if the silicone composition that can not carry out heat-agglomerating processing etc. as bond, shown in the comparative experiments example as described later, chemical resistance, the non-constant of mar proof.Particularly dipping is about 30 minutes the time in alkaline aqueous solution (3 weight %NaOH), and the silicone composition produces basic hydrolysis, and film is dissolved easily to be fallen.Therefore, use comprise the bond of silicone composition and the system that mixes with hollow silica in, in the situation of strong wiping as the outermost low-index layer of antireflection film with alkaline detergent, since the dissolving of low-index layer, the anti-reflective function forfeiture.

On the other hand, also proposed to use polyfunctional group acryl resin more than the difunctional, will mix the film forming technical scheme of low-index layer (Jap.P. spy open 2003-261797 communique, Jap.P. spy are opened the 2003-262703 communique, the Jap.P. spy opens the 2003-266602 communique) of porous silica particulate by damp process as bond.

But; according to discovering of the inventor; by the polyfunctional group acryl resin more than the difunctional is mixed the non-constant of film strength of the resulting film of back film forming with the porous silica particulate; even only the polyfunctional group acryl resin more than the difunctional is mixed with the porous silica particulate, can not form low-index layer with mar proof.In addition, in these patent documentations, directly form low-index layer, when still on base material, directly forming low-index layer like this, can not obtain the good films of the indispensable antireflection property of antireflection film such as minimum reflectance at substrate surface.And, in these patent documentations, use be porous silica particulate but not hollow silica particles, and the porous silica particulate can not fully reduce the refractive index of silicon dioxide, therefore, the refractive index of low-index layer can not reach fully low value.

Low-index layer as the superiors of antireflection film, not only refractive index is low is important, and permanance such as mar proof and chemical resistance also are very important, and as mentioned above, the application type antireflection film of the low-index layers that film properties is good and refractive index is low such as having mar proof, chemical resistance is not provided in the prior art.

II. be applicable on the display surface of various displays such as word processor, computer, CRT, plasm TV, LCD, organic EL, be used to prevent reflection of light and the antireflection film of guaranteeing high transmitance.

Up to now, as the antireflection film that is used for this purposes, the surface that has proposed transparent base film is provided with the antireflection film of high refractive index layer and low-index layer.In such antireflection film, utilize the refringence of high refractive index layer and low-index layer to obtain antireflection property.

In existing antireflection film, provide in a large number and come stacked SiO by evaporation or sputter ₂, MgF ₂Deng low-index layer and TiO ₂, high refractive index layer such as ITO the dry type antireflection film that becomes embrane method to form, but dry type becomes embrane method very time-consuming and cost is very high when film forming.

On the other hand, if utilize the film build method of damp process such as nick version rubbing method, then can make antireflection film with lower cost.

As the application type low-index layer, also proposed by bond fixedly particle diameter be the method for particulate of the low-refraction (n) of 1～100nm.Wherein, by the acrylic compounds bond fixedly silicon dioxide microparticle (n=1.47) though layer film strength height, but the refractive index of silicon dioxide microparticle is higher, be 1.47, thereby when using conventional bond, can not make the refractive index of formed low-index layer reach 1.49 or below it.

But in antireflection film, normally used base film is polyethylene terephthalate (PET) film or tri acetyl cellulose (TAC) film, in the PET film, considers from the thermotolerance aspect, can not carry out the heating more than 130 ℃.In utilizing the one-tenth embrane method of damp process, if the silicone composition that can not carry out heat-agglomerating processing etc. as bond, then chemical resistance, the non-constant of mar proof.Particularly dipping is about 30 minutes the time in alkaline aqueous solution (3 weight %NaOH), and the silicone composition produces basic hydrolysis, and film is dissolved easily to be fallen.Therefore, use comprise the bond of silicone composition and the system that mixes with hollow silica in, in with the strong situation of wiping such as alkaline detergents as the outermost low-index layer of antireflection film, since the dissolving of low-index layer, the anti-reflective function forfeiture.

And in antireflection film, particularly in the antireflection film of Plasmia indicating panel, CRT purposes, further require that (400～450nm) reflectivity is low, the transmissivity height of the fully light of transmission blue-light-emitting, and short wavelength one side, transmitted colors are not with yellow in short wavelength's one side.

In the prior art, shown in common employed antireflection film composed as follows, the reflectance spectrum of these antireflection films as shown in Figure 3.

Form 1: low-index layer (n=1.45)/high index of refraction hard conating (n=1.71)/PET film

Form 2: low-index layer (n=1.45)/high index of refraction hard conating (n=1.68)/TAC film

In above-mentioned

composition

1,2, the thickness of high refractive index layer and low-index layer is 1/4 wavelength (1/4 λ) of blooming.Forming in 1, antireflection property is insufficient, at this moment, is forming in 2, and minimum reflectance is about about 0.4% at wavelength 550nm place, be lower, and near the reflectivity wavelength 450nm is about 4.5%, and rising is arranged.Because like this at the reflectivity height of short wavelength's one side, thereby form in 2 the fully light of transmission blue-light-emitting at this.In addition, if the transmissivity of short wavelength's one side is low,, therefore, for example in display, when taking place, white light but has yellow then through the transmission light belt yellow behind this film.

Do not change above-mentioned composition 2,, proposed forming in 2, increase the thickness of high refractive index layer a little, reduce the method (forming 3) of the thickness of low-index layer a little in order to reduce the reflectivity of short wavelength's one side.

That is, forming in 1, with thickness coating high refractive index layer and the low-index layer of about 1/4 λ of blooming, still, forming in 3, the thickness of high refractive index layer is that the thickness of 0.32 λ, low-index layer is 0.22 λ.With this composition 3 with form 1 reflectance spectrum that compares as shown in Figure 4.

If increase the thickness of high refractive index layer like this, then the reflectivity of short wavelength's one side reduces, and the reflectivity height of wavelength 400nm, is 3.5%.In addition, minimum reflectance also rises a little, and therefore, even the reflectivity of short wavelength's one side reduces, the observability reflectivity has still risen, and this is a difficult problem.In addition, although the reflectivity of short wavelength's one side is to have reduced, 3.5% still is too high, needs all abundant low antireflection film of exploitation minimum reflectance and observability reflectivity.

Therefore, the applicant has proposed before this on transparent base film, stack gradually the light absorption type antireflection film (Japanese patent application (special hope) 2002-318349 number) of hard conating, transparency conducting layer, light absorbing zone, low-index layer, perhaps on transparent base film, stack gradually the antireflection film of hard conating, electric conductivity light absorbing zone and low-index layer.

For example, figure 5 illustrates and on transparent base film, stack gradually hard conating, transparency conducting layer, light absorbing zone and low-index layer, the thickness of hard conating is that the thickness of 5～10 μ m, transparency conducting layer is 0.35 λ, light absorbing zone (deceive/acryl resin by carbon black/titanium, n=1.63, k=0.35) thickness be that (silicon dioxide microparticle/acrylic acid particulate, thickness n=1.495) they are the reflectance spectrum of the light absorption type antireflection film (forming 4) of 0.175 λ for 0.15 λ and low-index layer.

As shown in Figure 5, by being formed in the light absorption type antireflection film of the special composition that forms transparency conducting layer, light absorbing zone and low-index layer on the hard conating, can realize the low-down antireflection film of reflectivity of short wavelength's one side.

Low-index layer as the superiors of antireflection film, not only its low-refraction is important, and permanance such as mar proof and chemical resistance also are very important, and as mentioned above, the application type antireflection film of the low-index layers that film properties is good and refractive index is low such as having mar proof, chemical resistance is not provided in the prior art, as yet.

Therefore, need a kind ofly not cause the transparent resin film deterioration, can on transparent resin film, form the low low-index layer of refractive index, and can produce the application type antireflection film that performances such as mar proof, chemical resistance are also good continuously.

On the other hand, in the antireflection film of the Plasmia indicating panel of antiradar reflectivity that requires short wavelength's one side and low transmissivity and CRT purposes,, can obtain good effect by adopting above-mentioned composition 4, even but form in 4 at this, still there is the problem that needs solution.

In the antireflection film (forming 1) of the routine of not using light absorbing zone, even in low-index layer, produce streak, transmissivity also can change hardly, therefore, even it is also not obvious a spot of damage to occur, and in the situation of the light absorption type antireflection film of this composition 4, if a spot of breakage appears in low-index layer, light absorbing zone also can be peeled off, and it is very high that the transmissivity at the light absorbing zone place of peeling off becomes, therefore, damage becomes very obvious.Therefore, in the antireflection film that uses this light absorbing zone, require the mar proof of low-refraction very high.

But in the situation of the film strength that improves low-index layer, the refractive index of low-index layer is n=1.49, becomes very high, can not realize sufficient low-refractionization.In above-mentioned composition 4, if the refractive index height of low-index layer, then in order would to obtain 0.5% or minimum reflectance below it, must increase the thickness of light absorbing zone, still, if increase the thickness of light absorbing zone, then exist transmissivity to reduce, become 70% or its following problem.

III. be applicable at various displays such as word processor, computer, CRT, plasm TV, LCD, organic EL, and in automobile, buildings, the glass pane of electric car and the picture glass of drawing etc., use antireflection film to guarantee high transmitance in order to prevent reflection of light.

On the other hand, if utilize the film build method of damp process such as nick version rubbing method, then can make antireflection film with lower cost.As the application type antireflection film, as shown in figure 21, mainly use on the surface of the formed transparent base film 21 of synthetic resin, stack gradually the antireflection film of hard conating 23, high refractive index layer 24 and low-index layer 25 from lower floor's one side.In addition, also have on base film, to form the electric conductivity high refractive index layer that has high refractive index layer and hard conating simultaneously, on it, form the antireflection film of low-index layer then.

As the application type low-index layer, also proposed by bond fixedly particle diameter be the method for particulate of the low-refraction (n) of 1～100nm.Wherein, by the acrylic compounds bond fixedly silicon dioxide microparticle (n=1.47) though layer film strength height, but the refractive index of silicon dioxide microparticle is higher, be about 1.47, thereby when using conventional bond, can not make the refractive index of formed low-index layer reach 1.49 or below it.

But in antireflection film, normally used base film is polyethylene terephthalate (PET) film or tri acetyl cellulose (TAC) film, in the PET film, considers from the thermotolerance aspect, can not carry out the heating more than 130 ℃.In utilizing the one-tenth embrane method of damp process, if the silicone composition that can not carry out heat-agglomerating processing etc. as bond, then chemical resistance, the non-constant of mar proof.Particularly dipping is about 30 minutes the time in alkaline aqueous solution (3 weight %NaOH), and the silicone composition produces basic hydrolysis, and film is dissolved easily to be fallen.Therefore, use comprise the bond of silicone composition and the system that mixes with hollow silica in, in the situation of strong wiping as the outermost low-index layer of antireflection film with alkaline detergent, since the dissolving of low-index layer, the anti-reflective function forfeiture.

But; according to discovering of the inventor; by the polyfunctional group acryl resin more than the difunctional is mixed the non-constant of film strength of the resulting film of back film forming with the porous silica particulate; even only the polyfunctional group acryl resin more than the difunctional is mixed with the porous silica particulate, can not form low-index layer with mar proof.In addition, in these patent documentations, directly form low-index layer, when still on base material, directly forming low-index layer like this, can not obtain the good films of the indispensable antireflection property of antireflection film such as minimum reflectance at substrate surface.And, in these patent documentations, use be porous silica particulate but not hollow silica particles, and porous silica can not fully reduce the refractive index of silicon dioxide, therefore, the refractive index of low-index layer can not reach fully low value.

IV. in Plasmia indicating panel (PDP), use the electromagnetic screen transmitance window material (PDP front surface filtrator) as purpose such as shielding electromagnetic wave, shielding near infrared ray, shielding neon usually.In addition, also continually developed the direct adhesion type gas discharge panel that is used to improve visuality.These have all given anti-reflective function in order to reduce external light reflection to the surface.

Figure 38 a opens the sectional view of the disclosed electromagnetic wave shielding transmitance of 2002-341779 window material 31 for the Jap.P. spy, this electromagnetic wave shielding transmitance window material 31 uses bonding intermediate coat 34A, clear binder 34B and the bonding agent 34C of using as bonding agent, with outermost antireflection film 33, as the near infrared screened film 35 stacked integrations of copper/pet layer etching-film 40, transparency carrier 32 and the innermost layer of electromagnetic wave shielding film, partly paste electric conductivity adhesive tape 37 with its integration at the end face of this duplexer with near the outer edge of this end face.In addition, the size of electromagnetic wave shielding film 40 and transparency carrier 32 much at one, in its marginal portion according to from a face around pasting electric conductivity adhesive tape 38 to the mode of another face.

33A is that transparent base film, 33B are antireflection film, usually, constitutes by stack gradually hard conating, high refractive index layer and low-index layer on transparent base.35A is that transparent base film, 35B are the near infrared absorption layer.38A, 37A are metal forming, and 38B is a bonding coat.41 is Copper Foil, and 42 is light absorbing zone, and 43 is transparent base film, and 44 is transparent adhesive layer.

In addition, Figure 38 b represents that the Jap.P. spy opens the sectional view of the disclosed gas discharge type luminescent panel of 2002-341781, in Figure 38 b, uses same-sign to represent for the parts with Figure 38 a performance identical function.This gas discharge type luminescent panel 60 uses bonding agent

intermediate coat

34A, 34B, the 34C as bonding agent, with outermost antireflection film 33, as the folded etching-film 40 of the copper/pet layer of electromagnetic wave shielding film, near infrared screened film 35, the 50 stacked integrations of luminophor panel body, at the end face of this duplexer with partly paste electric conductivity adhesive tape 37 near the outer edge of this end face and make its integration.

In addition, high refractive index layer and low-index layer as the anti-reflection layer that constitutes antireflection film, propose the dry type that a large amount of passing through utilize evaporation or sputter and become the embrane method film forming and the high refractive index layer and the low-index layer of film forming, but become in the embrane method in dry type, film forming procedure is time-consuming and cost is high, thereby utilizes the wet type of figure rubbing method to become embrane method just becoming main method.

As mentioned above, in the display surface of PDP etc., generally be used to reduce the antireflection film of outer reflection of light, particularly in the situation of PDP, the excitation the when color when antireflection film need improve light-off, bright lamp.But,, thereby be very difficult to carry out the adjustment of color because Plasmia indicating panel is luminous by the discharge of rare gas.Particularly in the situation of application type antireflection film, the high index of refractionization of the low-refractionization of low-index layer, high refractive index layer is that limited (for example, in low-index layer, its limit is about n=1.46, in high refractive index layer, its limit is about n=1.68.), in addition, color, raising excitation in order to strengthen reflected colour must have smooth reflectivity Characteristics in the visible region.In addition, in as outermost antireflection film, soil resistance also is necessary.

V. in panel display boards such as LCD, organic EL, CRT,, give anti-reflective function usually in order to prevent external light reflection.Up to now, in order to give this anti-reflective function, for example in the situation of CRT, disclosing by dry types such as sputtering method or vapour deposition methods becomes embrane method directly to form the method for antireflection film on the glass substrate on surface, on the transparency carrier film, paste the method for the antireflection film that forms by damp process such as dry process or nick version rubbing methods etc., wherein, utilize the method for dry process to have the shortcoming that film formation time is long, cost is high.Therefore, recently, mainly use damp process, still, the antireflection film that damp process forms is poorer than the antireflection film that forms by dry process aspect anti-reflective function, and this also is a shortcoming.

In addition, in the situation of LCD, used usually and formed trickle concavo-convex anti-dazzle film on the surface, since LCD is used to the TV purposes by damp process, the same with CRT, bring into use transparent (free from glare) antireflection film, have a composite membrane of above-mentioned anti-dazzle function and anti-reflective function simultaneously.

In addition, organic EL since be emissive type and the briliancy height, thereby do not need high antireflection, but in outdoor application, then require to reduce external light reflection raising visuality.

In addition, even in,, also require to prevent external light reflection in order to realize more high quality images and raising visuality with the contact-type display panel of PDA that uses LCD as representative.

On the other hand, for the displaying show window of artistic products and ornament etc., also require to prevent external light reflection so that can clearly distinguish the color of display material itself.

Therefore, in the prior art,, on the show window material, become embrane method to form antireflection film with dry type usually for special exhibit.That is,, and interfere pattern, aspect such as painted all to have problems, therefore adopt dry type to become embrane method usually because the show window material that wet type becomes embrane method to form can not obtain sufficient anti-reflective function under existing situation.But present situation is because the show window material price that dry type becomes embrane method to obtain is high, thereby and be not suitable for common show window material, and only be suitable for the show window material of special exhibit.

As mentioned above, in existing antireflection technique, the antireflection film that becomes embrane method to obtain owing to dry type costs an arm and a leg, thereby wishes to use wet type to become embrane method, still, becomes in the embrane method in wet type, and the raising of antireflection property is limited.That is, the high index of refractionization of the low-refractionization of low-index layer, high refractive index layer is limited (for example, its limit is about n=1.46 in the low-index layer, and its limit is about n=1.68 in the high refractive index layer).Therefore, can not realize the further raising of antireflection property.In addition, in order to improve excitation and to improve visual, must have smooth reflectivity Characteristics at visible-range, in addition, particularly in the show window material applications, in order to distinguish the color of display material itself, require to reduce change color (aberration), and existing antireflection film is difficult to satisfy the characteristic of these requirements.In addition, also must have soil resistance as outermost antireflection film.

VI. in recent years, consider that from efficent use of resources and aspect such as prevent the pollution of the environment the solar cell that sunshine is converted into electric energy is paid attention to by the people just day by day, and is constantly developing.

Solar cell usually forms structure as shown in figure 43: the diaphragm seal by ethylene-vinyl acetate copolymer (EVA)

resin film

113A, 113B between transparency protected parts 111 of the face side of sensitive surface one side and inner surface side guard block (rear cover material) 112, and with solar cell 114, be that arresting element such as silicone is sealed.

Such solar module 110 is made by the following method: stack gradually the transparency protected parts 111 of face side, diaphragm seal eva film 113A, used for solar batteries parts 114, sealing EVA resin film 113B and rear cover material 112 such as glass substrate; by heating and melting EVA and make its crosslinking curing, thus gluing integration.

Up to now; as the transparency protected parts of the face side of solar module; can use glass substrate without any processing; in using the common solar module of glass substrate as the transparency protected parts of face side; in this glass substrate; about 4% sunshine is reflected, thereby can not be converted into energy with being equivalent to this catoptrical sunshine, and this is the reason that causes hindering the raising of solar module generating efficiency.

It is also conceivable that in order to be used to reduce the anti-reflective function of external light reflection and to apply surface working giving as the surface of the glass substrate of the transparency protected parts of solar module face side; but present situation but is; the technology that cost and aspect of performance are fit to practicability can not be provided at, thereby any surface working can not be implemented.

On the other hand, at various displays such as word processor, computer, CRT, plasm TV, LCD, organic EL, and in the glass pane of automobile, buildings, electric car etc., in order to prevent that reflection of light is to guarantee high transmitance, use is provided with the antireflection film of high refractive index layer and low-index layer on the transparent base film surface, particularly form the antireflection film of high refractive index layer and low-index layer because cost of manufacture is cheap, thereby be widely adopted by damp process such as nick version rubbing methods.

Therefore, can think that such application type antireflection film also is applicable in the solar module, in existing antireflection film, antireflection property is insufficient, the particularly high ultraviolet conductively-closed of sun power, therefore, use such antireflection film, can cause generating efficiency to reduce sometimes on the contrary.

Summary of the invention

I. the 1st aspect the object of the present invention is to provide a kind ofly can not cause the transparent base film deterioration, can form the low low-index layer of refractive index easily, and can produce continuously, the application type antireflection film of function admirables such as mar proof, chemical resistance.

The antireflection film of the 1st aspect is a kind of hard conating that stacks gradually on transparent base film; the formed reflectance coating of high refractive index layer and low-index layer; perhaps on transparent base film, stack gradually the formed antireflection film of electric conductivity high index of refraction hard conating and low-index layer; it is characterized in that: this low-index layer is by being under the atmosphere gas of 0～10000ppm at oxygen concentration; by the right irradiation ultraviolet radiation of filming; its curing is obtained; wherein this is filmed and comprises: the silicon dioxide microparticle of hollow (hereinafter referred to as " hollow silica "); polyfunctional group (methyl) acrylic compounds; (methyl) acrylic compounds that promptly has (methyl) acryloyl group more than 2 or 2, Photoepolymerizationinitiater initiater.

The refractive index of employed hollow silica is low in the 1st aspect, is effective as the material of low-index layer.In addition, by selecting polyfunctional group (methyl) acrylic compounds, can give mar proof, chemical resistance, soil resistance, and can form good low-index layer as the bond composition.And, the low-index layer of the 1st aspect is cured by irradiation ultraviolet radiation under specific hypoxia condition, therefore need not heat, and then, the deterioration that can not cause transparent resin film can form in producing continuously that refractive index is very low, mar proof, the good low-index layer of chemical resistance.

Promptly; the inventor carries out the tracking test shown in the comparative experiments example as described later at above-mentioned prior art; found that: when forming low-index layer by the polyfunctional group acryl resin more than the difunctional is mixed with the porous silica particulate; film strength is very low; even only the polyfunctional group acryl resin more than the difunctional is mixed in the hollow silica particles, mar proof also can not improve fully.Find that in addition even directly form low-index layer at substrate surface, the indispensable antireflection property of antireflection films such as minimum reflectance institute is also still not enough.

Also find in addition, in the porous silica particulate, can not fully reduce the refractive index of silicon dioxide,, must use hollow silica for further low-refractionization.

Based on these opinions, the inventor finds: at first, form about film, by forming transparent base film/hard conating, high refractive index layer/low-index layer, perhaps, transparent base film/electric conductivity high index of refraction hard conating/low-index layer improves antireflection property.And, by irradiation ultraviolet radiation under the low-down condition of oxygen concentration bond is solidified, significantly improve the mar proof of low-index layer, wherein, only when using special acryl resin, can obtain very strong mar proof and chemical resistance, thereby finish the antireflection film of the 1st aspect as bond.

According to the 1st aspect, can provide a kind of and can not cause the transparent resin film deterioration, the low low-index layer of refractive index can be on transparent resin film, formed at short notice, and the application type antireflection film of function admirables such as mar proof, chemical resistance can be produced continuously.

II. the purpose of the 2nd aspect is to provide a kind of and can cause the transparent resin film deterioration, can on transparent resin film, form the low low-index layer of refractive index, and can produce the application type antireflection film of function admirables such as mar proof, chemical resistance continuously.

The 2nd aspect relates in particular to and stack gradually the formed antireflection film of hard conating, transparency conducting layer, light absorbing zone and low-index layer on transparent base film, perhaps on transparent base film, stack gradually hard conating, electric conductivity light absorbing zone and the formed antireflection film of low-index layer, wherein, by forming the low-index layer that refractive index is low and mar proof is good, can provide the reflectivity of short wavelength's one side low, can fully see through the light of blue-light-emitting, low, the not yellowy light absorption type of the transmitted colour antireflection film of transmissivity of short wavelength's one side.

The antireflection film of the 2nd aspect is to stack gradually hard conating on transparent base film; transparency conducting layer; the formed antireflection film of light absorbing zone and low-index layer; perhaps on transparent base film, stack gradually hard conating; the formed antireflection film of electric conductivity light absorbing zone and low-index layer; it is characterized in that; this low-index layer is by being under the atmosphere gas of 0～10000ppm at oxygen concentration; by its curing being obtained to the irradiation ultraviolet radiation of filming; this silicon dioxide microparticle (hereinafter referred to as " hollow silica ") of filming and comprising hollow wherein; polyfunctional group (methyl) acrylic compounds; (methyl) acrylic compounds that promptly has two or more (methyl) acryloyl groups; Photoepolymerizationinitiater initiater; and minimum reflectance is 0.5% or below it; the transmissivity of wavelength 550nm is 70% or more than it; the reflectivity of wavelength 400nm is 2% or below it.

The refractive index of employed hollow silica is low in the 2nd aspect, is effective as the material of low-index layer.In addition,, mar proof, chemical resistance, soil resistance can be given, good low-index layer can be formed by selecting polyfunctional group (methyl) acrylic compounds as the bond composition.And, the low-index layer of the 2nd aspect makes its curing by irradiation ultraviolet radiation under specific hypoxia condition, therefore need not heat, and then, the deterioration that can not cause transparent resin film can form in producing continuously that refractive index is very low, mar proof, the good low-index layer of chemical resistance.Therefore, can realize minimum reflectance be 0.5% or its transmissivity following, hard conating 550nm be 70% or its reflectivity above, wavelength 400nm be 2% or its following antireflection film.

Promptly; the inventor follows the trail of test at above-mentioned prior art; found that: when forming low-index layer by the polyfunctional group acryl resin more than the difunctional is mixed with the porous silica particulate; film strength is very low; even only the polyfunctional group acryl resin more than the difunctional is mixed in the hollow silica particles, mar proof also can not improve fully.Find that in addition even directly form low-index layer at substrate surface, the indispensable antireflection property of antireflection films such as minimum reflectance institute is also still not enough.

Based on these opinions, the inventor finds: at first, form about film, by forming transparent base film/hard conating/transparency conducting layer/light absorbing zone/low-index layer, perhaps, form transparent base film/easy adhesive layer/hard conating/electric conductivity light absorbing zone/low-index layer, improve antireflection property.And, by irradiation ultraviolet radiation under the low-down condition of oxygen concentration bond is solidified, significantly improve the mar proof of low-index layer, wherein, only when using special acryl resin, can obtain very strong mar proof and chemical resistance, thereby finish the antireflection film of the 2nd aspect as bond.

According to the 2nd aspect, can provide a kind of and can not cause the transparent resin film deterioration, the low low-index layer of refractive index can be on transparent resin film, formed at short notice, and the application type antireflection film of function admirables such as mar proof, chemical resistance can be produced continuously.

Especially,, in being provided with the antireflection film of light absorbing zone, can form the obviously good low-down low-index layer of refractive index of mar proof, thereby can reduce the thickness of light absorbing zone, improve transmissivity according to the antireflection film of the 2nd aspect.Therefore, can realize minimum reflectance be 0.5% or its transmissivity following, hard conating 550nm be 70% or its reflectivity above, wavelength 400nm be 2% or it is following, the antireflection film of high-transmission rate, antiradar reflectivity, be suitable for Plasmia indicating panel and CRT purposes.

III. the purpose of the 3rd aspect is to provide a kind of and can cause the transparent resin film deterioration, can easily form the low low-index layer of refractive index, and can produce continuously, the application type antireflection film of function admirables such as mar proof, chemical resistance.

The antireflection film of the 3rd aspect is to stack gradually easy adhesive layer on transparent base film; hard conating; the formed antireflection film of high refractive index layer and low-index layer; or on transparent base film, stack gradually easy adhesive layer; the formed antireflection film of high index of refraction hard conating and low-index layer; it is characterized in that; this low-index layer is by being under the atmosphere gas of 0～10000ppm at oxygen concentration; by its curing being obtained to the irradiation ultraviolet radiation of filming; the silicon dioxide microparticle (hereinafter referred to as " hollow silica ") that this is filmed and comprises hollow; polyfunctional group (methyl) acrylic compounds; (methyl) acrylic compounds that promptly has two or more (methyl) acryloyl groups, Photoepolymerizationinitiater initiater.

The refractive index of employed hollow silica is low in the 3rd aspect, is effective as the material of low-index layer.In addition,, mar proof, chemical resistance, soil resistance can be given, good low-index layer can be formed by selecting polyfunctional group (methyl) acrylic compounds as the bond composition.And, the low-index layer of the 3rd aspect makes its curing by irradiation ultraviolet radiation under specific hypoxia condition, therefore need not heat, and then, the deterioration that can not cause transparent resin film can form in producing continuously that refractive index is very low, mar proof, the good low-index layer of chemical resistance.

Promptly; the inventor follows the trail of test at above-mentioned prior art; found that: when the polyfunctional group acryl resin more than the difunctional is mixed the formation low-index layer with the porous silica particulate; film strength is very low; even only the polyfunctional group acryl resin more than the difunctional is mixed in the hollow silica particles, mar proof also can not improve fully.Find that in addition even directly form low-index layer at substrate surface, the indispensable antireflection property of antireflection films such as minimum reflectance institute is also still not enough.

Based on these opinions, the inventor finds: at first, form about film, by forming transparent base film/easy adhesive layer/hard conating, high refractive index layer/low-index layer, perhaps, form transparent base film/easy adhesive layer/electric conductivity high index of refraction hard conating/low-index layer, improve antireflection property.And, by irradiation ultraviolet radiation under the low-down condition of oxygen concentration bond is solidified, significantly improve the mar proof of low-index layer, wherein, only when using special acryl resin, can obtain very strong mar proof and chemical resistance, thereby finish the antireflection film of the 3rd aspect as bond.

According to the 3rd aspect, can provide a kind of and can not cause the transparent resin film deterioration, the low low-index layer of refractive index can be on transparent resin film, formed at short notice, and the application type antireflection film of function admirables such as mar proof, chemical resistance can be produced continuously.

IV. the purpose of the 4th aspect is to provide a kind of antireflection property of outermost anti-reflection layer good (minimizing of external light reflection, the minimizing of reflected colour), in addition also good high visual electromagnetic wave shielding transmitance window material and the gas discharge type luminescent panel of soil resistance.

The electromagnetic wave shielding window material of the 4th aspect is by forming to major general's electro-magnetic screen layer and transparency carrier, the stacked integration of outermost anti-reflection layer, it is characterized in that: this anti-reflection layer has high refractive index layer and is arranged on low-index layer on this high refractive index layer, and this low-index layer is to form by silicon dioxide microparticle (hereinafter referred to as " hollow silica "), polyfunctional group (methyl) acrylic compounds, filming of Photoepolymerizationinitiater initiater that photocuring contains hollow.

The gas discharge type luminescent panel of the 4th aspect is by luminescent panel body, the electro-magnetic screen layer, the stacked integration of outermost anti-reflection layer that are arranged on the front surface of this luminescent panel body are formed, it is characterized in that: this anti-reflection layer has high refractive index layer, is arranged on the low-index layer on this high refractive index layer, and this low-index layer is to form by silicon dioxide microparticle (hereinafter referred to as " hollow silica "), polyfunctional group (methyl) acrylic compounds, filming of Photoepolymerizationinitiater initiater that photocuring contains hollow.

The refractive index of employed hollow silica is low in the 4th aspect, is effective as the material of low-index layer.In addition,, mar proof, chemical resistance, soil resistance can be given, good low-index layer can be formed by selecting polyfunctional group (methyl) acrylic compounds as the bond composition.And the low-index layer of the 4th aspect makes its curing by irradiation ultraviolet radiation, therefore need not heat, and then, when using transparent resin film, can not cause its deterioration as base material yet, can form low-index layer with continuous production.

According to the 4th aspect, can provide a kind of antireflection property of outermost anti-reflection layer good (minimizing of external light reflection, the minimizing of reflected colour), in addition also good high visual electromagnetic wave shielding transmitance window material and the gas discharge type luminescent panel of soil resistance.

V. the purpose of the 5th aspect is to provide a kind of antireflection property good (minimizing of external light reflection, the minimizing of reflected colour, change color reduce) that is arranged on the anti-reflection layer on surface, and then also good high visual panel display board and the show window material of soil resistance.

The panel display board of the 5th aspect is a kind of panel display board that is provided with anti-reflection layer on the surface, wherein this anti-reflection layer possesses high refractive index layer, is arranged on the low-index layer on this high refractive index layer, it is characterized in that: this low-index layer is to form by silicon dioxide microparticle (hereinafter referred to as " hollow silica "), polyfunctional group (methyl) acrylic compounds, filming of Photoepolymerizationinitiater initiater that photocuring contains hollow.

The show window material of the 5th aspect is a kind of show window material that is provided with anti-reflection layer on the surface, wherein this anti-reflection layer possesses high refractive index layer, is arranged on the low-index layer on this high refractive index layer, it is characterized in that: this low-index layer is to form by silicon dioxide microparticle (hereinafter referred to as " hollow silica "), polyfunctional group (methyl) acrylic compounds, filming of Photoepolymerizationinitiater initiater that photocuring contains hollow.

The refractive index of employed hollow silica is low in the 5th aspect, is effective as the material of low-index layer.In addition,, mar proof, chemical resistance, soil resistance can be given, good low-index layer can be formed by selecting polyfunctional group (methyl) acrylic compounds as the bond composition.And the low-index layer of the 5th aspect makes its curing by irradiation ultraviolet radiation, therefore need not heat, and then, can not cause its deterioration when using transparent resin film as base material, can be to form low-index layer in the continuous production.

According to the 5th aspect, a kind of antireflection property good (minimizing of external light reflection, the minimizing of reflected colour, change color reduce) that is arranged on lip-deep anti-reflection layer can be provided, and then also good high visual panel display board and the show window material of soil resistance.

VI. the purpose of the 6th aspect is by form the high anti-reflection layer of external light reflection rate impingement rate low, sun power on the surface, the high efficiency solar cell assembly that provides a kind of generating efficiency to improve.

The solar module of the 6th aspect is to form with parts by battery by sealed solar between transparency protected parts of face side and inner surface side guard block; it is characterized in that: be the solar module that is formed with anti-reflection layer on the surface of the transparency protected parts of this face side; this anti-reflection layer possesses high refractive index layer and the low-index layer that is arranged on this high refractive index layer, and this low-index layer is the silicon dioxide microparticle (hereinafter referred to as " hollow silica ") that contains hollow by photocuring; polyfunctional group (methyl) acrylic compounds; filming of Photoepolymerizationinitiater initiater forms.

The refractive index of employed hollow silica is low in the 6th aspect, is effective as the material of low-index layer.In addition,, mar proof, chemical resistance, soil resistance can be given, good low-index layer can be formed by selecting polyfunctional group (methyl) acrylic compounds as the bond composition.And the low-index layer of the 6th aspect makes its curing by irradiation ultraviolet radiation, therefore need not heat, and then, even use transparent resin film, can not cause its deterioration as base material yet, can form low-index layer with continuous production.

According to the 6th aspect, by forming the high anti-reflection layer of external light reflection rate impingement rate low, sun power on the surface, the high efficiency solar cell assembly that provides a kind of antireflection efficient to improve.

Description of drawings

Fig. 1 is the diagrammatic cross-section of the formation of the conventional application type antireflection film of expression.

Fig. 2 is the diagrammatic cross-section of the formation of expression light absorption type antireflection film.

Fig. 3 is the reflected light spectrogram of existing antireflection film.

Fig. 4 is the reflected light spectrogram of existing antireflection film.

Fig. 5 is the reflected light spectrogram of light absorption type antireflection film.

Fig. 6 is the reflected light spectrogram of experimental example B-1.

Fig. 7 is the reflected light spectrogram of experimental example B-2.

Fig. 8 is the reflected light spectrogram of experimental example B-3.

Fig. 9 is the reflected light spectrogram of experimental example A-1.

Figure 10 is the reflected light spectrogram of experimental example A-2.

Figure 11 is the reflected light spectrogram of experimental example A-3.

Figure 12 is the reflected light spectrogram of experimental example B-4.

Figure 13 is the reflected light spectrogram of experimental example B-5.

Figure 14 is the reflected light spectrogram of experimental example B-6.

Figure 15 is the reflected light spectrogram of experimental example B-7.

Figure 16 is the reflected light spectrogram of experimental example A-4.

Figure 17 is the reflected light spectrogram of experimental example A-5.

Figure 18 is the reflected light spectrogram of experimental example A-6.

Figure 19 is the reflected light spectrogram of experimental example B-8.

Figure 20 is the reflected light spectrogram of experimental example B-9.

Figure 21 is the diagrammatic cross-section of the formation of the conventional application type antireflection film of expression.

Figure 22 is the reflected light spectrogram of experimental example b-1.

Figure 23 is the reflected light spectrogram of experimental example b-2.

Figure 24 is the reflected light spectrogram of experimental example b-3.

Figure 25 is the reflected light spectrogram of experimental example a-1.

Figure 26 is the reflected light spectrogram of experimental example a-2.

Figure 27 is the reflected light spectrogram of experimental example a-3.

Figure 28 is the reflected light spectrogram of experimental example b-4.

Figure 29 is the reflected light spectrogram of experimental example b-5.

Figure 30 is the reflected light spectrogram of experimental example b-6.

Figure 31 is the reflected light spectrogram of experimental example b-7.

Figure 32 is the reflected light spectrogram of experimental example a-4.

Figure 33 is the reflected light spectrogram of experimental example a-5.

Figure 34 is the reflected light spectrogram of experimental example a-6.

Figure 35 is the reflected light spectrogram of experimental example b-8.

Figure 36 is the reflected light spectrogram of experimental example b-9.

Figure 37 is the sectional view of the formation example of employed antireflection film in the 4th aspect of expression.

Figure 38 a is the diagrammatic cross-section of an example of the existing electromagnetic wave shielding transmitance window material of expression, and Figure 38 b is the diagrammatic cross-section of an example of the existing gas discharge type luminescent panel of expression.

Figure 39 is the diagrammatic cross-section of the formation example of employed antireflection film in the 5th aspect of expression.

Figure 40 is the figure of the thickness of expression high refractive index layer to the influence of reflectivity.

Figure 41 is the figure of the thickness of expression high refractive index layer to the influence of reflectivity.

Figure 42 is the diagrammatic cross-section of the surperficial anti-reflection layer of the embodiment of the solar module of the 6th aspect of expression.

Figure 43 is the sectional view of the structure of expression solar module.

Figure 44 is the figure of the thickness of expression high refractive index layer and low-index layer to the influence of reflectivity.

Embodiment

I. the embodiment of the 1st aspect

Below describe at the embodiment of the antireflection film of the 1st aspect.

As shown in Figure 1, the antireflection film of the 1st aspect has stacked gradually hard conating 2, high refractive index layer 3 and low-index layer 4 on transparent base film 1.Perhaps, in Fig. 1, electric conductivity high index of refraction hard conating is set, to replace hard conating and high refractive index layer.

In aspect the 1st, as base material 1, can list polyester, polyethylene terephthalate (PET), polybutylene terephthalate, polymethylmethacrylate (PMMA), acrylic resin, polycarbonate (PC), polystyrene, cellulosic triacetate (TAC), polyvinyl alcohol (PVA), Polyvinylchloride, Vingon, tygon, ethylene-vinyl acetate copolymer, polyurethane, viscose paper etc., the transparent membrane of preferred PET, PC, PMMA.

The thickness of base film 1 can be generally the scope of 1 μ m～10mm according to suitably decisions such as the desired characteristics of the purposes of resulting antireflection film (for example, intensity, film).

As hard conating 2, the hard conating of preferred synthetic resin, particularly, preferred ultraviolet curing resin, the combination of especially preferred multi-functional acrylate and silicon dioxide microparticle.The thickness of this hard conating 2 is preferably 2～20 μ m.

High refractive index layer 3 is preferably the synthetic resin that comprises metal oxide microparticle, as synthetic resin, and preferred especially ultraviolet hardening synthetic resin, especially preferred acrylic resin, epoxy resin, styrene resin, most preferably acrylic resin.In addition, as metal oxide microparticle, be preferably selected from ITO, TiO ₂, ZrO ₂, CeO ₂, Al ₂O ₃, Y ₂O ₃, La ₂O ₃And Ho ₂O ₃At least a kind or multiple high refractive index metal oxide particulate in the group of being formed, preferred especially TiO ₂Particulate, ITO particulate.

Ratio about metal oxide microparticle in the high refractive index layer 3 and synthetic resin, the synthetic resin deficiency if metal oxide microparticle is too much, then the film strength of high refractive index layer reduces, otherwise,, then can not fully improve refractive index if metal oxide microparticle is very few, therefore, with respect to the total amount of metal oxide microparticle and synthetic resin, the ratio of metal oxide microparticle is 10～60 volume %, is preferably 20～50 volume % especially.

The thickness of such high refractive index layer 3 is preferably about 80～100nm.In addition, the refractive index of this high refractive index layer 3 is preferably 1.65 or more than it, be preferably 1.66～1.85 especially, in this case, be controlled at 1.39～1.47 by the refractive index with low-index layer 4, the minimum reflectance that can obtain surface reflectivity is 1% or the good antireflection film of antireflection property below it.Particularly the refractive index of low-index layer 4 is controlled at 1.45 or the situation below it in, the minimum reflectance that can further improve antireflection, can also make surface reflectivity is 0.5% or antireflection film below it.

In aspect the 1st, low-index layer 4 be by under the atmosphere gas of the oxygen concentration of 0～10000ppm by the irradiation ultraviolet radiation of filming is obtained, wherein this is filmed and comprises bond composition and the Photoepolymerizationinitiater initiater that hollow silica, polyfunctional group (methyl) acrylic compounds form.

Hollow silica is a hollow shelly silicon dioxide microparticle, and its mean grain size is 10～200nm, is preferably 10～150nm especially.The mean grain size of this hollow silica is difficult to reduce the refractive index of hollow silica, and if greater than 200nm, then can have the problem of the diffuse reflection of light and the surfaceness increase of formed low-index layer etc. during less than 10nm.

Hollow silica has the low air of refractive index (refractive index=1.0) in hollow inside, therefore, its refractive index is compared remarkable reduction with conventional silicon dioxide (refractive index=1.46).The refractive index of hollow silica is that the volume ratio by its hollow space is determined, refractive index is preferably about 1.20～1.40 usually.

In addition, the refractive index of hollow silica: n (hollow silica) is the refractive index of the air of the refractive index from the silicon dioxide that constitutes hollow minute particle shell portion: n (silicon dioxide), inside: n (air), calculates according to following formula.

The percent by volume of n (hollow silica)=n (silicon dioxide) * silicon dioxide

As mentioned above, n (silicon dioxide) is about 1.47, and n (air) is 1.0, very low, and therefore, the refractive index of such hollow silica is very low.

In addition, use the refractive index of low-index layer of the 1st aspect of such hollow silica: n (low-index layer) is the refractive index of the refractive index by hollow silica: n (hollow silica) and bond composition: n (bond), calculates according to following formula.

N (low-index layer)=

The volume ratio of the bond in volume ratio+n (the bond) * low-index layer of the hollow silica in n (hollow silica) * low-index layer.

Wherein, except special fluorine-containing class bond, therefore the refractive index of bond is generally about 1.50～1.55,, increase the percent by volume of the hollow silica in the low-index layer, to the refractive index of low-index layer to reduce be important.

In aspect the 1st, the content of the hollow silica in the low-index layer is many more, then can form the low-index layer of low-refraction more, can access the good antireflection film of antireflection property, and along with the content of bond composition reduces relatively, the film strength of low-index layer reduces, and mar proof, permanance reduce.But the reduction of the film strength that increase caused of hollow silica combined amount can remedy by the surface treatment of hollow silica, in addition, also can replenish film strength by the kind of the bond composition selecting to be mixed.

In aspect the 1st, by the surface treatment of hollow silica and the selection of bond composition, the content that preferably makes the hollow silica in the low-index layer is 20～55 weight %, be in particular 30～50 weight %, to realize the low-refractionization of low-index layer, make refractive index about 1.39～1.45, guarantee mar proof simultaneously.

Then, polyfunctional group (methyl) acrylic compounds as the bond composition of the low-index layer of the 1st aspect is described.

This polyfunctional group (methyl) acrylic compounds is a principal ingredient with following general formula (I) represented 6 functional groups (methyl) acrylic compounds and/or represented 4 functional groups (methyl) acrylic compounds of following general formula (II) preferably, and preferably comprises 50 weight % in whole bond compositions or more than it, be preferably 90 weight % or more than it especially.

[changing 1]

(in the above-mentioned general formula (I), A ¹～A ⁶Represent acryloyl group, methacryl, α-fluorine acryloyl group or trifluoromethyl acryloyl group independently of one another,

N, m, o, p, q, r represent 0～2 integer independently of one another,

R ¹～R ⁶Represent that independently of one another carbon number is that carbon number that 1～3 alkylidene or one or more hydrogen atoms are replaced by fluorine atom is 1～3 the alkylidene of fluoridizing.)

[changing 2]

(in the above-mentioned general formula (II), A ¹¹～A ¹⁴Represent acryloyl group, methacryl, α-fluorine acryloyl group or trifluoromethyl acryloyl group independently of one another,

S, t, u, v represent 0～2 integer independently of one another,

R ¹¹～R ¹⁴Represent that independently of one another carbon number is that carbon number that 1～3 alkylidene or one or more hydrogen atoms are replaced by fluorine atom is 1～3 the alkylidene of fluoridizing.)

As represented 6 functional groups (methyl) acrylic compounds of above-mentioned general formula (I), can list the compound that the H of the ethylene oxide adduct of for example dipentaerythritol acrylate, dipentaerythritol acrylate or oxirane is replaced by F, these compounds can use a kind separately, also two or more can be used in combination.

In addition, as represented 4 functional groups (methyl) acrylic compounds of above-mentioned general formula (II), can list the compound that the H of ethylene oxide adduct of tetramethylol methane tetraacrylate, tetramethylol methane tetraacrylate (1～8) for example or oxirane is replaced by F, these compounds can use a kind separately, also two or more can be used in combination.

As the bond composition, can be used in combination a kind or represented 6 functional groups (methyl) acrylic compounds and a kind or represented 4 functional groups (methyl) acrylic compounds of multiple above-mentioned general formula (II) of multiple above-mentioned general formula (I).

Above-mentioned general formula (I), (II) represented polyfunctional group (methyl) acrylic compounds, represented 6 functional groups (methyl) acrylic compounds hardness height and the mar proof of particularly above-mentioned general formula (I) is good, can form the high low-index layer of mar proof effectively.

In addition, in aspect the 1st, as the bond composition, 4 functional groups (methyl) acrylic compounds that preferably that above-mentioned general formula (I) is represented 6 functional groups (methyl) acrylic compounds and/or above-mentioned general formula (II) are represented, be used in combination with represented fluorine-containing difunctional (methyl) acrylic compounds of following general formula (III) or specific fluorine-containing polyfunctional group (methyl) acrylic compounds, by using these bond compositions, can give mar proof and soil resistance to low-index layer.In addition, the refractive index of 4 functional groups (methyl) acrylic compounds that these bond compositions are more represented than represented 6 functional groups (methyl) acrylic compounds of above-mentioned general formula (I) or above-mentioned general formula (II) is lower, therefore, even reduce the combined amount of hollow silica, also can form the low low-index layer of refractive index.

A ^a-O-(CH ₂) _xa-Rf-(CH ₂) _xb-O-A ^b......(III)

(in above-mentioned general formula (III), A ^a, A ^bRepresent acryloyl group, methacryl, α-fluorine acryloyl group or trifluoromethyl acryloyl group independently of one another, Rf represents perfluorinated alkylidene, and xa, xb represent 0～3 integer independently of one another.)

As represented fluorine-containing difunctional (methyl) acrylic compounds of above-mentioned general formula (III), for example can list 2,2,3,3,4,4-hexafluoro pentanediol diacrylates etc., these compounds can use a kind separately, also can be with 2 kinds or multiple being used in combination.

In addition, above-mentioned specific polyfunctional group (methyl) acrylic compounds, promptly, have 6 or more a plurality of fluorine atom and molecular weight in 1 molecule and be 1000 or (methyl) acrylic compounds of its 3～6 following functional groups and in 1 molecular weight, have 10 or more a plurality of fluorine atom and molecular weight is that (methyl) acrylic compounds of 1000～5000 6～15 functional groups can be used a kind separately, also two or more can be used in combination.

Also a kind or multiple above-mentioned fluorine-containing difunctional (methyl) acrylic compounds can be used in combination with a kind or multiple fluorine-containing polyfunctional group (methyl) acrylic compounds.

Though, can realize the low-refractionization of low-index layer by using above-mentioned fluorine-containing difunctional (methyl) acrylic compounds, realize the raising of soil resistance, if its combined amount is too much, then mar proof reduces.Therefore, in total bond composition preferred mix 5 weight % or more than it, fluorine-containing difunctional (methyl) acrylic compounds of preferred especially 5～10 weight %.

In addition, though by using above-mentioned fluorine-containing polyfunctional group (methyl) acrylic compounds, also can realize the low-refractionization of low-index layer, realize the raising of soil resistance, if its combined amount is too much, then mar proof reduces.Therefore, in total bond composition preferred mix 5 weight % or more than it, fluorine-containing polyfunctional group (methyl) acrylic compounds of preferred especially 5～10 weight %.

In addition, in the situation that is used in combination fluorine-containing difunctional (methyl) acrylic compounds and fluorine-containing polyfunctional group (methyl) acrylic compounds, preferably in total bond composition, fluorine-containing difunctional (methyl) acrylic compounds and fluorine-containing polyfunctional group (methyl) acrylic compounds are mixed 5 weight % or its above, preferred especially 5～10 weight % altogether.

Employed hollow silica in aspect the 1st, its particle diameter is greater than the particle diameter of the conventional silicon dioxide microparticle that is mixed in the existing low-index layer (about particle diameter 5～20nm), therefore, even in the situation of using identical bond composition, compare with the situation of mixed silica particulate, the film strength of formed low-index layer has the tendency that dies down, and by this hollow silica being applied suitable surface treatment, can improve adhesion with the bond composition, improve the film strength of formed low-index layer, improve mar proof.

As the surface treatment of this hollow silica, preferably use represented end group (methyl) the acrylic silane coupling agent of following general formula (IV), it is acrylic acid modified that end group (methyl) is implemented on the surface of hollow silica.

[changing 3]

(in above-mentioned general formula (IV), R ²¹Expression hydrogen atom, fluorine atom or methyl,

R ²²The expression carbon number is that carbon number that 1～8 alkylidene or 1 or more a plurality of hydrogen atom are replaced by fluorine atom is 1～8 the alkylidene of fluoridizing,

R ²³～R ²⁵Represent that independently of one another hydrogen atom or carbon number are 1～4 alkyl.)

As such end group (methyl) acrylic silane coupling agent, can list for example CH ₂=CH-COO-(CH ₂) ₃-Si-(OCH ₃) ₃, CH ₂=C (CH ₃)-COO-(CH ₂) ₃-Si-(OCH ₃) ₃Deng, these compounds can use a kind separately, also can be with 2 kinds or multiple being used in combination.

For acrylic acid modified by using such end group (methyl) acrylic silane coupling agent that end group (methyl) is implemented on the surface of hollow silica, preferably make the mixed liquor of hollow silica and end group (methyl) acrylic silane coupling agent carry out hydro-thermal reaction at 100～150 ℃, perhaps, this mixed liquor irradiating microwaves is made its reaction.That is, when only mixing end group (methyl) acrylic silane coupling agent and hollow silica, can not carry out surface chemical modification, can not obtain needed surface modification effect with end group (methyl) acrylic silane coupling agent.In utilizing the situation of hydro-thermal reaction, if temperature of reaction is low, it is acrylic acid modified then can not to carry out sufficient end group (methyl).But if this temperature of reaction is too high, then reactivity reduces on the contrary, so hydrothermal temperature is preferably 100～150 ℃.In addition, the hydro-thermal reaction time is generally about 0.1～10 hour according to the difference of temperature of reaction and different.On the other hand, in utilizing the situation of microwave, if design temperature is low excessively, it is acrylic acid modified to carry out sufficient end group (methyl), and therefore, based on reason same as described above, design temperature is preferably 90～150 ℃.It is the microwave of 2.5GHz that this microwave is fit to frequency of utilization, if utilize microwave irradiation, it is acrylic acid modified to carry out end group (methyl) usually in the short time about 10～60 minutes.In addition, as the mixed liquor that is used for this reaction, for example can list the reaction solution that the silane coupling agent of water, the 0.04 weight % of acetic acid, the 1 weight % of alcoholic solvent (mixed solvent of 1: 4 (weight ratio) of isopropyl alcohol and isobutyl alcohol), the 3 weight % of hollow silica with 3.8 weight %, 96 weight % is made.

By utilizing such end group (methyl) acrylic silane coupling agent that chemical modification is carried out on the surface of hollow silica, hollow silica is combined securely with the bond composition, even in the more situation of the combined amount of hollow silica, also can form the good low-index layer of mar proof, can realize the low-refractionization of low-index layer by the combined amount that improves hollow silica.

In addition, hollow silica also can be carried out the modification of end group fluorinated alkyl to the surface by the represented end group fluorinated alkyl silane coupling agent of following general formula (V), in this case, the end group fluorinated alkyl modification that utilizes end group fluorinated alkyl silane coupling agent to carry out, preferably, undertaken by hydro-thermal method or microwave irradiation method carrying out end group (methyl) when acrylic acid modified under the identical condition with above-mentioned end group (methyl) the acrylic silane coupling agent that utilizes.

[changing 4]

(in above-mentioned general formula (V), R ³¹～R ³³Represent that independently of one another hydrogen atom or carbon number are 1～4 alkyl, ya represents 1～8 integer, and yb represents 1～3 integer.)

In addition, as above-mentioned end group fluorinated alkyl silane coupling agent, can list for example C ₈F ₁₇-(CH ₂) ₂-Si-(OCH ₃) ₃, C ₆F ₁₃-(CH ₂) ₂-Si-(OCH ₃) ₃Deng, these compounds can use a kind separately, also can be with 2 kinds or multiple being used in combination.

By using such end group fluorinated alkyl silane coupling agent that chemical modification is carried out on the surface of hollow silica, can improve the soil resistance of formed low-index layer.

The low-index layer of the 1st aspect is to above-mentioned bond composition irradiation ultraviolet radiation it to be solidified to form in the presence of Photoepolymerizationinitiater initiater, as this Photoepolymerizationinitiater initiater, can use a kind of イ Le ガキユア 184,819,651,1173,907 that Xiba Special Chemical Product Co.,Ltd for example makes etc. or multiple, its combined amount is preferably 3～10phr with respect to the bond composition.When the combined amount of Photoepolymerizationinitiater initiater is lower than this scope, can not carry out sufficient crosslinking curing, and if be higher than this scope, then the film strength of low-index layer reduces.

The low-index layer of the 1st aspect is by with hollow silica, as polyfunctional group (methyl) acrylic compounds of bond composition and Photoepolymerizationinitiater initiater according to the rules the composition that mixes of ratio be applied on high refractive index layer or the electric conductivity high index of refraction hard conating, by irradiation ultraviolet radiation under the atmosphere gas of the oxygen concentration of 0～10000ppm it is solidified to form, wherein, if the oxygen concentration in the ultraviolet ray irradiation atmosphere gas surpasses 1000ppm, then traumatic resistance significantly reduces, therefore, be controlled at 1000ppm or below it, be preferably 200ppm or below it.

The thickness of such low-index layer is preferably 85～110nm.

In aspect the 1st, in order on base film 1, to form hard conating 2, high refractive index layer 3 and low-index layer 4, perhaps form electric conductivity high index of refraction hard conating and low-index layer 4, the uncured resin combination (resin combination that mixes above-mentioned particulate as required) of preferred coating, then irradiation ultraviolet radiation.In this case, can every coating make its curing afterwards for 1 layer, perhaps be coated with after 3 layers or 2 layers, solidify together.

Concrete grammar as coating can list the coating fluid that will make the solubilize of bond composition with the toluene equal solvent and obtain, and is dry then with coatings such as intaglio plate spreaders, then utilizes the method for ultraviolet curing.According to this wet type rubbing method, have at a high speed evenly and the advantage of film forming at low cost.After coating, be cured, thereby played the effect that improves cohesive, raising film hardness, and need not heating, can produce antireflection film continuously by irradiation ultraviolet radiation.

The antireflection film of the 1st aspect like this is used for PDP or the front surface filtrator of liquid crystal panel or the window material of vehicle or special building of OA device, can guarantee good transmitance and permanance.

Below by enumerating embodiment and comparative example more specific description is carried out in the 1st aspect.

In addition, in following content, various characteristics, physical property are estimated according to following method.

The mensuration of＜refractive index 〉

Do not having on the P ET film of easy adhesive layer (" eastern レ Le ミラ one ", thickness 50 μ m), be the thickness coating low-index layer film-forming compositions of about 1/4 λ and make its curing with optical wavelength with respect to 550nm.Condition of cure is: ultraviolet cumulative exposure is 300mJ/cm ², the oxygen concentration when solidifying is 150ppm.Then, on uncoated face, paste black ethene adhesive tape, measure reflectivity, from the minimum reflectance calculating refractive index of this reflectance spectrum.

The mensuration of＜mar proof (frictional property of anti-the rubber) 〉

At thickness is on the TAC film (" TAC film " that the Off イ of Fuji Le system company makes) of 50 μ m, coating hard conating (" Z7503 " that JSR makes), and dry then, curing, forming thickness is 5 μ m, pencil hardness 3H or its above hard conating.Condition of cure is: ultraviolet cumulative exposure is 300mJ/cm ², the oxygen concentration when solidifying is 150ppm.Then, coating comprises the high refractive index layer film-forming compositions (" Ei-3 " that big Japanese coating (strain) is made) of ITO particulate and polyfunctional group acyclic compound and Photoepolymerizationinitiater initiater, dry, curing, the about 90nm of formation thickness, refractive index are 1.67～1.68 high refractive index layer.Condition of cure is: ultraviolet cumulative exposure is 300mJ/cm ², the oxygen concentration when solidifying is 150ppm.

Then, coating low-index layer film-forming compositions on high refractive index layer, dry, curing, the low-index layer of the about 95nm of formation thickness.Condition of cure is: ultraviolet cumulative exposure is 800mJ/cm ², the oxygen concentration when solidifying is 150ppm.

Antireflection film (reflected colour: purple), use plastic eraser to wipe at such manufacturing with about 4.9 * 10 ⁴N/m ²Its surface of load pressure reciprocating friction (low-refraction laminar surface).If the film of low-index layer is destroyed, then the variation of purple → redness → yellow slowly takes place in reflected colour, therefore with the reciprocal time till this color initial change as anti-rubber friction number of times, this anti-rubber friction number of times is is abrasion resistance properties good (zero) more than 100 times or 100 times the time, be bad (*) when being lower than 100 times.

＜minimum reflectance 〉

At the antireflection film that the method identical with the evaluation method of above-mentioned mar proof made, to paste black belt at inside surface (side opposite), and measure reflectance spectrum with 5 ° of normal reflections with film forming face, minimum reflectivity at this moment is designated as minimum reflectance.This minimum reflectance all is 0.5% or below it in " embodiment ".

＜chemical resistance 〉

Film forming face one at the antireflection film of the method manufacturing identical with the evaluation method of above-mentioned mar proof is sidelong tulle, drip the NaOH aqueous solution of several 3 weight %, cover Disposable paper cup in order to prevent the water evaporation in the NaOH aqueous solution from the top, placed 30 minutes down at 25 ℃.Then, tulle is taken away, with pure water washing, the reflected colour by the visualization antireflection film has no change, reflected colour is unconverted be designated as that chemical resistance good (zero), reflected colour change be designated as chemical resistance not good (*).

＜bond intensity 〉

In the bond composition, add 5phr Photoepolymerizationinitiater initiater (" イ Le ガキユア 184 (the イ Le ガキユア-184) " that Xiba Special Chemical Product Co.,Ltd makes, it is coated on the PET film " A4300 " that has two-sided easy adhesive layer of Japan's textile company manufacturing, then, oxygen concentration be under the atmosphere gas of 100ppm with metal halide lamp with 1000mJ/cm ²The accumulation light quantity carry out ultraviolet ray irradiation, it is solidified, forming thickness is the bonding agent layer of 8 μ m, at this bonding agent layer, the micro Vickers hardness meter that uses FISHERSCOPE company to make, 1 μ m measures Vickers hardness with depth of needling.

＜soil resistance 〉

Antireflection film at the method manufacturing identical with the evaluation method of above-mentioned mar proof, at the magic stroke superfine wire (redness) of its film forming face one side with the manufacturing of ZEBRA company,, the magic pen is designated as soil resistance good (zero) if can not ruling, if and can rule, then be designated as soil resistance not good (*).

In addition, as hollow silica, use mean grain size to be 60nm, refractive index n=about 1.30 or the hollow silica below it.

[embodiment]

Below, at the antireflection film of the 1st aspect, the experimental example of the effect that the performance that enumerating proves variety of way improves.

Experimental example 1

In order to carry out the evaluation of bond composition,, measure hardness by said method at the bond composition shown in the table 1.

In addition, the Photoepolymerizationinitiater initiater " イ Le ガキユア-184 " that in this bond composition, adds 5phr, add hollow silica, and make the total amount of Photoepolymerizationinitiater initiater and bond: hollow silica=62.5: 37.5 (weight %), obtain the low-index layer film-forming compositions, use said composition, detect mar proof and chemical resistance by said method, the result is as shown in table 1.

[table 1]

No	The bond composition			Bond	Chemical resistance	Mar proof
	The bond composition			Bond		Mar proof		Kind	Functional group's number	Molecular weight	Hardness (N/mm ²)	Anti-rubber friction number of times (inferior)	Estimate
	1	2-hydroxyethylmethacry,ate ※ 1	1	116		Can't measure	×	Kind	Functional group's number	Molecular weight	Hardness (N/mm ²)	Anti-rubber friction number of times (inferior)	Estimate	1	×
2	1	2-hydroxyethylmethacry,ate ※ 1	1	116	Dihydroxymethyl tristane diacrylate ※ 1	Can't measure	×	2	328	318	○	5	×	1	×
2	3	Trimethylolpropane triacrylate ※ 1	3	296	Dihydroxymethyl tristane diacrylate ※ 1	356	○	2	328	318	○	5	×	20	×
4	3	Trimethylolpropane triacrylate ※ 1	3	296	Pentaerythritol triacrylate ※ 1	356	○	3	298	423	○	30	×	20	×
4	5	Tetramethylol methane tetraacrylate ※ 1	4	352	Pentaerythritol triacrylate ※ 1	419	○	3	298	423	○	30	×	100	○
6	5	Tetramethylol methane tetraacrylate ※ 1	4	352	Dipentaerythritol acrylate ※ 1	419	○	6	580	476	○	175	○	100	○
6	7	U-15HA※2	15	2076	Dipentaerythritol acrylate ※ 1	473	○	6	580	476	○	175	○	35	×
8	7	U-15HA※2	15	2076	EA-6320※3	473	○	3	924	291	○	2	×	35	×
8	9	U-6HPA※4	6	818	EA-6320※3	156	○	3	924	291	○	2	×	25	×

※ 1: common prosperity company makes

※ 2: Xin Zhong village chemical industrial company makes (15 functional groups, high hardness type acrylic compounds oligomer)

※ 3: Xin Zhong village chemical industrial company makes (non-high hardness type)

※ 4: Xin Zhong village chemical industrial company makes (high hardness type urethane acrylate)

According to table 1 as can be known, for the bond composition, be not that functional group is many more just good more, if molecular weight increases, functional group's number is very many, although hardness rises, mar proof reduces.Therefore, though that mostly functional group's number is is good, if above to a certain degree molecular weight, hollow silica is as the performance degradation of bond.

Therefore, represented 6 functional groups of above-mentioned general formula (I), (II) or 4 functional groups (methyl) the acrylic compounds bond that is suitable as very much hollow silica.At this moment, chemical resistance is all good.

Experimental example 2

For the pre-treatment to hollow silica is estimated,, hollow silica is carried out pre-treatment as shown in table 2 by following method.In addition, as silane coupling agent, acrylic acid modified silane compound " the KBM-5103 " (CH that uses chemical company of SHIN-ETSU HANTOTAI to make ₂=CH-COO-(CH ₂) ₃-Si-(OCH ₃) ₃).

Pretreatment process (1): the acetic acid of 3.8 weight % hollow silica, 96 weight % alcoholic solvents (mixed solvent of isopropyl alcohol and isobutyl alcohol 19: 81 (weight ratio)), 3 weight %, the water of 1 weight %, the made reactant liquor of silane coupling agent of 0.04 weight % are put into the withstand voltage rustless steel container that PTFE (teflon) is posted in inside, and hydro-thermal was synthesized 4 hours under the temperature shown in the table 2.

Pretreatment process (2): will put into the microwave generator that Tokyo Electronics Inc. makes with the reaction solution that above-mentioned pre-treating method (1) similarly prepares, the microwave that 15 minutes frequencies of irradiation are 2.5GHz under the design temperature shown in the table 2.Because microwave generator reacts in open system, so reaction dissolvent can seethe with excitement.

Pretreatment process (3): and above-mentioned pretreatment process (1) preparation feedback solution similarly, then, do not apply any energy.

In addition, the silicon dioxide microparticle of preparing no hole (is produced " IPA-ST " (particle diameter 10～20nm)) that chemical company makes daily, this silicon dioxide microparticle and above-mentioned pretreatment process (1) is similarly carried out pre-treatment.

Use is without the hollow silica of pre-treatment, hollow silica through pre-treatment, silicon dioxide microparticle without pre-treatment, silicon dioxide microparticle through pre-treatment, in experimental example 1, to be evaluated as the best dipentaerythritol acrylate of mar proof as the bond composition, the polymerization initiator " イ Le ガキユア-184 " that in this bond composition, adds 5phr, make the total amount of Photoepolymerizationinitiater initiater and bond: particulate (hollow silica or silicon dioxide microparticle)=55: 45 (weight ratio), prepare the low-index layer film-forming compositions respectively, detect refractive index and chemical resistance and mar proof by said method, the result is as shown in table 2.

[table 2]

No.	Particle species	Have or not surface treatment	Surface treatment method		Refractive index	Chemical resistance	Anti-rubber friction number of times (inferior)	Comprehensive evaluation
			Surface treatment method						Method	Design temperature (℃)
			1	Silicon dioxide microparticle					Method	Design temperature (℃)	Do not have	-	-	1.50	○	＞500	×
2	Silicon dioxide microparticle	Have	1	Silicon dioxide microparticle	(1) hydro-thermal	120	1.50	○	＞500	×	Do not have	-	-	1.50	○	＞500	×
2	Silicon dioxide microparticle	Have	3	Hollow silica	(1) hydro-thermal	120	1.50	○	＞500	×	Do not have	-	-	1.42	○	25	×
4	Hollow silica	Have	3	Hollow silica	(3) reactionless	-	1.42	○	25	×	Do not have	-	-	1.42	○	25	×
4	Hollow silica	Have	5	Hollow silica	(3) reactionless	-	1.42	○	25	×	Have	(1) hydro-thermal	70	1.42	○	30	×
6	Hollow silica	Have	5	Hollow silica	(1) hydro-thermal	120	1.42	○	125	○	Have	(1) hydro-thermal	70	1.42	○	30	×
6	Hollow silica	Have	7	Hollow silica	(1) hydro-thermal	120	1.42	○	125	○	Have	(1) hydro-thermal	150	1.42	○	100	○
8	Hollow silica	Have	7	Hollow silica	(2) microwave	80	1.42	○	20	×	Have	(1) hydro-thermal	150	1.42	○	100	○
8	Hollow silica	Have	9	Hollow silica	(2) microwave	80	1.42	○	20	×	Have	(2) microwave	105	1.42	○	100	○

As shown in Table 2:

No.1,2 uses the silicon dioxide microparticle in no hole, no matter whether carry out pre-treatment, although mar proof is all very good, refractive index does not reduce, and the silicon dioxide microparticle that does not have the hole as can be known is not suitable as low-index material.

During in use empty silicon dioxide, though that the refractive index of the low-index layer as No.3 is reduced to is very low, if the ratio of hollow silica increases, then film strength reduces, and mar proof worsens.

And when in hollow silica, only adding silane coupling agent, film strength no change almost as No.4.

Even use hydro-thermal method that hollow silica and silane coupling agent are reacted, when temperature of reaction is 70 ℃ as No.5 mar proof no change almost, still, temperature of reaction mar proof in the time of 120～150 ℃ is very good as No.6,7.

In addition, use microwave, when when design temperature is 80 ℃, making it to react, mar proof no change almost as No.8, but temperature of reaction is provided with when reacting than the highland, mar proof improves very big as No.9.

Therefore,, the acrylic acid modified method of end group of hollow silica is arranged, can significantly improve mar proof by any that adopts hydro-thermal method or microwave irradiation method as can be known as the method for the mar proof of the low-index layer that improve to use hollow silica.

In addition, chemical resistance is all fine.

Experimental example 3

In order to study the effect of the raising soil resistance that the fluorinated silane coupling agent produced, fluorinated silane coupling agent " the KBM-7803 " (C that uses chemical company of SHIN-ETSU HANTOTAI to make ₈F ₁₇-(CH ₂) ₂-Si-(OCH ₃) ₃) as silane coupling agent, the same with the pretreatment process (1) of experimental example 2, under 120 ℃ temperature of reaction, carry out the pre-treatment of hollow silica by hydro-thermal method.

In addition and the pretreatment process of experimental example 2 (3) similarly only add the fluorinated silane coupling agent, the hollow silica that do not react of preparation.

Use is without the hollow silica of pre-treatment, the hollow silica of process pre-treatment, in experimental example 1, to be evaluated as the best dipentaerythritol acrylate of mar proof as the bond composition, the polymerization initiator " イ Le ガキユア-184 " that in this bond composition, adds 5phr, make the total amount of Photoepolymerizationinitiater initiater and bond: hollow silica=62.5: 37.5 (weight ratio), prepare the low-index layer film-forming compositions respectively, detect refractive index and chemical resistance and mar proof by said method, the result is as shown in table 3.

[table 3]

No.	Hollow silica has or not surface treatment	Surface treatment method	Refractive index	Anti-rubber friction number of times (inferior)	Soil resistance	Chemical resistance	Comprehensive evaluation
No.	Hollow silica has or not surface treatment	Surface treatment method	Refractive index	Anti-rubber friction number of times (inferior)	Soil resistance	Chemical resistance	Comprehensive evaluation	1	Do not have	-	1.432	175	×	○	○
2	Have	(3) reactionless	1.428	90	○	○	×	1	Do not have	-	1.432	175	×	○	○
2	Have	(3) reactionless	1.428	90	○	○	×	3	Have	(2) hydro-thermal	1.428	120	○	○	◎

As shown in Table 3, owing to reduced the combined amount of hollow silica a little, in No.1, mar proof is very good, but does not have soil resistance, and as No.2, if add the fluorinated silane coupling agent any reaction does not take place, though soil resistance becomes well, film strength has but reduced.As No.3, if through the reaction of fluorinated silane coupling agent and hollow silica and modification hollow silica, then can when being endowed soil resistance, film strength also strengthen.And refractive index also improves.

In addition, chemical resistance is all fine.

Experimental example 4

In order to study the effect that fluorine-containing difunctional (methyl) acrylic compounds and fluorine-containing polyfunctional group (methyl) acrylic compounds are brought, dipentaerythritol acrylate to mar proof the best in the experimental example 1, with the blending constituent shown in the table 4 with blending constituent: dipentaerythritol acrylate=10: 90 (weight ratio) mixes the material that obtains as the bond composition, the Photoepolymerizationinitiater initiater " イ Le ガキユア-184 " that in this bond composition, adds 5phr, make the total amount of Photoepolymerizationinitiater initiater and bond: hollow silica=70: 30 (weight ratio) (wherein, only dipentaerythritol acrylate in No.1, the total amount of Photoepolymerizationinitiater initiater and bond composition: hollow silica=62.5: 37.5 (weight ratio)), preparation low-index layer film-forming compositions, detect refractive index and mar proof and soil resistance by said method, the result is as shown in table 4.

[table 4]

No	Blending constituent	Refractive index	Anti-rubber friction number of times (inferior)	Soil resistance	Comprehensive evaluation
No	Blending constituent	Refractive index	Anti-rubber friction number of times (inferior)	Soil resistance	Comprehensive evaluation	1	-	1.43	175	×	○
2	CH ₂＝CH-COO-CH ₂-CF ₃	1.43	50	×	×	1	-	1.43	175	×	○
2	CH ₂＝CH-COO-CH ₂-CF ₃	1.43	50	×	×	3	CH ₂＝CH-COO-CH ₂-C ₈F ₁₇	1.43	20	○	×
4	Fluorine-containing difunctional (methyl) acrylic compounds	1.43	125	○	○	3	CH ₂＝CH-COO-CH ₂-C ₈F ₁₇	1.43	20	○	×
4	Fluorine-containing difunctional (methyl) acrylic compounds	1.43	125	○	○	5	Bifunctional monomer's (molecular weight about 300)	1.43	35	○	×
6	Bifunctional monomer's (molecular weight about 400)	1.43	5	○	×	5	Bifunctional monomer's (molecular weight about 300)	1.43	35	○	×
6	Bifunctional monomer's (molecular weight about 400)	1.43	5	○	×	7	Trifunctional monomer (molecular weight about 400)	1.43	100	○	○
8	Trifunctional monomer (molecular weight about 500)	1.43	100	○	○	7	Trifunctional monomer (molecular weight about 400)	1.43	100	○	○
8	Trifunctional monomer (molecular weight about 500)	1.43	100	○	○	9	Four-functional group monomer (molecular weight about 600)	1.43	100	○	○
10	Six functional groups monomer (molecular weight about 1000)	1.43	100	○	○	9	Four-functional group monomer (molecular weight about 600)	1.43	100	○	○

As shown in Table 4:

In not adding the No.1 of blending constituent,, but there is not soil resistance though mar proof is enough.Mix the simple function group fluorinated acrylic monomers as the No.2,3 of blending constituent in or mix among the No.5,6 of difunctional acrylic monomers as blending constituent, mar proof is reduced to very low.In contrast, in the No.4,7～10 that has mixed represented fluorine-containing difunctional (methyl) acrylic compounds of general formula (III) or fluorine-containing polyfunctional group of the present invention (methyl) acrylic compounds, can when improving mar proof, obtain soil resistance.

[comparative example]

Comparative experiments example 1

Open 2003-202406 communique, Jap.P. spy as above-mentioned Jap.P. spy and open the 2003-202960 communique, use silicone bond composition to prepare low-index layer, measure the film strength of this moment and the experiment of chemical resistance.

The preparation method of bond composition is as described below.

At first, in 208 weight portion methyl triethoxysilane, ethyl triethoxysilane or tetraethoxysilane, add 356 weight portion methyl alcohol, and then mix the hydrochloric acid ([H of 18 weight parts waters and 18 weight portion 0.01N ₂O]: [OR]=0.5), stir.In 25 ℃ calibration cell, stirred this mixed solution 2 hours.Then, mix this silanes bond and hollow silica, be modulated into bond: hollow silica=65: 35 (weight ratio).Further, use isopropyl alcohol to dilute and reach 8 weight % until total solid constituent, with it as the low-index layer film-forming compositions.

This low-index layer film-forming compositions is applied on the high refractive index layer, and except carrying out 30 minutes the thermal treatment under 120 ℃ and above-mentioned experimental example is similarly checked chemical resistance and mar proof (anti-rubber friction number of times), the result is as shown in table 5.

[table 5]

No.	The bond composition	Chemical resistance	Anti-rubber friction number of times (inferior)	Comprehensive evaluation
No.	The bond composition	Chemical resistance	Anti-rubber friction number of times (inferior)	Comprehensive evaluation	1	Methyl triethoxysilane	×	15	×
2	Ethyl triethoxysilane	×	15	×	1	Methyl triethoxysilane	×	15	×
2	Ethyl triethoxysilane	×	15	×	3	Tetramethoxy-silicane	×	25	×

As shown in Table 5, when using silicone bond composition, be merely able to form chemical resistance, the significantly reduced low-index layer of mar proof.

Comparative experiments example 2

Mar proof, chemical resistance, antireflection property when then above-mentioned Jap.P. spy being opened 2003-261797 communique, Jap.P. spy and opens 2003-262703 communique, Jap.P. spy and open that the 2003-266602 communique is disclosed directly to form low-index layer on base material are studied.

At first, the method of putting down in writing by these patent documentations forms the low-index layer film-forming compositions on transparent base, described film-forming compositions be by various multi-functional acrylates and hollow silica according to the multi-functional acrylate: the ratio of hollow silica=65: 35 (weight ratio) mixes.This low-index layer film-forming compositions is applied on the PET film " A4100 " that has easy adhesive layer that Japan spinning company makes, under indoor atmosphere gas with ultraviolet cumulative exposure 800mJ/cm ²Shine and make its curing, the low-index layer of the about 95nm of formation thickness.Oxygen concentration during curing is about 20%.

At the antireflection film that on the PET film, directly forms low-index layer like this, check its mar proof (anti-rubber friction number of times) and chemical resistance by said method, the result is as shown in table 6.

In addition, measure minimum reflectance,, confirm that antireflection property is poor all above 1.0% by said method.

[table 6]

No.	The bond composition		Anti-rubber friction number of times (inferior)	Soil resistance	Comprehensive evaluation
	The bond composition					Kind	Functional group's number
	1	Glycol diacrylate				Kind	Functional group's number	2	＜10	×	Antireflection property is low, and mar proof, chemical resistance are also low when using the silicone bond
2	1	Glycol diacrylate	1,6 hexanediol diacrylate	2	＜10	×		2	＜10	×
2	3	Trimethylolpropane triacrylate	1,6 hexanediol diacrylate	2	＜10	×	3	＜10	×
4	3	Trimethylolpropane triacrylate	Tetramethylol methane tetraacrylate	4	＜10	×	3	＜10	×
4	5	Dipentaerythritol acrylate	Tetramethylol methane tetraacrylate	4	＜10	×	6	＜10	×

As shown in Table 6, directly form in the antireflection film of low-index layer on substrate surface, antireflection property is low.And, the poor adhesion of substrate surface and low-index layer, so mar proof compares when using the silicone bond also low.Therefore, only in hollow silica, mix the polyfunctional group acryl resin and can not guarantee mar proof fully, and chemical resistance is also very poor.

Comparative experiments example 3

According to the result of comparative experiments example 2, whether be the reason that cause performance bad to the inventor in order to verify if directly forming the such membrane structure of low-index layer at substrate surface, then changes membrane structure and carried out following experiment.

On (" TAC film " that the Off イ of Fuji Le system company makes) on the TAC film of thick 50 μ m, coating hard conating (" Z7503 " that JSR makes), dry solidification forms thick 5 μ m, pencil hardness 3H or its above hard conating then.Condition of cure is: ultraviolet cumulative exposure is 300mJ/cm ², the oxygen concentration when solidifying is 150ppm.Then, coating comprises the high refractive index layer film-forming compositions (" Ei-3 " that big Japanese coating (strain) is made) of ITO particulate and polyfunctional group acyclic compound and Photoepolymerizationinitiater initiater, dry, curing, the about 90nm of formation thickness, refractive index are 1.67～1.68 high refractive index layer.Condition of cure is: ultraviolet cumulative exposure is 300mJ/cm ², the oxygen concentration when solidifying is 150ppm.

Then, comparative experiments example 2 prepared low-index layer film-forming compositions are coated on the high refractive index layer dry, curing, the low-index layer of the about 95nm of formation thickness respectively.Condition of cure is: ultraviolet cumulative exposure is 800mJ/cm ², the oxygen concentration when solidifying is about 20% of indoor atmosphere gas.

(reflected colour: purple), check its mar proof (anti-rubber friction number of times) and chemical resistance by said method, the result is as shown in table 7 at the antireflection film of such manufacturing.

In addition, measuring minimum reflectance by said method, all is 0.5% or below it, confirms that antireflection improves.

[table 7]

No.	The bond composition		Anti-rubber friction number of times (inferior)	Chemical resistance	Comprehensive evaluation
	The bond composition					Kind	Functional group's number
	1	Glycol diacrylate				Kind	Functional group's number	2	＜10	×	Antireflection property is improved, but mar proof, chemical resistance are still low
2	1	Glycol diacrylate	1,6 hexanediol diacrylate	2	＜10	×		2	＜10	×
2	3	Trimethylolpropane triacrylate	1,6 hexanediol diacrylate	2	＜10	×	3	＜10	×
4	3	Trimethylolpropane triacrylate	Tetramethylol methane tetraacrylate	4	＜10	×	3	＜10	×
4	5	Dipentaerythritol acrylate	Tetramethylol methane tetraacrylate	4	＜10	×	6	＜11	×

As shown in Table 7, compare with the comparative experiments example 3 that on base material, directly forms low-index layer, antireflection property improves, in addition, though because the cohesive of low-index layer is improved, therefore mar proof has improvement slightly, but the mar proof distance is also far as the level of the commodity of antireflection film, and chemical resistance is also very poor.

By the contrast of above-mentioned experimental example and comparative experiments example as can be known, not only use hollow silica as particulate and use difunctional or more multi-functional (methyl) acrylic compounds as the bond composition, according to the 1st aspect, by layer structure made transparent base film/hard conating/high refractive index layer/low-index layer, when further under the low oxygen concentration condition of 0～10000ppm, low-index layer being carried out ultraviolet ray irradiation and solidify, can effectively improve mar proof, chemical resistance and antireflection property.

II. the embodiment of the 2nd aspect

Embodiment at the antireflection film of the 2nd aspect describes below.

As shown in Figure 2, the antireflection film of the 2nd aspect stacks gradually easy adhesive layer 12, hard conating 13, transparency conducting layer 14, light absorbing zone 15 and low-index layer 16 and forms on transparent base film 11.Perhaps, in Fig. 2, the electric conductivity light absorbing zone is set to replace transparency conducting layer and light absorbing zone.

In aspect the 2nd, as base film 11, can list polyester, polyethylene terephthalate (PET), polybutylene terephthalate, polymethylmethacrylate (PMMA), acrylic resin, polycarbonate (PC), polystyrene, cellulosic triacetate (TAC), polyvinyl alcohol (PVA), Polyvinylchloride, Vingon, tygon, ethylene-vinyl acetate copolymer, polyurethane, viscose paper etc., the transparent membrane of preferred PET, PC, PMMA.

The thickness of base film 11 can be generally 1 μ m～10mm according to suitably decisions such as the desired characteristics of the purposes of resulting antireflection film (for example, intensity, film).

As transparent base film, preferred especially PET film, in the situation of PET film, being coated with refractive index in the above-mentioned hard conating side of this PET film is 1.55～1.61 and thickness when being the easy adhesive layer of 75～95nm, minimum reflectance reduces, does not have and interfere, so preferred.

Easily adhesive layer 12 is used to improve the cohesive of 13 pairs of base films 11 of hard conating, uses usually in heat-curing resins such as copolymer polyester resin and urethane resin and mixes SiO ₂, ZrO ₂, TiO ₂, Al ₂O ₃Deng metal oxide microparticle, preferred mean grain size is that metal oxide microparticle about 1～100nm is regulated the material of refractive index.In addition, can also only just refractive index be controlled to be 1.58 with resin.

Hard conating 13 on this transparent base film 11 can form by common hard paints such as acrylic resins of painting, silicone resins.The known uv absorption material that can mix as required in this hard conating about 0.05～5 weight % is given the ultraviolet screener performance to it.The thickness of hard conating 13 is preferably about 2～20 μ m.

In aspect the 2nd, the refractive index of this hard conating 13 is 1.48～1.55, in this case, and when the refractive index with easy adhesive layer 12 is designated as n _a, the refractive index of transparent base film 11 is designated as n _b, the refractive index of hard conating 13 is designated as n _HCThe time, when

(n _b+n _HC)/2-0.03≤n _a≤(n _b+n _HC)/2+0.03

Particularly, (n _b+ n _HC)/2-0.01≤n _a≤ (n _b+ n _HC)/2+0.01,

Easily the thickness T of adhesive layer 12 satisfies:

(550/4)×(1/n _a)-10nm≤T≤(550/4)×(1/n _a)+10nm

Particularly

(550/4) * (1/n _a)-5nm≤T≤(550/4) * (1/n _aDuring the scope of)+5nm, can obtain obviously good antireflection property, so preferably.

Transparency conducting layer 14 on the hard conating 13 preferably forms by the following method: will be selected from ATO (antimony-doped tin oxide), ZnO, Sb ₂O ₅, SnO ₂, ITO (indium tin oxide) and In ₂O ₃At least a electrically conductive microparticle in the group of being formed is mixed in the bond compositions such as acrylic compounds; form coating fluid; this coating fluid is applied on the hard conating 13 on the easy adhesive layer 12 that is formed at transparent base film 11; and preferably resulting filming carried out photocuring, thereby form transparency conducting layer.

The blending ratio of electrically conductive microparticle in this coating fluid and bond composition can wait suitably by the refractive index of formed transparency conducting layer 14 and determine, preferred combination agent composition: electrically conductive microparticle=100: 200～700 (weight ratio).

The thickness of such transparency conducting layer 14 is preferably 80～200nm.Can not obtain sufficient electric conductivity when the thickness of transparency conducting layer 14 is thinner than this scope, the sheet resistance value of resulting antireflection film raises.And if transparency conducting layer 14 is blocked up, then optical property (antireflection property) extremely reduces.

In addition, the mean grain size of employed electrically conductive microparticle is preferably 5～100nm in the formation of transparency conducting layer 14.

Light absorbing zone 15 can form by the following method: will be preferably selected from least a kind of light absorption particulate in the group that metal oxide, metal nitride and carbon forms, the potpourri of preferred especially carbon black particle and titanium nitride particulate is mixed in the bond composition such as acrylic compounds, form coating fluid, this coating fluid is applied on the transparency conducting layer 14, and preferably resulting filming is carried out photocuring and formed light absorbing zone 15.

The light absorption particulate in this coating fluid and the blending ratio of bond composition can wait suitably according to the attenuation coefficient of formed light absorbing zone 15 and determine, in aspect the 2nd, by with the blending ratio of this light absorption particulate and bond composition at the bond composition: suitably adjust in the scope of light absorption particulate=100～100～700, when then the complex index of refraction of light absorbing zone being designated as n+ik, form the light absorbing zone of n=1.45～1.75, k=0.1～0.35, can obtain good antireflection, so preferred.

The thickness of such light absorbing zone 15 is preferably 20～100nm.If the thickness of light absorbing zone 15 is thicker than this scope, then transmissivity reduces.But, if the thickness of light absorbing zone 15 is thin excessively, then can not obtain enough antireflection properties, so not preferred.

In addition; in forming the situation of electric conductivity light absorbing zone with replacement transparency conducting layer and light absorbing zone; the electric conductivity light absorbing zone preferably forms by the following method: electric conductivity light absorption particulates such as carbon black are mixed in the bond composition such as acrylic compounds and form coating fluid; this coating fluid is applied on the hard conating, and preferably resulting filming is carried out photocuring and formed the electric conductivity light absorbing zone.

The electric conductivity light absorption particulate in this coating fluid and the blending ratio of bond composition can wait suitably according to the attenuation coefficient of formed electric conductivity light absorbing zone and determine, in aspect the 2nd, by with the blending ratio of this electric conductivity light absorption particulate and bond composition at the bond composition: suitably adjust in the scope of electric conductivity light absorption particulate=100～100～700, when the complex index of refraction with the electric conductivity light absorbing zone is designated as n+ik, form n=1.45～1.75, the electric conductivity light absorbing zone of k=0.1～0.35, can obtain good antireflection, so preferred.

The thickness of such electric conductivity light absorbing zone is preferably 20～100nm.If the thickness of electric conductivity light absorbing zone is thicker than this scope, then transmissivity reduces.But, if the thickness of electric conductivity light absorbing zone is thin excessively, then can not obtain enough antireflections, so not preferred.

In aspect the 2nd, low-index layer 16 be by under the atmosphere gas of the oxygen concentration of 0～10000ppm by to the irradiation ultraviolet radiation of filming, its curing is obtained, and wherein this is filmed and comprises hollow silica and polyfunctional group (methyl) bond composition that acrylic compounds constituted and photopolymer initiating agent.

Hollow silica is the silicon dioxide microparticle of hollow shelly, and its mean grain size is 10～200nm, is preferably 10～150nm.The mean grain size of this hollow silica is difficult to reduce the refractive index of hollow silica during less than 10nm, and when surpassing 200nm, the problem of the diffuse reflection of light or the surfaceness increase of formed low-index layer etc. takes place.

Hollow silica has the low air of refractive index (refractive index=1.0) in hollow inside, therefore, its refractive index significantly is lower than common silicon dioxide (refractive index=1.46).The refractive index of hollow silica is that the volume ratio by its hollow space is determined, is preferably about 1.20～1.40 usually.

In addition, the refractive index of hollow silica: n (hollow silica) is the refractive index from the silicon dioxide of the shell part that constitutes hollow minute particle: the refractive index of the air of n (silicon dioxide), inside: n (air), calculated by following formula.

As mentioned above, n (silicon dioxide) is about 1.47, and n (air) is 1.0, and is very low, and therefore, the refractive index of such hollow silica is very low.

In addition, use the refractive index of low-index layer of the 2nd aspect of such hollow silica: n (low-index layer) is the refractive index of the refractive index from hollow silica: n (hollow silica) and bond composition: n (bond), calculates according to following formula.

N (low-index layer)=

In aspect the 2nd, the content of the hollow silica in the low-index layer is many more, then can form the low-index layer of low-refraction more, can access the good antireflection film of antireflection property, and along with the content of bond composition reduces relatively, the film strength of low-index layer reduces, and mar proof, permanance reduce.But, the reduction of the film strength that increase caused of hollow silica combined amount can remedy by the surface treatment of hollow silica, in addition, also can replenish film strength by the kind of the bond composition selecting to be mixed.

In aspect the 2nd, by the surface treatment of hollow silica and the selection of bond composition, hollow silica content in the low-index layer is preferably 20～50 weight %, be preferably 25～50 weight % especially, to realize the low-refractionization of low-index layer, guarantee mar proof when making refractive index about 1.39～1.45.

Then, describe at polyfunctional group (methyl) acrylic compounds as the bond composition of the low-index layer of the 2nd aspect.

This polyfunctional group (methyl) acrylic compounds is a principal ingredient with following general formula (I) represented 6 functional groups (methyl) acrylic compounds and/or represented 4 functional groups (methyl) acrylic compounds of following general formula (II) preferably, and preferably comprises 50 weight % in whole bond compositions or more than it, be preferably 80 weight % especially.

[changing 5]

N, m, o, p, q, r represent 0～2 integer independently of one another,

[changing 6]

S, t, u, v represent 0～2 integer independently of one another,

In addition, as represented 4 functional groups (methyl) acrylic compounds of above-mentioned general formula (II), can list compound that the H of ethylene oxide adduct of tetramethylol methane tetraacrylate, tetramethylol methane tetraacrylate (1～8) for example or oxirane replaced by F etc., these compounds can use a kind separately, also two or more can be used in combination.

As bond, can be used in combination a kind or multiple represented 6 functional groups (methyl) acrylic compounds and a kind or multiple represented 4 functional groups (methyl) acrylic compounds of above-mentioned general formula (II) of above-mentioned general formula (I).

In addition, in aspect the 2nd, as the bond composition, 4 functional groups (methyl) acrylic compounds that preferably that above-mentioned general formula (I) is represented 6 functional groups (methyl) acrylic compounds and/or above-mentioned general formula (II) are represented, be used in combination with represented fluorine-containing difunctional (methyl) acrylic compounds of following general formula (III) or specific fluorine-containing polyfunctional group (methyl) acrylic compounds, by using these bond compositions, can give mar proof and soil resistance to low-index layer.In addition, the refractive index of 4 functional groups (methyl) acrylic compounds that these bond compositions are more represented than represented 6 functional groups (methyl) acrylic compounds of above-mentioned general formula (I) or above-mentioned general formula (II) is lower, therefore, even the combined amount of hollow silica reduces, also can form the low low-index layer of refractive index.

A ^a-O-(CH ₂) _xa-Rf-(CH ₂) _xb-O-A ^b......(III)

In addition, though by using above-mentioned fluorine-containing polyfunctional group (methyl) acrylic compounds, can realize the low-refractionization of low-index layer, realize the raising of soil resistance, if its combined amount is too much, then mar proof reduces.Therefore, in total bond composition preferred mix 5 weight % or more than it, polyfunctional group (methyl) acrylic compounds of preferred especially 5～10 weight %.

Employed hollow silica in aspect the 2nd, its particle diameter is greater than the particle diameter of the conventional silicon dioxide microparticle that is mixed in the existing low-index layer (about particle diameter 5～20nm), therefore, even in the situation of using identical bond composition, compare with the situation of mixed silica particulate, the film strength of formed low-index layer has the tendency that dies down, and by this hollow silica being applied suitable surface treatment, can improve adhesion with the bond composition, improve the film strength of formed low-index layer, improve mar proof.

[changing 7]

For acrylic acid modified by using such end group (methyl) acrylic silane coupling agent that the hollow silica surface is implemented end group (methyl), preferably make the mixed liquor of hollow silica and end group (methyl) acrylic silane coupling agent carry out hydro-thermal reaction at 100～150 ℃, perhaps, this mixed liquor irradiating microwaves is made its reaction.That is, when only mixing end group (methyl) acrylic silane coupling agent and hollow silica, can not carry out surface chemical modification, can not obtain needed surface modification effect with end group (methyl) acrylic silane coupling agent.In utilizing the situation of hydro-thermal reaction, if temperature of reaction is low, it is acrylic acid modified then can not to carry out sufficient end group (methyl).But if this temperature of reaction is too high, then reactivity reduces on the contrary, so hydrothermal temperature is preferably 100～150 ℃.In addition, the hydro-thermal reaction time is generally about 0.1～10 hour according to the difference of temperature of reaction and different.On the other hand, in utilizing the situation of microwave, if design temperature is low excessively, it is acrylic acid modified to carry out sufficient end group (methyl), and therefore, based on reason same as described above, design temperature is preferably 90～150 ℃.It is the microwave of 2.5GHz that this microwave is fit to frequency of utilization, if utilize microwave irradiation, it is acrylic acid modified to carry out end group (methyl) usually in the short time about 10～60 minutes.In addition, as the mixed liquor that is used for this reaction, can list the reaction solution that the silane coupling agent of water, the 0.04 weight % of acetic acid, the 1 weight % of alcoholic solvent (mixed solvent of 1: 4 (weight ratio) of isopropyl alcohol and isobutyl alcohol), the 3 weight % of the hollow silica of for example using 3.8 weight %, 96 weight % is made.

[changing 8]

The low-index layer of the 2nd aspect is to above-mentioned bond composition irradiation ultraviolet radiation it to be solidified to form in the presence of Photoepolymerizationinitiater initiater, as this Photoepolymerizationinitiater initiater, can use a kind of イ Le ガキユア 184,819,651,1173,907 that Xiba Special Chemical Product Co.,Ltd for example makes etc. or multiple, its combined amount is preferably 3～10phr with respect to the bond composition.When the combined amount of Photoepolymerizationinitiater initiater is lower than this scope, can not carry out sufficient crosslinking curing, and if be higher than this scope, then the film strength of low-index layer reduces.

The low-index layer of the 2nd aspect is by with hollow silica, as polyfunctional group (methyl) acrylic compounds of bond composition and Photoepolymerizationinitiater initiater according to the rules the composition that mixes of ratio be applied on high refractive index layer or the electric conductivity high index of refraction hard conating, by irradiation ultraviolet radiation under the atmosphere gas of the oxygen concentration of 0～10000ppm it is solidified to form, wherein, if the oxygen concentration in the ultraviolet ray irradiation atmosphere gas surpasses 1000ppm, then traumatic resistance significantly reduces, therefore, be controlled at 1000ppm or below it, be preferably 200ppm or below it.

The thickness of such low-index layer is preferably 85～110nm.

In aspect the 2nd, in order on the base film 11 that is formed with easy adhesive layer 12, to form hard conating 13, transparency conducting layer 14, light absorbing zone 15, low-index layer 16, perhaps form hard conating, electric conductivity light absorbing zone and low-index layer, the uncured resin combination (resin combination that mixes above-mentioned particulate as required) of preferred coating, then irradiation ultraviolet radiation.In this case, can every coating make its curing afterwards for 1 layer, perhaps be coated with after 3 layers or 2 layers, solidify together.

As the concrete grammar of coating, can list the coating fluid that will bond be become grade solubilize to obtain, with coatings such as intaglio plate spreaders, drying is then then utilized the method for ultraviolet curing.According to this wet type rubbing method, have at a high speed evenly and the advantage of film forming at low cost.Be cured by irradiation ultraviolet radiation in this coating back, thereby played the effect that improves cohesive, raising film hardness, and need not heating, can produce antireflection film continuously.

The antireflection film of the 2nd aspect like this is applicable to the PDP of OA device or the front surface filtrator of liquid crystal panel, can guarantee good transmitance and permanance.

Below by enumerating embodiment, comparative example and experimental example more specific description is carried out in the 2nd aspect.

Embodiment 1～4, comparative example 1～3

Be coated with each layer in the following order, by under the oxygen concentration of 150ppm, whole layer being shone 800mJ/cm ²Ultraviolet ray make its curing.

At first, the thick TAC film of 50 μ m (" the TAC film " that the Off イ of Fuji Le system company makes, form on the PET film that refractive index is 1.57, the easy adhesive layer of the about 85nm of thickness) on, coating hard conating (" Z7503 " of JSR manufacturing).The thickness of formed hard conating is that 8 μ m, pencil hardness are 3H.Then, coating comprises the transparency conducting layer film-forming compositions (" Ei-3 " that big Japanese coating (strain) is made) of ITO particulate and urethane acrylate and Photoepolymerizationinitiater initiater.The thickness of formed transparency conducting layer is about 0.35 λ, refractive index is 1.68.

Then, coating is the potpourri of the carbon black of 90nm or titanium black (TiN is a principal ingredient, and median particle diameter is 60nm) and the イ Le ガキユア 184,819 that makes as the tetramethylol methane tetraacrylate of bond with as the Xiba Special Chemical Product Co.,Ltd of Photoepolymerizationinitiater initiater as the median particle diameter of light absorbing zone film-forming compositions.With respect to tetramethylol methane tetraacrylate, use the Photoepolymerizationinitiater initiater of 5phr.Light absorbing zone is deceived the potpourri of particulate and the ratio of bond by changing carbon black and titanium, changes attenuation coefficient, forms the light absorbing zone of refractive index as shown in table 8, attenuation coefficient and thickness.In addition, the attenuation coefficient of this light absorbing zone is 0.35 to the maximum.

In addition, be coated with the combination as shown in table 8 and the low-index layer composition of proportioning, form the low-index layer of refractive index as shown in table 8 and thickness.

In addition, in embodiment 1～4,, use the hollow silica of mean grain size as 60nm, refractive index n=about 1.30 as hollow silica.In addition, in comparative example 1～3,, use silicon dioxide microparticle (" IPA-ST " (particle diameter 10～20nm)) that daily output chemical company makes that does not have the hole as silicon dioxide.In addition, the polyfunctional group acrylic compounds of employed bond is pentaerythrite six acrylate in embodiment 1～4, and employed acrylic compounds is a tetramethylol methane tetraacrylate in the comparative example 1～3.As Photoepolymerizationinitiater initiater, add the イ Le ガキユア 184 of 5phr with respect to bond.

Change the refractive index of low-index layer by the blending ratio of change bond as shown in table 8 and particulate.

At the antireflection film that obtains like this, paste black ethene adhesive tape at inside surface (uncoated face), the spectrophotometer " U-4000 " that uses Hitachi to make manufacturing is measured minimum reflectance, the reflectivity of 400nm and the transmissivity of wavelength 550nm, and the result is as shown in table 8.

In addition, with 4.9 * 10 ⁴N/m ²Load wipe this antireflection film of reciprocating friction (low-refraction laminar surface) with plastic eraser, if the ruined words of film, this reflected colour can change, therefore, reciprocal time till its color begun to change is checked mar proof as anti-rubber friction number of times, and the result is as shown in table 8.In addition, the target property of this light absorption type antireflection film is: minimum reflectance 0.5% with reflectivity interior, wavelength 400nm be 2% or below it, the transmissivity of wavelength 550nm is 70% to be more than 100 times or 100 times with interior, anti-erasing rubber friction number of times.

[table 8]

Example		Light absorbing zone			Low-index layer					Optical property			Anti-rubber friction number of times (inferior)	Comprehensive evaluation
		Light absorbing zone			Low-index layer					Optical property					Refractive index n	Attenuation coefficient k	Thickness	Particulate	Bond	Bond: particulate (weight ratio)	Refractive index n	Thickness	Minimum reflectance (%)	Reflectivity 400nm (%)	Transmissivity 550nm (%)
		Embodiment	1	1.64	0.35	0.1λ	Hollow silica	The multi-functional acrylate	65∶35	1.43	0.18λ	0.21			Refractive index n	Attenuation coefficient k	Thickness	Particulate	Bond	Bond: particulate (weight ratio)	Refractive index n	Thickness	Minimum reflectance (%)	Reflectivity 400nm (%)	Transmissivity 550nm (%)	0.7	72	＞100	○
2	1.61		1	1.64	0.35	0.1λ	Hollow silica	The multi-functional acrylate	65∶35	1.43	0.18λ	0.21	0.3	0.1λ	Hollow silica	The multi-functional acrylate	65∶35	1.43	0.18λ	0.37	0.53	75	＞100	○		0.7	72	＞100	○
2	1.61		3	1.58	0.25	0.1λ	Hollow silica	The multi-functional acrylate	65∶35	1.43	0.18λ	0.28	0.3	0.1λ	Hollow silica	The multi-functional acrylate	65∶35	1.43	0.18λ	0.37	0.53	75	＞100	○	0.45	78	＞100	○
4	1.58		3	1.58	0.25	0.1λ	Hollow silica	The multi-functional acrylate	65∶35	1.43	0.18λ	0.28	0.3	0.07λ	Hollow silica	The multi-functional acrylate	65∶35	1.43	0.19λ	0.21	0.61	80	＞100	◎	0.45	78	＞100	○
4	1.58		Comparative example	1	1.64	0.35	0.14λ	Silicon dioxide	Acrylate	20∶80	1.495	0.175λ	0.3	0.07λ	Hollow silica	The multi-functional acrylate	65∶35	1.43	0.19λ	0.21	0.61	80	＞100	◎	0.36	1.61	66	＞100	△
2	1.64	0.35		1	1.64	0.35	0.14λ	Silicon dioxide	Acrylate	20∶80	1.495	0.175λ	0.12λ	Silicon dioxide	Acrylate	20∶80	1.495	0.175λ	0.5	1.2	68	＞100	△		0.36	1.61	66	＞100	△
2	1.64	0.35		3	1.64	0.35	0.1λ	Silicon dioxide	Acrylate	20∶80	1.495	0.18λ	0.12λ	Silicon dioxide	Acrylate	20∶80	1.495	0.175λ	0.5	1.2	68	＞100	△	0.54	1.01	72	＞100	△

Following as shown in Table 8 content.

Promptly, comparative example 1～3 has shown that using refractive index is various performances under the situation of 1.495 low-index layer, in order to surpass 70% satisfying under the condition of the frictional property of anti-rubber the more than 100 times or 100 times transmissivity, therefore must reduce the thickness of light absorbing zone, if and transmissivity surpasses 70%, when making the absorption layer attenuation, minimum reflectance can surpass 0.5%.

In contrast, use in low-index layer among the embodiment 1～4 of hollow silica and firm acrylic resin, the frictional property of anti-the erasing rubber is very good, and can make the low-index layer of low-refraction.Therefore, even the thickness of light absorbing zone reduces and the attenuation coefficient of light absorbing zone reduces, minimum reflectance also remains on 0.5% or below it, wherein, can also make minimum reflectance and be 0.5% or its following and transmissivity surpass 80% antireflection film.

In addition, with the antireflection film that this membrane structure is made, the reflectivity of its wavelength 400nm all is 2% or below it.

＜experimental example 〉

Enumerate experimental example below and show the above-mentioned of the thickness of stipulating easy adhesive layer and refractive index

(n _b+n _HC)/2-0.03≤n _a≤(n _b+n _HC)/2+0.03

And

(550/4) * (1/n _a)-10nm≤T≤(550/4) * (1/n _aThe basis of)+10nm.

If antireflection film does not have hard conating, then mar proof, pencil height reduce, and easily film are caused damage, therefore, form hard conating usually.As its structure, modal is to make PET film/hard conating/high refractive index layer/low-index layer.

Hard conating is in order to improve hardness, further mixing acrylic acid modified silicon dioxide microparticle at the polyfunctional group acrylic monomers of routine to the potpourri of oligomer forms, the common refractive index of the acrylic monomers of hard conating or oligomer is about 1.49～1.55, the refractive index of silicon dioxide microparticle is about 1.47, therefore, the refractive index of hard conating is about 1.49～1.55.On the other hand, the refractive index of PET film is about 1.65, and is very big with the difference of the refractive index of hard conating.

If form hard conating having on the base film of very large refringence in this way, then produce distinctive spectrum, minimum reflectance uprises when making antireflection film.

For the method that addresses this problem, reduces minimum reflectance comprises the thickness of controlling easy adhesive layer and the method for refractive index.

At first, forming hard conating/high refractive index layer/low-index layer is the anti-reflection layer of following composition.

[table 9]

	Refractive index	Blooming (λ) (under 550nm)	Thickness (nm)	Form
	Refractive index	Blooming (λ) (under 550nm)	Thickness (nm)	Form	Hard conating	1.50	8	2930	SiO ₂Particulate/polyfunctional group acrylic compounds
High refractive index layer	1.68	0.25	81	ITO particulate/polyfunctional group acrylic compounds	Hard conating	1.50	8	2930	SiO ₂Particulate/polyfunctional group acrylic compounds
High refractive index layer	1.68	0.25	81	ITO particulate/polyfunctional group acrylic compounds	Low-index layer	1.43	0.25	96	Hollow silica/polyfunctional group acrylic compounds

Shown in following experimental result easily which kind of degree change the thickness of adhesive layer and the minimum reflectance that refractive index makes anti-reflection layer produce when this anti-reflection layer of coating.

Below, the experimental example that is fit to the 2nd aspect is expressed as " experimental example A ", the experimental example that will be equivalent to comparative example is expressed as " experimental example B ".

In addition, the refractive index n of base film _bBe 1.65, the refractive index n of hard conating _HCBe 1.50, therefore, (n _b+ n _HC)/2 ≈ 1.58.

The reflectance spectrum of each experimental example is shown in Fig. 6～20, and in addition, minimum reflectance is as shown in table 10.

[table 10]

Experimental example	The refractive index of easy adhesive layer	The refractive index of easy adhesive layer and (n _b+n _HC)/2 poor	The thickness (nm) of easy adhesive layer	The thickness of easy adhesive layer and (550/4) * (1/n _a) poor	Minimum reflectance	Comprehensive evaluation
Experimental example	The refractive index of easy adhesive layer		The thickness (nm) of easy adhesive layer		Minimum reflectance	Comprehensive evaluation	B-1	-	-	-	-	0.48	×
B-2	1.55	-3	20	-69	0.38	×	B-1	-	-	-	-	0.48	×
B-2	1.55	-3	20	-69	0.38	×	B-3	1.54	-0.04	89	±0	0.21	×
A-1	1.56	-0.02	88	±0	0.19	○	B-3	1.54	-0.04	89	±0	0.21	×
A-1	1.56	-0.02	88	±0	0.19	○	A-2	1.58	±0	87	±0	0.19	○
A-3	1.60	+0.02	86	±0	0.19	○	A-2	1.58	±0	87	±0	0.19	○
A-3	1.60	+0.02	86	±0	0.19	○	B-4	1.62	+0.04	85	±0	0.3	×
B-5	1.64	+0.06	84	±0	0.4	×	B-4	1.62	+0.04	85	±0	0.3	×
B-5	1.64	+0.06	84	±0	0.4	×	B-6	1.58	0	57	-30	0.21	×
B-7	1.58	0	67	-20	0.2	×	B-6	1.58	0	57	-30	0.21	×
B-7	1.58	0	67	-20	0.2	×	A-4	1.58	0	77	-10	0.19	○
A-5	1.58	0	87	±0	0.19	○	A-4	1.58	0	77	-10	0.19	○
A-5	1.58	0	87	±0	0.19	○	A-6	1.58	0	97	+10	0.19	○
B-8	1.58	0	107	+20	0.21	×	A-6	1.58	0	97	+10	0.19	○
B-8	1.58	0	107	+20	0.21	×	B-9	1.58	0	117	+30	0.23	×

Not having the experimental example B-1 of easy adhesive layer and be provided with the reflectivity of experimental example B-2 of conventional easy adhesive layer (refractive index 1.55, thickness 20nm) all high on the PET film, is 0.35～0.45%.

Experimental example B-3～B～5 and experimental example A-1～A-3 with respect to the light of 550nm, correctly be controlled at 1/4 λ (0.25 λ), change the refractive index of easy adhesive layer with the blooming of easy adhesive layer.Blooming is that 0.25 λ is meant that the thickness of easy adhesive layer correctly satisfies (550/4) * (1/n _a).

With easily gluing refraction index changing is 1.54,1.56,1.58,1.60,1.62.From the reflectance spectrum of each experimental example and the minimum reflectance of this moment as can be seen, if easily the refractive index of adhesive layer is near (n _b+ n _HC)/2, then minimum reflectance reduces, particularly (n _b+ n _HCVery high anti-reflection effect can be observed in)/2 ± 0.02 o'clock.But, if easily the refractive index of adhesive layer is away from (n _b+ n _HCThe tendency that minimum reflectance also rises then can be observed in)/2.

Experimental example B-3...n=1.54d=(550/4) * (1/n _a)

Experimental example A-1...n=1.56d=(550/4) * (1/n _a)

Experimental example A-2...n=1.58d=(550/4) * (1/n _a)

Experimental example A-3...n=1.60d=(550/4) * (1/n _a)

Experimental example B-4...n=1.62d=(550/4) * (1/n _a)

Experimental example B-5...n=1.64d=(550/4) * (1/n _a)

Experimental example B-6～B-9 and embodiment A-5, A-6 have shown the influence of the thickness of easy adhesive layer, that is, easily the thickness of adhesive layer departs from (550/4) * (1/n _a) time situation.

Be set at (n from refractive index with easy adhesive layer _b+ n _HC)/2, promptly correctly be set at 1.58 and change the reaction spectrum of each experimental example of thickness of easy adhesive layer and the minimum reflectance of this moment as can be known, when the refractive index of easy adhesive layer exists

(n _b+n _HC)/2-0.03≤n _a≤(n _b+n _HC)/2+0.03

Scope in, and thickness exists

(550/4)×(1/n _a)-10nm≤T≤(550/4)×(1/n _a)+10nm

Scope in the time, minimum reflectance reduces.

Experimental example B-6...n=1.58d=(550/4) * (1/n _a)-30[nm] (57nm)

Experimental example B-7...n=1.58d=(550/4) * (1/n _a)-20[nm] (67nm)

Experimental example A-4...n=1.58d=(550/4) * (1/n _a)-10[nm] (77nm)

Experimental example A-5...n=1.58d=(550/4) * (1/n _a) [nm] (87nm)

Experimental example B-7...n=1.58d=(550/4) * (1/n _a)+10[nm] (97nm)

Experimental example B-8...n=1.58d=(550/4) * (1/n _a)+20[nm] (107nm)

Experimental example B-9...n=1.58d=(550/4) * (1/n _a)+30[nm] (117nm)

By these results as can be known, in the situation of using conventional hard conating (n=1.50), scope about 1.58 in the refractive index of easy adhesive layer, that thickness is 77～97nm can obtain very good preventing reflection characteristic.Thereby confirm,, can eliminate simultaneously because the spot shape reflected colour inequality that refringence caused of hard conating and base film by such setting.

III. the embodiment of the 3rd aspect

Embodiment at the antireflection film of the 3rd aspect describes below.

As shown in figure 21, the antireflection film of the 3rd aspect stacks gradually easy adhesive layer 22, hard conating 23, high refractive index layer 24 and low-index layer 25 and forms on transparent base film 21.Perhaps, in Figure 21, the high index of refraction hard conating is set to replace hard conating and high refractive index layer.

In aspect the 3rd, as base film 21, can list polyester, polyethylene terephthalate (PET), polybutylene terephthalate, polymethylmethacrylate (PMMA), acrylic resin, polycarbonate (PC), polystyrene, cellulosic triacetate (TAC), polyvinyl alcohol (PVA), Polyvinylchloride, Vingon, tygon, ethylene-vinyl acetate copolymer, polyurethane, viscose paper etc., the transparent membrane of preferred PET, PC, PMMA.

The thickness of base film 21 can be generally the scope of 1 μ m～10mm according to suitably decisions such as the desired characteristics of the purposes of resulting antireflection film (for example, intensity, film).

Easily adhesive layer 22 is used to improve the cohesive of 23 pairs of base films 21 of hard conating, uses usually and mix SiO in heat-curing resins such as copolymer polyester resin and urethane resin ₂, ZrO ₂, TiO ₂, Al ₂O ₃Deng metal oxide microparticle, preferred mean grain size is that metal oxide microparticle about 1～100nm is regulated the material of refractive index.In addition, can also only just refractive index be controlled to be 1.58 with resin.

Hard conating 23 is preferably the material of synthetic resin, is preferably ultraviolet hardening synthetic resin especially, preferred especially polyfunctional group acryl resin.The thickness of this hard conating 23 is preferably 2～20 μ m.

In aspect the 3rd, the refractive index of this hard conating 23 is 1.48～1.55 scope, in this case, and when the refractive index with easy adhesive layer 22 is designated as n _a, the refractive index of transparent base film 21 is designated as n _b, the refractive index of hard conating 23 is designated as n _HCThe time, if

(n _b+n _HC)/2-0.03≤n _a≤(n _b+n _HC)/2+0.03

Particularly, (n _b+ n _HC)/2-0.01≤n _a≤ (n _b+ n _HC)/2+0.01,

And easily the thickness T of adhesive layer 22 satisfies:

(550/4)×(1/n _a)-10nm≤T≤(550/4)×(1/n _a)+10nm

Particularly

(550/4)×(1/n _a)-5nm≤T≤(550/4)×(1/n _a)+5nm，

Scope the time, can obtain obviously good antireflection property, so preferably.

High refractive index layer 24 preferably comprises and is selected from SnO ₂The electric conductivity high index of refraction particulate that is constituted with ITO and be selected from TiO ₂, ZrO ₂And CeO ₂The represented 6 functional group's acrylic compounds of at least a high index of refraction particulate in the particulate group that the high index of refraction particulate that is constituted is formed and following general formula (VI) are as the bond composition of principal ingredient.

[changing 9]

(in above-mentioned general formula (VI), A ⁴¹～A ⁴⁶Represent acryloyl group, methacryl, α-fluorinated acrylamide acyl group or trifluoromethyl acryloyl group independently of one another.)

The average primary particle diameter of the high index of refraction particulate of this high refractive index layer is preferably 10～150nm, the average primary particle diameter of preferred especially high index of refraction particulate is 30～40nm, with this primary particle size is the center, particle size distribution range is wide, in total particulate, primary particle size is that the accumulation number of the following particulate of 30nm or its is 20% or more than it, for example be 20～30%, primary particle size is that the accumulation number of the above particulate of 45nm or its is 20% or more than it, it for example is 20～60% particulate, can carry out the high density of high index of refraction particulate fills, can form the high high refractive index layer of refractive index, so preferred.

In addition, from improving refractive index and keeping the aspect of the anti-charging property of high refractive index layer to consider, as the high index of refraction particulate, preferred combination is used electric conductivity high index of refraction particulate and superelevation refractive index particulate, particularly, preferred electric conductivity high index of refraction particulate: superelevation refractive index particulate=80: 20～50: 50 (volume ratio) is preferably 27: 18 (volume ratio) especially.If electric conductivity high index of refraction particulate is more than this scope, then the refractive index of high refractive index layer reduces, and if superelevation refractive index particulate is too many, then can not obtain anti-charged effect.

In addition, as the high index of refraction particulate of high refractive index layer 24, also preferably following (i) or (ii).

(i) on the anatase titanium dioxide particulate, cover the particulate that the ITO particulate is made, and the average primary particle diameter of titanium dioxide fine particles is that 5～80nm, the formed cover thickness of ITO particulate are above, the 5～20nm for example of 5nm or its.

(ii) on the rutile titanium dioxide particulate, cover the particulate that the ITO particulate is made, and the aspect ratio of titanium dioxide fine particles is 3～10, the formed cover thickness of ITO particulate is 5nm or it is above, 5～20nm for example.

If above-mentioned (i) or high index of refraction particulate (ii), particularly high index of refraction particulate (ii), reach the aspect ratio height, can form the effect of conductive network effectively.Preferably the high index of refraction particulate of above-mentioned (i) and above-mentioned (ii) high index of refraction particulate are used in combination.

Represented 6 functional groups (methyl) acrylic compounds of above-mentioned general formula (VI) as the bond composition of high refractive index layer 24, specifically, can list dipentaerythritol acrylate and ethylene oxide adduct thereof, these compounds can use a kind separately, also can be in conjunction with 2 kinds or multiple use.

About high index of refraction particulate in the high refractive index layer 24 and above-mentioned bond components in proportions, if the high index of refraction particulate is too much, bond composition deficiency, then the film strength of high refractive index layer reduces, on the contrary, if the high index of refraction particulate is very few, then can not fully improve refractive index, therefore, with respect to the total amount of high index of refraction particulate and bond, the ratio of high index of refraction particulate is preferably 10～60 volume %, is preferably 20～50 volume % especially.

The thickness of such high refractive index layer 24 is preferably about 80～100nm.In addition, the refractive index of high refractive index layer 24 is preferably 1.65 or more than it, be preferably 1.66～1.85 especially, in this case, refractive index by low-index layer 25 is set to 1.39～1.47, and the minimum reflectance that can make surface reflectivity is 1% or its following good antireflection film of antireflection property.Particularly the refractive index of low-index layer 25 is made as 1.45 or its when following, the minimum reflectance that can further improve antireflection, can also form surface reflectivity is 0.5% or its following antireflection film.

In aspect the 3rd, low-index layer 25 forms by the following method: under the atmosphere gas of the oxygen concentration of 0～10000ppm, by to the irradiation ultraviolet radiation of filming it being solidified to form, wherein this is filmed and comprises hollow silica and formed bond composition of polyfunctional group (methyl) acrylic compounds and Photoepolymerizationinitiater initiater.

Hollow silica is the silicon dioxide microparticle of hollow shelly, and its mean grain size is 10～200nm, is preferably 10～150nm.If the mean grain size of this hollow silica less than 10nm, then is difficult to reduce the refractive index of hollow silica,, then produce the problem of the diffuse reflection of light and the surfaceness increase of formed low-index layer etc. if greater than 200nm.

Hollow silica, empty therein inside have the low air of refractive index (refractive index=1.0), and therefore, its refractive index significantly is lower than common silicon dioxide (refractive index=1.46).The refractive index of hollow silica is that the volume ratio by its hollow space is determined, is preferably about 1.20～1.40 usually.

In addition, use the refractive index of low-index layer of the 3rd aspect of such hollow silica: n (low-index layer) is the refractive index of the refractive index from hollow silica: n (hollow silica) and bond composition: n (bond), calculates according to following formula.

N (low-index layer)=

In aspect the 3rd, the content of the hollow silica in the low-index layer is many more, then can form the low-index layer of low-refraction more, can access the good antireflection film of antireflection property, and along with the content of bond composition reduces relatively, the film strength of low-index layer reduces, and mar proof, permanance reduce.But the reduction of the film strength that increase caused of hollow silica combined amount can remedy by the surface treatment of hollow silica, in addition, also can replenish film strength by the kind of the bond composition selecting to be mixed.

In aspect the 3rd, by the surface treatment of hollow silica and the selection of bond composition, hollow silica content in the low-index layer is preferably 20～55 weight %, be preferably 30～50 weight % especially, to realize the low-refractionization of low-index layer, make refractive index about 1.39～1.45, guarantee mar proof simultaneously.

Then, polyfunctional group (methyl) acrylic compounds at the bond composition of the low-index layer of the 3rd aspect describes.

[changing 10]

N, m, o, p, q, r represent 0～2 integer independently of one another,

[changing 11]

S, t, u, v represent 0～2 integer independently of one another,

As the bond composition, can be used in combination a kind or multiple represented 6 functional groups (methyl) acrylic compounds and a kind or multiple represented 4 functional groups (methyl) acrylic compounds of above-mentioned general formula (II) of above-mentioned general formula (I).

In addition, in aspect the 3rd, as the bond composition, 4 functional groups (methyl) acrylic compounds that preferably that above-mentioned general formula (I) is represented 6 functional groups (methyl) acrylic compounds and/or above-mentioned general formula (II) are represented, be used in combination with represented fluorine-containing difunctional (methyl) acrylic compounds of following general formula (III) or specific fluorine-containing polyfunctional group (methyl) acrylic compounds, by using these bond compositions, can give mar proof and soil resistance to low-index layer.In addition, the refractive index of 4 functional groups (methyl) acrylic compounds that these bond compositions are more represented than represented 6 functional groups (methyl) acrylic compounds of above-mentioned general formula (I) or above-mentioned general formula (II) is lower, therefore, even the combined amount of hollow silica reduces, also can form the low low-index layer of refractive index.

A ^a-O-(CH ₂) _xa-Rf-(CH ₂) _xb-O-A ^b......(III)

Employed hollow silica in aspect the 3rd, its particle diameter is greater than the particle diameter of the conventional silicon dioxide microparticle that is mixed in the existing low-index layer (about particle diameter 5～20nm), therefore, even in the situation of using identical bond composition, compare with the situation of mixed silica particulate, the film strength of formed low-index layer has the tendency that dies down, and by this hollow silica being applied suitable surface treatment, can improve adhesion with the bond composition, improve the film strength of formed low-index layer, improve mar proof.

[changing 12]

For acrylic acid modified by using such end group (methyl) acrylic silane coupling agent that the hollow silica surface is implemented end group (methyl), preferably make the mixed liquor of hollow silica and end group (methyl) acrylic silane coupling agent carry out hydro-thermal reaction at 100～150 ℃, perhaps, this mixed liquor irradiating microwaves is made its reaction.That is, when only mixing end group (methyl) acrylic silane coupling agent and hollow silica, can not carry out surface chemical modification, can not obtain needed surface modification effect with end group (methyl) acrylic silane coupling agent.In utilizing the situation of hydro-thermal reaction, if temperature of reaction is low, it is acrylic acid modified then can not to carry out sufficient end group (methyl).But if this temperature of reaction is too high, then reactivity reduces on the contrary, so hydrothermal temperature is preferably 100～150 ℃.In addition, the hydro-thermal reaction time is generally about 0.1～10 hour according to the difference of temperature of reaction and different.On the other hand, in utilizing the situation of microwave, if design temperature is low excessively, it is acrylic acid modified to carry out sufficient end group (methyl), and therefore, based on reason same as described above, design temperature is preferably 90～150 ℃.It is the microwave of 2.5GH z that this microwave is fit to frequency of utilization, if utilize microwave irradiation, it is acrylic acid modified to carry out end group (methyl) usually in the short time about 10～60 minutes.In addition, as the mixed liquor that is used for this reaction, can list the reaction solution that the silane coupling agent of water, the 0.04 weight % of acetic acid, the 1 weight % of alcoholic solvent (mixed solvent of 1: 4 (weight ratio) of isopropyl alcohol and isobutyl alcohol), the 3 weight % of hollow silica with 3.8 weight %, 96 weight % is made.

[changing 13]

The low-index layer of the 3rd aspect is to above-mentioned bond composition irradiation ultraviolet radiation it to be solidified to form in the presence of Photoepolymerizationinitiater initiater, as this Photoepolymerizationinitiater initiater, can use a kind of イ Le ガキユア 184,819,651,1173,907 that Xiba Special Chemical Product Co.,Ltd for example makes etc. or multiple, its combined amount is preferably 3～10phr with respect to the bond composition.When the combined amount of Photoepolymerizationinitiater initiater is lower than this scope, can not carry out sufficient crosslinking curing, and if be higher than this scope, then the film strength of low-index layer reduces.

The low-index layer of the 3rd aspect is by with hollow silica, as polyfunctional group (methyl) acrylic compounds of bond composition and Photoepolymerizationinitiater initiater according to the rules the composition that mixes of ratio be applied on high refractive index layer or the electric conductivity high index of refraction hard conating, by irradiation ultraviolet radiation under the atmosphere gas of the oxygen concentration of 0～10000ppm it is solidified to form, wherein, if the oxygen concentration in the ultraviolet ray irradiation atmosphere gas surpasses 1000ppm, then traumatic resistance significantly reduces, therefore, be controlled at 1000ppm or below it, be preferably 200ppm or below it.

The thickness of such low-index layer is preferably 85～110nm.

In aspect the 3rd, in order on the base film 21 that is formed with easy adhesive layer 22, to form hard conating 23, high refractive index layer 24 and low-index layer 25, perhaps form electric conductivity high refractive index layer and low-index layer, the uncured resin combination (resin combination that mixes above-mentioned particulate as required) of preferred coating, then irradiation ultraviolet radiation.In this case, can every coating make its curing afterwards for 1 layer, perhaps be coated with after 3 layers or 2 layers, solidify together.

The antireflection film of the 3rd aspect like this is used for PDP or the front surface filtrator of liquid crystal panel or the window material of vehicle or special building of OA device, can guarantee good transmitance.

Below by enumerating embodiment, comparative example and experimental example more specific description is carried out in the 3rd aspect.

Embodiment 5

On the PET film of the thick 50 μ m of the easy adhesive layer that is formed with the about 80nm of thickness, be coated with hard conating (" Z7503 " that JSR makes), dry then, solidify, form thick 5 μ m, pencil hardness 3H or its above hard conating from the teeth outwards.Condition of cure is: ultraviolet cumulative exposure is 300mJ/cm ², the oxygen concentration when solidifying is 150ppm.

The refractive index n of employed easy adhesive layer _aBe 1.58, the refractive index n of PET film _bBe 1.65, the injecting layer n of formed hard conating _HCBe 1.495, (n _b+ n _HC)/2=1.57 is with n _aAbout equally.In addition, easily the thickness of adhesive layer is 80nm, with (550/4) * (1/n _a)=87nm about equally.

Then, coating comprises the high refractive index layer film-forming compositions (" Ei-3 " of Japanese coating strain formula meeting company manufacturing greatly) of ITO particulate and polyfunctional group acyclic compound and Photoepolymerizationinitiater initiater, dry, solidify, forming thickness, to be about 90nm, refractive index be 1.67～1.68 high refractive index layer.Condition of cure is: ultraviolet cumulative exposure is 300mJ/cm ², the oxygen concentration when solidifying is 150ppm.

In addition, the Photoepolymerizationinitiater initiater " イ Le ガキユア-184 " that in as the dipentaerythritol acrylate of bond composition, adds 5phr, add hollow silica (mean grain size is 60nm, refractive index n=about 1.30), make the total amount of Photoepolymerizationinitiater initiater and bond: hollow silica=62.5: 37.5 (weight %), used as the low-index layer film-forming compositions.

At the antireflection film that makes by said method, detect mar proof, minimum reflectance, chemical resistance by following method, the result is as shown in table 11.

＜mar proof 〉

Use plastic eraser to wipe with about 4.9 * 10 ⁴N/m ²Load pressure reciprocating friction antireflection film (reflected colour: surface purple).If the film of low-index layer is destroyed, then the variation of purple → redness → yellow slowly takes place in reflected colour, therefore with the reciprocal time till this color initial change as anti-rubber friction number of times, this anti-rubber friction number of times is is abrasion resistance properties good (zero) more than 100 times or 100 times the time, be bad (*) when being lower than 100 times.

＜minimum reflectance 〉

Paste black belt in inner surface side (side opposite with film forming face), and measure reflectance spectrum with 5 ° of normal reflections, the minimum reflectivity of this moment is designated as minimum reflectance.

＜chemical resistance 〉

On the film forming face of antireflection film, put tulle, drip the NaOH aqueous solution of several 3 weight %, cover Disposable paper cup from the top, placed 30 minutes down at 25 ℃ in order to prevent the evaporation of water in the NaOH aqueous solution.Then, tulle is taken away, with pure water washing, the reflected colour by visual judgement antireflection film has no change, reflected colour does not change be designated as that chemical resistance good (zero), reflected colour change be designated as chemical resistance not good (*).

In addition, by the refractive index of following method mensuration low-index layer, the result is as shown in table 11.

The mensuration of＜refractive index 〉

Not having on the PET film of easy adhesive layer (" eastern レ Le ミラ-", thickness 50 μ m), is the thickness coating low-index layer film-forming compositions of about 1/4 λ with the optical wavelength with respect to 550nm, makes its curing.Condition of cure is: ultraviolet cumulative exposure is 300mJ/cm ², the oxygen concentration when solidifying is 150ppm.Then, on uncoated face, paste black ethene adhesive tape, measure reflectivity, from the minimum reflectance calculating refractive index of this reflectance spectrum.

Comparative example 4

In embodiment 5, except use does not have the base film of easy adhesive layer and embodiment 5 similarly make antireflection film, similarly check mar proof, minimum reflectance, chemical resistance, measure the refractive index of its low-index layer simultaneously, the result is as shown in table 11.

[table 11]

	Have or not easy adhesive layer	Mar proof	Minimum reflectance (%)	Chemical resistance	Refractive index
	Have or not easy adhesive layer	Mar proof	Minimum reflectance (%)	Chemical resistance	Refractive index	Embodiment
5	Have	○	0.19	○	1.43	Embodiment
5	Have	○	0.19	○	1.43	Comparative example 4	Do not have	○	0.48	○	1.43

Experimental example 5

For the influence of the filling rate of the high index of refraction particulate of studying high refractive index layer to the refractive index of high refractive index layer, use the high index of refraction particulate of the material of combination as shown in table 12 as high refractive index layer, perhaps, as the bond composition, use A in the above-mentioned general formula (VI) ⁴¹～A ⁴⁶Be the compound of propenyl, and with the high index of refraction microparticle formulations shown in the table 12, preparation high refractive index layer film-forming compositions.

In addition, employed high index of refraction particulate is as follows in this experimental example, and in the high refractive index layer film-forming compositions, all according to electric conductivity high index of refraction particulate: the ratio of superelevation refractive index particulate=27: 18 (volume fraction) is mixed.

[electric conductivity high index of refraction particulate]

A-1: the ITO dispersion liquid that big Nippon Paint Co., Ltd. makes

(the mean grain size of ITO: 60nm)

A-2: the ITO dispersion liquid that big Nippon Paint Co., Ltd. makes

(the mean grain size of ITO: 35nm)

A-3: the ITO that the catalyst company that changes into makes " the superfine A of ELCOMP "

(the mean grain size of ITO: 50nm)

A-4: the ITO that the catalyst company that changes into makes " the superfine B of ELCOMP "

(the mean grain size of ITO: 65nm)

A-5: catalyst changes into the ITO dispersion liquid that company makes

(the mean grain size of ITO: 40nm)

[superelevation refractive index particulate]

B-1: the TiO that big Nippon Paint Co., Ltd. makes ₂Dispersion liquid

(TiO ₂Mean grain size: 100nm)

B-2: the TiO that big Nippon Paint Co., Ltd. makes ₂(Detitanium-ore-type) " the superfine D of ELCOMP "

(TiO ₂Mean grain size: 40nm)

B-3: the TiO that Chinese paint company is made ₂(rutile-type)

(TiO ₂Mean grain size: 40nm)

B-4: the TiO that Chinese paint company is made ₂(Detitanium-ore-type)

(TiO ₂Mean grain size: 8nm)

B-5: the TiO that Chinese paint company is made ₂(Detitanium-ore-type)

(TiO ₂Mean grain size: 20nm)

At this high refractive index layer film-forming compositions, by transmission electron microscope the size distribution of the primary particle size in the composition is investigated, the result is as shown in table 12.

Is that the thickness of about 1/4 λ is coated on the PET film (" eastern レ Le ミラ one ", thickness 50 μ m) that does not have easy adhesive layer with this high refractive index layer film-forming compositions with the optical wavelength with respect to 550nm, solidifies.Condition of cure is: ultraviolet cumulative exposure 300mJ/cm ², the oxygen concentration when solidifying is 150ppm.Then, paste black ethene adhesive tape on the uncoated face of film, measure reflectivity, from the minimum reflectance calculating refractive index of this reflectance spectrum, the result is as shown in table 12.

[table 12]

No.	The combined amount of the high index of refraction particulate in the high refractive index layer film-forming compositions (volume %)											The size-grade distribution of high index of refraction particulate (volume %)	Refractive index	Estimate
															Electric conductivity high index of refraction particulate			Superelevation refractive index particulate					Amount to	Primary particle size is that 30nm or its are following	Primary particle size is that 45nm or its are above
	A-1	A-2	A-3	A-4	A-5	B-1	B-2	B-3	B-4	B-5					Electric conductivity high index of refraction particulate			Superelevation refractive index particulate
	A-1	A-2	A-3	A-4	A-5	B-1	B-2	B-3	B-4	B-5	1	15				15	20				50	＜10				＞90	1.71	△
2	30					20					1	15	50	0		15	20				50	＜10	100	1.71	△	＞90	1.71	△
2	30					20					3		50	0	15	15	20				50	＜15	100	1.71	△	＞70	1.72	△
4	30						10	10			3		50	25	15	15	20				50	＜15	70	1.73	○	＞70	1.72	△
4	30						10	10			5	30	50	25				5	10	5	50	25	70	1.73	○	60	1.73	○
6		30							10	10	5	30	50	30				5	10	5	50	25	50	1.73	○	60	1.73	○

As shown in Table 12, be 30nm or the high index of refraction particulate below it and 40nm or the high index of refraction particulate more than it, can improve the loading of high index of refraction particulate, form the high refractive index layer that refractive index obviously improves by the suitable primary particle size that uses.

Experimental example 6

(n _b+n _HC)/2-0.03≤n _a≤(n _b+n _HC)/2+0.03

And

(550/4) * (1/n _a)-10nm≤T≤(550/4) * (1/n _aThe basis of)+10nm.

[table 13]

Shown in following experimental result easily which kind of degree change the thickness of adhesive layer and refractive index bring to the minimum reflectance of anti-reflection layer when this anti-reflection layer of coating.

Below, the experimental example that is fit to the 3rd aspect is expressed as " experimental example a ", the experimental example that will be equivalent to comparative example is expressed as " experimental example b ".

The reflectance spectrum of each experimental example is shown in Figure 25～36, and in addition, minimum reflectance is as shown in table 14.

[table 14]

Experimental example	The refractive index of easy adhesive layer	The refractive index of easy adhesive layer and (n _b+n _HC)/2 poor	The thickness (nm) of easy adhesive layer	The thickness of easy adhesive layer and (550/4) * (1/n _a) poor	Minimum reflectance (%)	Comprehensive evaluation
Experimental example	The refractive index of easy adhesive layer		The thickness (nm) of easy adhesive layer		Minimum reflectance (%)	Comprehensive evaluation	b-1	-	-	-	-	0.48	×
b-2	1.55	-3	20	-69	0.38	×	b-1	-	-	-	-	0.48	×
b-2	1.55	-3	20	-69	0.38	×	b-3	1.54	-0.04	89	±0	0.21	×
a-1	1.56	-0.02	88	±0	0.19	○	b-3	1.54	-0.04	89	±0	0.21	×
a-1	1.56	-0.02	88	±0	0.19	○	a-2	1.58	±0	87	±0	0.19	○
a-3	1.60	+0.02	86	±0	0.19	○	a-2	1.58	±0	87	±0	0.19	○
a-3	1.60	+0.02	86	±0	0.19	○	b-4	1.62	+0.04	85	±0	0.3	×
b-5	1.64	+0.06	84	±0	0.4	×	b-4	1.62	+0.04	85	±0	0.3	×
b-5	1.64	+0.06	84	±0	0.4	×	b-6	1.58	0	57	-30	0.21	×
b-7	1.58	0	67	-20	0.2	×	b-6	1.58	0	57	-30	0.21	×
b-7	1.58	0	67	-20	0.2	×	a-4	1.58	0	77	-10	0.19	○
a-5	1.58	0	87	±0	0.19	○	a-4	1.58	0	77	-10	0.19	○
a-5	1.58	0	87	±0	0.19	○	a-6	1.58	0	97	+10	0.19	○
b-8	1.58	0	107	+20	0.21	×	a-6	1.58	0	97	+10	0.19	○
b-8	1.58	0	107	+20	0.21	×	b-9	1.58	0	117	+30	0.23	×

With easily gluing variations in refractive index is 1.54,1.56,1.58,1.60,1.62.From the reflectance spectrum of each experimental example and the minimum reflectance of this moment as can be seen, if easily the refractive index of adhesive layer is near (n _b+ n _HC)/2, then minimum reflectance reduces, particularly (n _b+ n _HCVery high anti-reflection effect can be observed in)/2 ± 0.02 o'clock.But, if easily the refractive index of adhesive layer is away from (n _b+ n _HCThe tendency that minimum reflectance rises then can be observed in)/2.

Experimental example b-3...n=1.54d=(550/4) * (1/n _a)

Experimental example a-1...n=1.56d=(550/4) * (1/n _a)

Experimental example a-2...n=1.58d=(550/4) * (1/n _a)

Experimental example a-3...n=1.60d=(550/4) * (1/n _a)

Experimental example b-4...n=1.62d=(550/4) * (1/n _a)

Experimental example b-5...n=1.64d=(550/4) * (1/n _a)

Experimental example b-6～b-9 and embodiment a-5, a-6 have shown the influence of the thickness of easy adhesive layer, that is, easily the thickness of adhesive layer breaks away from (550/4) * (1/n _a) time situation.

(n _b+n _HC)/2-0.03≤n _a≤(n _b+n _HC)/2+0.03

Scope in, and thickness exists

(550/4) * (1/n _a)-10nm≤T≤(550/4) * (1/n _aIn the time of in the scope of)+10nm, minimum reflectance reduces.

Experimental example b-6...n=1.58d=(550/4) * (1/n _a)-30[nm] (57nm)

Experimental example b-7...n=1.58d=(550/4) * (1/n _a)-20[nm] (67nm)

Experimental example a-4...n=1.58d=(550/4) * (1/n _a)-10[nm] (77nm)

Experimental example a-5...n=1.58d=(550/4) * (1/n _a) [nm] (87nm)

Experimental example b-7...n=1.58d=(550/4) * (1/n _a)+10[nm] (97nm)

Experimental example b-8...n=1.58d=(550/4) * (1/n _a)+20[nm] (107nm)

Experimental example b-9...n=1.58d=(550/4) * (1/n _a)+30[nm] (117nm)

IV. the embodiment of the 4th aspect

Describe at the electromagnetic wave shielding transmittance type window material of the 4th aspect and the embodiment of gas discharge type luminescent panel below.

The electromagnetic wave shielding transmittance type window material of the 4th aspect and the general structure of gas discharge type luminescent panel itself can be identical with the gas discharge type luminescent panel with existing electromagnetic wave shielding transmittance type window material, for example, can list, in electromagnetic wave shielding window material shown in Figure 38 a or the gas discharge type luminescent panel shown in Figure 38 b, use the electromagnetic wave shielding transmittance type window material and the gas discharge type luminescent panel of the antireflection film of the low-index layer that adopts the 4th aspect as antireflection film.

Below, describe at this antireflection film with reference to Figure 37.

The structure of this antireflection film 80 is as follows: on transparent base film 81, stack gradually hard conating 82, high refractive index layer 83 and low-index layer 84, form adhesive layer 85 on the face of an opposite side with this lamination surface, and paste mould release film 86.When this antireflection film 80 is used for gas discharge type luminescent panel shown in the electromagnetic wave shielding light-transmissive window material shown in Figure 38 a or Figure 38 b, peel off the mould release film 86 of antireflection film 80, and paste the outermost surface of electromagnetic wave shielding transmittance type window material or gas discharge type luminescent panel by adhesive layer 85.

In aspect the 4th, as base film 81, can list polyester, polyethylene terephthalate (PET), polybutylene terephthalate, polymethylmethacrylate (PMMA), acrylic resin, polycarbonate (PC), polystyrene, cellulosic triacetate (TAC), polyvinyl alcohol (PVA), Polyvinylchloride, Vingon, tygon, ethylene-vinyl acetate copolymer, polyurethane, viscose paper etc., the transparent membrane of preferred PET, PC, PMMA.

Under the common situation of the thickness of base film 81 is the scope of 100 μ m～188 μ m.

As hard conating 82, the hard conating of preferred synthetic resin, preferred especially ultraviolet hardening synthetic resin, the combination of preferred especially polyfunctional group acryl resin and silicon dioxide microparticle.The thickness of this hard conating 82 is preferably 2～20 μ m.

High refractive index layer 83 is preferably the material of the ultraviolet hardening of the bond composition that comprises metal oxide microparticle and have aromatic radical, as bond composition, can enumerate epoxy acrylate, urethane acrylate, contain the acrylate resin of bisphenol-A etc. with aromatic radical.In addition, as metal oxide microparticle, be preferably selected from ITO, TiO ₂, ZrO ₂, CeO ₂, Al ₂O ₃, Y ₂O ₃, La ₂O ₃And Ho ₂O ₃At least a kind or multiple high refractive index metal oxide particulate in the group of being formed, preferred especially TiO ₂Particulate, ITO particulate.

About metal oxide microparticle in the high refractive index layer 83 and bond components in proportions, the bond composition deficiency if metal oxide microparticle is too much, then the film strength of high refractive index layer reduces, otherwise,, then can not fully improve refractive index if metal oxide microparticle is very few, therefore, with respect to the total amount of metal oxide microparticle and bond composition, the ratio of metal oxide microparticle is preferably 10～60 volume %, is preferably 20～50 volume % especially.

The thickness of such high refractive index layer 83 is preferably about 80～100nm.In addition, the refractive index of this high refractive index layer 83 is preferably 1.65 or more than it, be preferably 1.66～1.85 especially, in this case, be controlled at 1.39～1.47 by the refractive index with low-index layer 84, the minimum reflectance that can obtain surface reflectivity is 1% or the good antireflection film of antireflection property below it.Particularly the refractive index of low-index layer 84 is controlled at 1.45 or the situation below it in, the minimum reflectance that can further improve antireflection, can also make surface reflectivity is 0.5% or antireflection film below it.

Low-index layer 84 be by under the atmosphere gas of the oxygen concentration of 0～10000ppm by the irradiation ultraviolet radiation of filming is obtained, wherein this is filmed and comprises bond composition and the Photoepolymerizationinitiater initiater that hollow silica, polyfunctional group (methyl) acrylic compounds form.

The empty therein inside of hollow silica has the low air of refractive index (refractive index=1.0), and therefore, its refractive index is compared remarkable reduction with conventional silicon dioxide (refractive index=1.46).The refractive index of hollow silica is that the volume ratio by its hollow space is determined, is preferably about 1.20～1.40 usually.

In addition, the refractive index of hollow silica: n (hollow silica) is the refractive index of the air of the refractive index by the silicon dioxide of the shell portion that constitutes hollow minute particle: n (silicon dioxide), inside: n (air), calculates according to following formula.

In addition, use the refractive index of low-index layer of the 4th aspect of such hollow silica: n (low-index layer) is the refractive index of the refractive index by hollow silica: n (hollow silica) and bond composition: n (bond), calculates according to following formula.

N (low-index layer)=

In aspect the 4th, the content of the hollow silica in the low-index layer is many more, then can form the low-index layer of low-refraction more, can access the good antireflection film of antireflection property, and along with the content of bond composition reduces relatively, the film strength of low-index layer reduces, and mar proof, permanance reduce.But the reduction of the film strength that increase caused of hollow silica combined amount can remedy by the surface treatment of hollow silica, in addition, also can replenish film strength by the kind of the bond composition selecting to be mixed.

In aspect the 4th, by the surface treatment of hollow silica and the selection of bond composition, hollow silica content in the low-index layer is preferably 20～55 weight %, be preferably 30～50 weight % especially, to realize the low-refractionization of low-index layer, make refractive index about 1.39～1.45, guarantee mar proof simultaneously.

Then, polyfunctional group (methyl) acrylic compounds at the bond composition of the low-index layer of the 4th aspect describes.

[changing 14]

N, m, o, p, q, r represent 0～2 integer independently of one another,

[changing 15]

S, t, u, v represent 0～2 integer independently of one another,

In addition, in aspect the 4th, as the bond composition, 4 functional groups (methyl) acrylic compounds that preferably that above-mentioned general formula (I) is represented 6 functional groups (methyl) acrylic compounds and/or above-mentioned general formula (II) are represented, be used in combination with represented fluorine-containing difunctional (methyl) acrylic compounds of following general formula (III) or specific fluorine-containing polyfunctional group (methyl) acrylic compounds, by using these bond compositions, can give mar proof and soil resistance to low-index layer.In addition, the refractive index of 4 functional groups (methyl) acrylic compounds that these bond compositions are more represented than represented 6 functional groups (methyl) acrylic compounds of above-mentioned general formula (I) or above-mentioned general formula (II) is lower, therefore, even the combined amount of hollow silica reduces, also can form the low low-index layer of refractive index.

A ^a-O-(CH ₂) _xa-Rf-(CH ₂) _xb-O-A ^b......(III)

Employed hollow silica in aspect the 4th, its particle diameter is greater than the particle diameter of the conventional silicon dioxide microparticle that is mixed in the existing low-index layer (about particle diameter 5～20nm), therefore, even in the situation of using identical bond composition, compare with the situation of mixed silica particulate, the film strength of formed low-index layer has the tendency that dies down, and by this hollow silica being applied suitable surface treatment, can improve adhesion with the bond composition, improve the film strength of formed low-index layer, improve mar proof.

[changing 16]

For acrylic acid modified by using such end group (methyl) acrylic silane coupling agent that the hollow silica surface is implemented end group (methyl), preferably make the mixed liquor of hollow silica and end group (methyl) acrylic silane coupling agent carry out hydro-thermal reaction at 100～150 ℃, perhaps, this mixed liquor irradiating microwaves is made its reaction.That is, when only mixing end group (methyl) acrylic silane coupling agent and hollow silica, can not carry out surface chemical modification, can not obtain needed surface modification effect with end group (methyl) acrylic silane coupling agent.In utilizing the situation of hydro-thermal reaction, if temperature of reaction is low, it is acrylic acid modified then can not to carry out sufficient end group (methyl).But if this temperature of reaction is too high, then reactivity reduces on the contrary, so hydrothermal temperature is preferably 100～150 ℃.In addition, the hydro-thermal reaction time is generally about 0.1～10 hour according to the difference of temperature of reaction and different.On the other hand, in utilizing the situation of microwave, if design temperature is low excessively, it is acrylic acid modified to carry out sufficient end group (methyl), and therefore, based on reason same as described above, design temperature is preferably 90～150 ℃.It is the microwave of 2.5GHz that this microwave is fit to frequency of utilization, if utilize microwave irradiation, it is acrylic acid modified to carry out end group (methyl) usually in the short time about 10～60 minutes.In addition, as the mixed liquor that is used for this reaction, can enumerate the reaction solution that the silane coupling agent of water, the 0.04 weight % of acetic acid, the 1 weight % of alcoholic solvent (mixed solvent of 1: 4 (weight ratio) of isopropyl alcohol and isobutyl alcohol), the 3 weight % of the hollow silica of for example using 3.8 weight %, 96 weight % is made.

[changing 17]

The low-index layer of the 4th aspect is to above-mentioned bond composition irradiation ultraviolet radiation it to be solidified to form in the presence of Photoepolymerizationinitiater initiater, as this Photoepolymerizationinitiater initiater, can use a kind of イ Le ガキユア 184,819,651,1173,907 that Xiba Special Chemical Product Co.,Ltd for example makes etc. or multiple, its combined amount is preferably 3～10phr with respect to the bond composition.When the combined amount of Photoepolymerizationinitiater initiater is lower than this scope, can not carry out sufficient crosslinking curing, and if be higher than this scope, then the film strength of low-index layer reduces.

The low-index layer of the 4th aspect is by with hollow silica, as polyfunctional group (methyl) acrylic compounds of bond composition and Photoepolymerizationinitiater initiater according to the rules the composition that mixes of ratio be applied on high refractive index layer or the electric conductivity high index of refraction hard conating, by irradiation ultraviolet radiation under the atmosphere gas of the oxygen concentration of 0～10000ppm it is solidified to form, wherein, if the oxygen concentration in the ultraviolet ray irradiation atmosphere gas surpasses 1000ppm, then traumatic resistance significantly reduces, therefore, be controlled at 1000ppm or below it, be preferably 200ppm or below it.

The thickness of such low-index layer is preferably 85～110nm, is preferably about 100nm especially.

In aspect the 4th, in order on base film 81, to form hard conating 82, high refractive index layer 83 and low-index layer 84, preferably be coated with uncured resin combination (resin combination that mixes above-mentioned particulate as required), then irradiation ultraviolet radiation.In this case, can every coating make its curing afterwards for 1 layer, perhaps be coated with after 3 layers or 2 layers, solidify together.

Concrete grammar as coating can list the coating fluid that will make the solubilize of bond composition with the toluene equal solvent and obtain, and is dry then with coatings such as intaglio plate spreaders, then utilizes the method for ultraviolet curing.According to this wet type rubbing method, have at a high speed evenly and the advantage of film forming at low cost.Be cured by irradiation ultraviolet radiation in this coating back, thereby played the effect that improves cohesive, raising film hardness, and need not heating, can produce antireflection film continuously.

In addition, as the tackifier of the adhesive layer 85 that is formed at base film 81 inner surface side, transparent adhesives such as preferred acrylic compounds, the thickness of this adhesive layer 85 is generally about 1～100 μ m, is preferably especially about 25 μ m.

In addition, as mould release film 86, can use the thickness that forms with above-mentioned base film same material is preferably about 20～175 μ m, is preferably film about 35 μ m especially and has carried out the surperficial demoulding and handle the mould release film that obtains.

The electromagnetic wave shielding transmitance window material and the gas discharge type luminescent panel of the 4th aspect, as employed antireflection film in the gas discharge type luminescent panel shown in the electromagnetic wave shielding transmitance window material shown in Figure 38 a or Figure 38 b for example, can use antireflection film shown in Figure 38 to make, in addition, if for example be provided with the electromagnetic wave shielding transmitance window material and the gas discharge type luminescent panel of transparency carrier such as glass substrate at outermost surface, then can be by directly stacked above-mentioned high refractive index layer and low-index layer on this transparency carrier, and film forming is made.In addition, when pasting antireflection film on the transparency carriers such as glass substrate at outermost surface, this antireflection film can be the antireflection film that has omitted hard conating in Figure 37.

In the electromagnetic wave shielding transmitance window material and gas discharge type luminescent panel aspect the 4th, for example in the formed anti-reflection layer of the stacked film of above-mentioned antireflection film, high refractive index layer and low-index layer, by carrying out following adjustment, can realize high visual electromagnetic wave shielding transmitance window material and gas discharge type luminescent panel that better antireflection and soil resistance are good.

(1) easy adhesive layer is set between transparent base film and hard conating.Easily adhesive layer is used to improve the cohesive of hard conating and base film, uses usually and mix SiO in heat-curing resins such as copolymer polyester resin and urethane resin ₂, ZrO ₂, TiO ₂, Al ₂O ₃Deng metal oxide microparticle, preferred mean grain size is that metal oxide microparticle about 1～100nm is regulated the material of refractive index.In addition, when cost is raise, can adjust refractive index by the polymkeric substance that in structure, comprises a large amount of phenyl, bromine atoms, sulphur atom that mixes 0～50 weight %.

At this moment, if the refractive index of this hard conating is 1.48～1.55 scope, when the refractive index with easy adhesive layer is designated as n _a, the refractive index of transparent base film is designated as n _b, the refractive index of hard conating is designated as n _HCThe time,

(n _b+n _HC)/2-0.02≤n _a≤(n _b+n _HC)/2+0.02

Particularly, (n _b+ n _HC)/2-0.01≤n _a≤ (n _b+ n _HC)/2+0.01, and easily the thickness T of adhesive layer 2 satisfies:

(550/4)×(1/n _a)-10nm≤T≤(550/4)×(1/n _a)+10nm

Particularly

(550/4) * (1/n _a)-5nm≤T≤(550/4) * (1/n _a)+5nm, scope the time, can obtain obviously good antireflection property, so preferably.

This has following effect: with respect to the optical wavelength of 550nm, the refractive index of base film is substantially equal to the refractive index of hard conating, and has the effect of the reflection between elimination hard conating/base film.In aspect the 4th, this easy adhesive layer preferably is formed on the transparent base film when the shaping transparent base film.

(2) as the high index of refraction particulate of high refractive index layer, the preferred use is selected from SnO ₂The electric conductivity high index of refraction particulate and the TiO that are formed with ITO ₂, ZrO ₂And CeO ₂At least a kind of high index of refraction particulate in the particulate group that the superelevation refractive index particulate of being formed is formed, be used in combination the high index of refraction particulate of different-grain diameter, the average primary particle diameter that makes the high index of refraction particulate is 30～40nm, and be the center with this average primary particle diameter, particle size distribution range is wide, and in total particulate, primary particle size be the accumulation number of the following particulate of 30nm or its be 20% or it is above, for example be 20%～50%, primary particle size be the accumulation number of 45nm or its above particulate be 20% or it is above, for example be 20%～50%.

That is, in high refractive index layer, it is important comprising high index of refraction particulate as much as possible, like this, by being used in combination the high index of refraction particulate of different-grain diameter, can improve the loading of high index of refraction particulate in high refractive index layer, form the very high high refractive index layer of refractive index with high packed density.

In addition, as the high index of refraction particulate, from improving refractive index and keeping the aspect of the anti-charging property of high refractive index layer to consider, preferred combination is used electric conductivity high index of refraction particulate and superelevation refractive index particulate, preferred especially electric conductivity high index of refraction particulate: superelevation refractive index particulate=50～70: 50～30 (volume ratios), preferred especially 27: 18 (volume ratio).If electric conductivity high index of refraction particulate is more than this scope, then the refractive index of high refractive index layer reduces, if superelevation refractive index particulate is too much, then can not obtain anti-charged effect.

(3) as the bond composition of low-index layer,, improve soil resistance by using above-mentioned fluorine-containing bond composition.

(4) thickness by adjusting high refractive index layer and the thickness of low-index layer, realize visible-range average reflectance, need the low reflectionization under the wavelength of low reflectionization.For example, when the redness of illuminant colour is more weak, by increasing the thickness of high refractive index layer, perhaps increase the thickness of low-index layer, the wavelength (paddy wavelength) that makes minimum reflectance is to the displacement of long wave direction, by making the paddy wavelength reach red light wavelength, to improve red transmissivity, otherwise, when blueness is more weak, by reducing the thickness of high refractive index layer, perhaps reduce the thickness of low-index layer, make the paddy wavelength to the displacement of shortwave direction, by making the paddy wavelength reach blue light wavelength, improve blue transmissivity etc., make in this way, form anti-reflection layer with the reflection characteristic that adapts with purpose.

V. the form of the 5th aspect

Below, the panel display board of the 5th aspect and the embodiment of show window material are described.

The panel display board of the 5th aspect and show window material can be the structures of for example pasting antireflection film as shown in figure 39 on its surface.

The structure of this antireflection film 90 is: stack gradually hard conating 92, high refractive index layer 93 and low-index layer 94 on antireflection film 91, form adhesive layer 95 on the face of the opposition side of this lamination surface, paste mould release film 96.When the transparency carriers such as glass substrate of surface that this antireflection film 90 is used for panel display board or show window material, can peel off the mould release film 96 of antireflection film 90 and paste by adhesive layer 95 on the transparency carriers such as glass substrate of the surface of panel display board or show window material.

In this antireflection film 90, as base film 91, can list polyester, polyethylene terephthalate (PET), polybutylene terephthalate, polymethylmethacrylate (PMMA), acrylic resin, polycarbonate (PC), polystyrene, cellulosic triacetate (TAC), polyvinyl alcohol (PVA), Polyvinylchloride, Vingon, tygon, ethylene-vinyl acetate copolymer, polyurethane, viscose paper etc., the transparent membrane of preferred PET, PC, PMMA.

The thickness of base film 91 is generally the scope of 100 μ m～188 μ m.

As hard conating 92, the hard conating of preferred synthetic resin, preferred especially ultraviolet curing resin, the combination of preferred especially multi-functional acrylate and silicon dioxide microparticle.The thickness of this hard conating 92 is preferably 2～20 μ m.

High refractive index layer 93 is preferably the material of the ultraviolet hardening of the bond composition that comprises metal oxide microparticle and have aromatic radical, as bond composition, can enumerate epoxy acrylate, urethane acrylate, contain the acryl resin of bisphenol-A etc. with aromatic radical.In addition, as metal oxide microparticle, be preferably selected from ITO, TiO ₂, ZrO ₂, CeO ₂, Al ₂O ₃, Y ₂O ₃, La ₂O ₃And Ho ₂O ₃1 kind or multiple high refractive index metal oxide particulate in the group of being formed, preferred especially TiO ₂Particulate, ITO particulate.

Metal oxide microparticle and bond components in proportions about high refractive index layer 93, the bond composition deficiency if metal oxide microparticle is too much, then the film strength of high refractive index layer reduces, otherwise,, then can not fully improve refractive index if metal oxide microparticle is very few, therefore, with respect to the total amount of metal oxide microparticle and bond composition, the ratio of metal oxide microparticle is preferably 10～60 volume %, is preferably 20～50 volume % especially.

The thickness of such high refractive index layer 93 is preferably about 80～100nm.In addition, the refractive index of this high refractive index layer 93 is preferably 1.65 or more than it, be preferably 1.66～1.85 especially, in this case, be controlled at 1.39～1.47 by the refractive index with low-index layer 94, the minimum reflectance that can obtain surface reflectivity is 1% or the good antireflection film of antireflection property below it.Particularly the refractive index of low-index layer 94 is controlled at 1.45 or the situation below it in, the minimum reflectance that can further improve antireflection, can also make surface reflectivity is 0.5% or antireflection film below it.

In aspect the 5th, low-index layer 94 be by under the atmosphere gas of the oxygen concentration of 0～10000ppm by the irradiation ultraviolet radiation of filming is obtained, wherein this is filmed and comprises bond composition and the Photoepolymerizationinitiater initiater that hollow silica, polyfunctional group (methyl) acrylic compounds form.

Hollow silica is the silicon dioxide microparticle of hollow shelly, and its mean grain size is 10～200nm, is preferably 10～150nm especially.The mean grain size of this hollow silica is difficult to reduce the refractive index of hollow silica, and if greater than 200nm, then can have the problem of the diffuse reflection of light and the surfaceness increase of formed low-index layer etc. during less than 10nm.

Hollow silica has the low air of refractive index (refractive index=1.0) in hollow inside, therefore, its refractive index is compared remarkable reduction with conventional silicon dioxide (refractive index=1.46).The refractive index of hollow silica is that the volume ratio by its hollow space is determined, is preferably about 1.20～1.40 usually.

In addition, using the refractive index of the low-index layer of the present invention of such hollow silica: n (low-index layer) is refractive index by hollow silica: the refractive index of n (hollow silica) and bond composition: n (bond), calculate according to following formula.

N (low-index layer)=

In aspect the 5th, the content of the hollow silica in the low-index layer is many more, then can form the low-index layer of low-refraction more, can access the good antireflection film of antireflection property, and along with the content of bond composition reduces relatively, the film strength of low-index layer reduces, and mar proof, permanance reduce.But the reduction of the film strength that increase caused of hollow silica combined amount can remedy by the surface treatment of hollow silica, in addition, also can replenish film strength by the kind of the bond composition selecting to be mixed.

In aspect the 5th, by the surface treatment of hollow silica and the selection of bond composition, hollow silica content in the low-index layer is preferably 20～55 weight %, be preferably 30～50 weight % especially, to realize the low-refractionization of low-index layer, make refractive index about 1.39～1.45, guarantee mar proof simultaneously.

Then, polyfunctional group (methyl) acrylic compounds as the bond composition of the low-index layer of the 5th aspect is described.

[changing 18]

N, m, o, p, q, r represent 0～2 integer independently of one another,

[changing 19]

S, t, u, v represent 0～2 integer independently of one another,

In addition, in aspect the 5th, as the bond composition, 4 functional groups (methyl) acrylic compounds that preferably that above-mentioned general formula (I) is represented 6 functional groups (methyl) acrylic compounds and/or above-mentioned general formula (II) are represented, be used in combination with represented fluorine-containing difunctional (methyl) acrylic compounds of following general formula (III) or specific fluorine-containing polyfunctional group (methyl) acrylic compounds, by using these bond compositions, can give mar proof and soil resistance to low-index layer.In addition, the refractive index of 4 functional groups (methyl) acrylic compounds that these bond compositions are more represented than represented 6 functional groups (methyl) acrylic compounds of above-mentioned general formula (I) or above-mentioned general formula (II) is lower, therefore, even the combined amount of hollow silica reduces, also can form the low low-index layer of refractive index.

A ^a-O-(CH ₂) _xa-Rf-(CH ₂) _xb-O-A ^b......(III)

Employed hollow silica in aspect the 5th, its particle diameter is greater than the particle diameter of the conventional silicon dioxide microparticle that is mixed in the existing low-index layer (about particle diameter 5～20nm), therefore, even in the situation of using identical bond composition, compare with the situation of mixed silica particulate, the film strength of formed low-index layer has the tendency that dies down, and by this hollow silica being applied suitable surface treatment, can improve adhesion with the bond composition, improve the film strength of formed low-index layer, improve mar proof.

[changing 20]

For acrylic acid modified by using such end group (methyl) acrylic silane coupling agent that the hollow silica surface is implemented end group (methyl), preferably make the mixed liquor of hollow silica and end group (methyl) acrylic silane coupling agent carry out hydro-thermal reaction at 100～150 ℃, perhaps, this mixed liquor irradiating microwaves is made its reaction.That is, when only mixing end group (methyl) acrylic silane coupling agent and hollow silica, can not carry out surface chemical modification, can not obtain needed surface modification effect with end group (methyl) acrylic silane coupling agent.In utilizing the situation of hydro-thermal reaction, if temperature of reaction is low, it is acrylic acid modified then can not to carry out sufficient end group (methyl).But if this temperature of reaction is too high, then reactivity reduces on the contrary, so hydrothermal temperature is preferably 100～150 ℃.In addition, the hydro-thermal reaction time is generally about 0.1～10 hour according to the difference of temperature of reaction and different.On the other hand, in utilizing the situation of microwave, if design temperature is low excessively, it is acrylic acid modified to carry out sufficient end group (methyl), and therefore, based on reason same as described above, design temperature is preferably 90～150 ℃.It is the microwave of 2.5GHz that this microwave is fit to frequency of utilization, if utilize microwave irradiation, it is acrylic acid modified to carry out end group (methyl) usually in the short time about 10～60 minutes.In addition, as the mixed liquor that is used for this reaction, can list the reaction solution that the silane coupling agent of water, the 0.04 weight % of acetic acid, the 1 weight % of alcoholic solvent (mixed solvent of 1: 4 (weight ratio) of isopropyl alcohol and isobutyl alcohol), the 3 weight % of hollow silica with 3.8 weight %, 96 weight % is made.

[changing 21]

The low-index layer of the 5th aspect is to above-mentioned bond composition irradiation ultraviolet radiation it to be solidified to form in the presence of Photoepolymerizationinitiater initiater, as this Photoepolymerizationinitiater initiater, can use a kind of イ Le ガキユア 184,819,651,1173,907 that Xiba Special Chemical Product Co.,Ltd for example makes etc. or multiple, its combined amount is preferably 3～10phr with respect to the bond composition.When the combined amount of Photoepolymerizationinitiater initiater is lower than this scope, can not carry out sufficient crosslinking curing, and if be higher than this scope, then the film strength of low-index layer reduces.

The low-index layer of the 5th aspect is by with hollow silica, as polyfunctional group (methyl) acrylic compounds of bond composition and Photoepolymerizationinitiater initiater according to the rules the composition that mixes of ratio be applied on high refractive index layer or the electric conductivity high index of refraction hard conating, by irradiation ultraviolet radiation under the atmosphere gas of the oxygen concentration of 0～10000ppm it is solidified to form, wherein, if the oxygen concentration in the ultraviolet ray irradiation atmosphere gas surpasses 1000ppm, then traumatic resistance significantly reduces, therefore, be controlled at 1000ppm or below it, be preferably 200ppm or below it.

In aspect the 5th, in order on base film 91, to form hard conating 92, high refractive index layer 93 and low-index layer 94, preferably be coated with uncured resin combination (resin combination that mixes above-mentioned particulate as required), then irradiation ultraviolet radiation.In this case, can every coating make its curing afterwards for 1 layer, perhaps be coated with after 3 layers or 2 layers, solidify together.

In addition, as the tackifier of the adhesive layer 95 that is formed at base film 91 inner surface side, transparent adhesives such as preferred acrylic compounds, the thickness of this adhesive layer 95 is generally about 1～100 μ m, is preferably especially about 25 μ m.

In addition, as mould release film 96, can use to by the thickness that forms with above-mentioned base film same material be about 20～175 μ m, particularly the film about 35 μ m has been implemented the demoulding film that surperficial demoulding is handled.

The panel display board of the 5th aspect and show window material can be made by using such antireflection film 90, in addition, for example if be provided with the panel display board of transparency carrier such as glass substrate in outmost surface, then can be by directly stacked above-mentioned high refractive index layer and low-index layer and film forming be made on this transparency carrier.Equally, the show window material also can be made by direct stacked above-mentioned high refractive index layer and low-index layer and film forming on transparency carriers such as glass substrate.In addition, when pasting antireflection film on transparency carriers such as glass substrate, this antireflection film can also be the antireflection film that omits hard conating in Figure 39.

In the panel display board and show window material aspect the 5th, for example at above-mentioned antireflection film, by the formed anti-reflection layer of the stacked film of high refractive index layer and low-index layer in, by carrying out following adjustment, can realize better antireflection, high visual panel display board and show window material that soil resistance is good.

At this moment, the refractive index of this hard conating is 1.48～1.55 scope, when the refractive index with easy adhesive layer is designated as n _a, the refractive index of transparent base film is designated as n _b, the refractive index of hard conating is designated as n _HCThe time,

(n _b+n _HC)/2-0.02≤n _a≤(n _b+n _HC)/2+0.02

Particularly, (n _b+ n _HC)/2-0.01≤n _a≤ (n _b+ n _HC)/2+0.01, and easily the thickness T of adhesive layer satisfies:

(550/4)×(1/n _a)-10nm≤T≤(550/4)×(1/n _a)+10nm

Particularly

(550/4) * (1/n _a)-5nm≤T≤(550/4) * (1/n _aThe scope of)+5nm can obtain obviously good antireflection property, so preferred.

This has following effect: with respect to the optical wavelength of 550nm, the refractive index of base film is substantially equal to the refractive index of hard conating, and has the effect of the reflection between elimination hard conating/base film.In aspect the 5th, this easy adhesive layer preferably is formed on the transparent base film when the shaping transparent base film.

(2) as the high index of refraction particulate of high refractive index layer, the preferred use is selected from SnO ₂The electric conductivity high index of refraction particulate and the TiO that are formed with ITO ₂, ZrO ₂And CeO ₂At least a kind of high index of refraction particulate in the particulate group that the superelevation refractive index particulate of being formed is formed, and be used in combination the high index of refraction particulate of different-grain diameter, the average primary particle diameter that makes the high index of refraction particulate is 30～40nm, and be the center with this average primary particle diameter, particle size distribution range is wide, and in total particulate, primary particle size be the accumulation number of the following particulate of 30nm or its be 20% or it is above, for example be 20%～50%, primary particle size be the accumulation number of 45nm or its above particulate be 20% or it is above, for example be 20%～50%.

(3) as the bond composition of low-index layer, become to assign to improve soil resistance by using above-mentioned fluorine-containing bond.

(4) thickness by adjusting high refractive index layer and the thickness of low-index layer, realize visible-range average reflectance, need the low reflectionization under the wavelength of low reflectionization.For example, can under the condition of the wavelength that does not change minimum reflectance (paddy wavelength), increase the thickness that reduces low-index layer in the thickness of high refractive index layer, reflectivity under the paddy wavelength increases, and the average reflectance of visible-range reduces, thereby the surface reflection look that can make display is near neutral color.In addition, in the show window material,, can reduce visible reflectance fifty-fifty, reduce the actual color of the display material showed in the show window material and the difference (aberration) of the color of being seen by carrying out same thickness adjustment.

Below, in this way under the condition of the minimal reflection look that does not change anti-reflection layer, the structure that increases the thickness of high refractive index layer is described in detail.

Anti-reflection layer is stacked gradually by hard conating, high index of refraction, low-index layer and forms, and be that thickness with hard conating is that the thickness of about 2～10 μ m, high refractive index layer is that 1/4 λ forms with respect to the wavelength of 550nm, Film Thickness Ratio 1/4 λ by making formed this high refractive index layer is thicker, the reflectivity of short wavelength's one side can be reduced, and the transmissivity of the blue-light-emitting of short wavelength side can be improved.

For example, on TAC (" TAC " that the Off イ of Fuji Le system company makes) film, be coated with hard conating, high refractive index layer and low-index layer (" Z-7503 " that JSR makes) successively, high refractive index layer for high refractive index layer (n=1.68), the low-index layer that has added ITO particulate (" Ei-3 " that big Japanese coating is made) be comprise hollow silica tetramethylol methane tetraacrylate (" PE-4A " that common prosperity company makes) (n=1.43), the average reflectance when changing the thickness of high refractive index layer is as shown in table 15 below.

[table 15]

No.	High refractive index layer thickness (nm)	Low-index layer thickness (nm)	Average reflectance (%)	Comprehensive evaluation
No.	High refractive index layer thickness (nm)	Low-index layer thickness (nm)	Average reflectance (%)	Comprehensive evaluation	1	81	96	2.55	△
2	90	92	2.49	○	1	81	96	2.55	△
2	90	92	2.49	○	3	98	88	2.43	○
4	104	84	2.39	○	3	98	88	2.43	○
4	104	84	2.39	○	5	114	80	2.32	○
6	131	69	2.58	△	5	114	80	2.32	○

In addition, the reflectivity of No.1 and No.4 as shown in figure 40, No.1 and No.5,6 reflectivity are as shown in figure 41.

By these results as can be known, if increase the thickness of high refractive index layer, the reflectivity of short wavelength's one side reduces, average reflectance reduces, and more than if the thickness of high refractive index layer is increased to a certain degree, then minimum reflectance, average reflectance raise simultaneously, thereby the thickness of high refractive index layer is that 90nm～130nm is suitable as can be known.

The panel display board of the 5th aspect like this is suitable for LCD, panel display boards such as organic EL, CRT, and uses automobile navigation instrument, contact type panel of these displays etc.In addition, the show window material of the 5th aspect is particularly suitable for the displaying show window of senior showpieces such as artistic products, ornament, precious metal.

VI. the embodiment of the 6th aspect

Embodiment to the solar module of the 6th aspect describes below.

Figure 42 a～42c is the diagrammatic cross-section of anti-reflection layer part on surface of embodiment of the solar module of the 6th aspect of expression.The solar module of Figure 42 a is pasted with antireflection film 101A on the surface as the glass substrate 111 of the transparency protected parts of face side; the solar module of Figure 42 b is pasted with antireflection film 101B on the surface as the glass substrate 111 of the transparency protected parts of face side, and the solar module of Figure 42 c is as the direct formation anti-reflection layer 101C in the surface of the glass substrate 111 of the transparency protected parts of face side.

In addition, aspect the 6th, the primary structure of solar module itself is not special to be limited, and can adopt the solar module structure of routine as shown in figure 43.

Antireflection film 101A shown in Figure 42 a forms by stack gradually hard conating 103, high refractive index layer 104 and low-index layer 105 on transparent base film 102, and with on the face of the opposite side of this lamination surface, form adhesive layer 106.

In antireflection film 101A, as base film 102, can list polyester, polyethylene terephthalate (PET), polybutylene terephthalate, polymethylmethacrylate (PMMA), acrylic resin, polycarbonate (PC), polystyrene, cellulosic triacetate (TAC), polyvinyl alcohol (PVA), Polyvinylchloride, Vingon, tygon, ethylene-vinyl acetate copolymer, polyurethane, viscose paper etc., the transparent membrane of preferred PET, PC, PMMA.

The thickness of base film 102 is generally the scope of 100 μ m～188 μ m.

As hard conating 103, the hard conating of preferred synthetic resin, preferred especially ultraviolet curing resin, the combination of preferred especially multi-functional acrylate and silicon dioxide microparticle.The thickness of this hard conating 103 is preferably 2～20 μ m.

High refractive index layer 104 is preferably the material of the ultraviolet hardening of the bond composition that comprises metal oxide microparticle and have aromatic radical, as bond composition, can enumerate epoxy acrylate, urethane acrylate, contain the acrylate resin of bisphenol-A etc. with aromatic radical.In addition, as metal oxide microparticle, be preferably selected from ITO, TiO ₂, ZrO ₂, CeO ₂, Al ₂O ₃, Y ₂O ₃, La ₂O ₃And Ho ₂O ₃At least a kind or multiple high refractive index metal oxide particulate in the group of being formed, preferred especially TiO ₂Particulate, ITO particulate.

About metal oxide microparticle in the high refractive index layer 104 and bond components in proportions, the bond composition deficiency if metal oxide microparticle is too much, then the film strength of high refractive index layer reduces, otherwise,, then can not fully improve refractive index if metal oxide microparticle is very few, therefore, with respect to the total amount of metal oxide microparticle and bond composition, the ratio of metal oxide microparticle is preferably 10～60 volume %, is preferably 20～50 volume % especially.

The thickness of such high refractive index layer 104 is preferably about 80～100nm.In addition, the refractive index of this high refractive index layer 104 is preferably 1.65 or more than it, be preferably 1.66～1.85 especially, in this case, be controlled at 1.39～1.47 by the refractive index with low-index layer 105, the minimum reflectance that can obtain surface reflectivity is 1% or the good antireflection film of antireflection property below it.Particularly the refractive index of low-index layer 105 is controlled at 1.45 or the situation below it in, the minimum reflectance that can further improve antireflection, can also make surface reflectivity is 0.5% or antireflection film below it.

In aspect the 6th, low-index layer 105 be by under the atmosphere gas of the oxygen concentration of 0～10000ppm by its curing being obtained to the irradiation ultraviolet radiation of filming, wherein this is filmed and comprises bond composition and the Photoepolymerizationinitiater initiater that hollow silica, polyfunctional group (methyl) acrylic compounds form.

Hollow silica is the silicon dioxide microparticle of hollow shelly, and its mean grain size is preferably 10～200nm, is preferably 10～150nm especially.The mean grain size of this hollow silica is difficult to reduce the refractive index of hollow silica, and if greater than 200nm, then can have the problem of the diffuse reflection of light and the surfaceness increase of formed low-index layer etc. during less than 10nm.

In addition, use the refractive index of low-index layer of the 6th aspect of such hollow silica: n (low-index layer) is the refractive index of the refractive index by hollow silica: n (hollow silica) and bond composition: n (bond), calculates according to following formula.

N (low-index layer)=

In aspect the 6th, the content of the hollow silica in the low-index layer is many more, then can form the low-index layer of low-refraction more, can access the good antireflection film of antireflection property, and along with the content of bond composition reduces relatively, the film strength of low-index layer reduces, and mar proof, permanance reduce.But the reduction of the film strength that increase caused of hollow silica combined amount can remedy by the surface treatment of hollow silica, in addition, also can replenish film strength by the kind of the bond composition selecting to be mixed.

In aspect the 6th, by the surface treatment of hollow silica and the selection of bond composition, hollow silica content in the low-index layer is preferably 20～55 weight %, be preferably 30～50 weight % especially, to realize the low-refractionization of low-index layer, make refractive index about 1.39～1.45, guarantee mar proof simultaneously.

Then, polyfunctional group (methyl) acrylic compounds as the bond composition of the low-index layer of the 6th aspect is described.

[changing 22]

N, m, o, p, q, r represent 0～2 integer independently of one another,

[changing 23]

S, t, u, v represent 0～2 integer independently of one another,

In addition, in aspect the 6th, as the bond composition, 4 functional groups (methyl) acrylic compounds that preferably that above-mentioned general formula (I) is represented 6 functional groups (methyl) acrylic compounds and/or above-mentioned general formula (II) are represented, be used in combination with represented fluorine-containing difunctional (methyl) acrylic compounds of following general formula (III) or specific fluorine-containing polyfunctional group (methyl) acrylic compounds, by using these bond compositions, can give mar proof and soil resistance to low-index layer.In addition, the refractive index of 4 functional groups (methyl) acrylic compounds that these bond compositions are more represented than represented 6 functional groups (methyl) acrylic compounds of above-mentioned general formula (I) or above-mentioned general formula (II) is lower, therefore, even the combined amount of hollow silica reduces, also can form the low low-index layer of refractive index.

A ^a-O-(CH ₂) _xa-Rf-(CH ₂) _xb-O-A ^b......(III)

Employed hollow silica in aspect the 6th, its particle diameter is greater than the particle diameter of the conventional silicon dioxide microparticle that is mixed in the existing low-index layer (about particle diameter 5～20nm), therefore, even in the situation of using identical bond composition, compare with the situation of mixed silica particulate, the film strength of formed low-index layer has the tendency that dies down, and by this hollow silica being applied suitable surface treatment, can improve adhesion with the bond composition, improve the film strength of formed low-index layer, improve mar proof.

[changing 24]

[changing 25]

The low-index layer of the 6th aspect is to above-mentioned bond composition irradiation ultraviolet radiation it to be solidified to form in the presence of Photoepolymerizationinitiater initiater, as this Photoepolymerizationinitiater initiater, can use a kind of イ Le ガキユア 184,819,651,1173,907 that Xiba Special Chemical Product Co.,Ltd for example makes etc. or multiple, its combined amount is preferably 3～10phr with respect to the bond composition.When the combined amount of Photoepolymerizationinitiater initiater is lower than this scope, can not carry out sufficient crosslinking curing, and if be higher than this scope, then the film strength of low-index layer reduces.

The low-index layer of the 6th aspect is by with hollow silica, as polyfunctional group (methyl) acrylic compounds of bond composition and Photoepolymerizationinitiater initiater according to the rules the composition that mixes of ratio be applied on high refractive index layer or the electric conductivity high index of refraction hard conating, by irradiation ultraviolet radiation under the atmosphere gas of the oxygen concentration of 0～10000ppm it is solidified to form, wherein, if the oxygen concentration in the ultraviolet ray irradiation atmosphere gas surpasses 1000ppm, then traumatic resistance significantly reduces, therefore, be controlled at 1000ppm or below it, be preferably 200ppm or below it.

In aspect the 6th, in order on base film 102, to form hard conating 103, high refractive index layer 104 and low-index layer 105, preferably be coated with uncured resin combination (resin combination that mixes above-mentioned particulate as required), then irradiation ultraviolet radiation.In this case, can every coating make its curing afterwards for 1 layer, perhaps be coated with after 3 layers or 2 layers, solidify together.

In addition, as the tackifier of the adhesive layer 106 that is formed at base film 102 inner surface side, transparent adhesives such as preferred acrylic compounds, the thickness of this adhesive layer 106 is generally about 1～100 μ m, is preferably especially about 25 μ m.

The solar module of Figure 42 a is pasted with such antireflection film 101A on the glass substrate 111 as the transparency protected parts of face side; and when on transparency carriers such as glass substrate, pasting antireflection film like this; hard conating is not to be essential, it can be omitted.

The antireflection film 101B that the solar module of Figure 42 b will omit this hard conating sticks on the glass substrate 111 as the transparency protected parts of face side; on antireflection film 101B, hard conating is not set and on transparent base film 102, has directly formed high refractive index layer 104 and low-index layer 105; in addition, the structure with the solar module shown in above-mentioned Figure 42 a is identical.

In addition; shown in Figure 42 c; the solar module of the 6th aspect also can be on glass substrate 111 as the transparency protected parts of face side direct stacked high refractive index layer 104 and low-index layer 105 and film forming, and on glass substrate 111 direct formation anti-reflection layer 101C.

In the solar module aspect such the 6th, for example in the formed anti-reflection layer of the stacked film of above-mentioned antireflection film, high refractive index layer and low-index layer, by carrying out following adjustment, can realize the solar module of the high generating efficiency that better antireflection and soil resistance are good.

(n _b+n _HC)/2-0.02≤n _a≤(n _b+n _HC)/2+0.02

Particularly, (n _b+ n _HC)/2-0.01≤n _a≤ (n _b+ n _HC)/2+0.01,

And easily the thickness T of adhesive layer satisfies:

(550/4)×(1/n _a)-10nm≤T≤(550/4)×(1/n _a)+10nm

Particularly

This has following effect: with respect to the optical wavelength of 550nm, the refractive index of base film is substantially equal to the refractive index of hard conating, and has the effect of the reflection between elimination hard conating/base film.In aspect the 6th, this easy adhesive layer preferably is formed on the transparent base film when the shaping transparent base film.

(2) as the high index of refraction particulate of high refractive index layer, the preferred use is selected from SnO ₂The electric conductivity high index of refraction particulate and the TiO that are formed with ITO ₂, ZrO ₂And CeO ₂At least a kind of high index of refraction particulate in the particulate group that the superelevation refractive index particulate of being formed is formed, and the high index of refraction particulate of combination different-grain diameter, the average primary particle diameter that makes the high index of refraction particulate is 30～40nm, and be the center with this average primary particle diameter, particle size distribution range is wide, and in total particulate, primary particle size be the accumulation number of the following particulate of 30nm or its be 20% or it is above, for example be 20%～30%, primary particle size be the accumulation number of 45nm or its above particulate be 20% or it is above, for example be 20%～60%.

(3) as the bond of low-index layer,, improve soil resistance by using above-mentioned fluorine-containing bond composition.

(4) by adjusting the thickness of high refractive index layer and low-index layer, for example, by thickness that reduces high refractive index layer or the thickness that reduces low-index layer, the wavelength (paddy wavelength) that makes the minimum reflectance of anti-reflection layer is to the displacement of shortwave direction, reduce the reflectivity of the high ultraviolet range of sun power, improve energy conversion efficiency.

Below, to adjusting the thickness of high refractive index layer and/or low-index layer in this way, the minimum reflectance of anti-reflection layer is described to the method for shortwave direction displacement.

In anti-reflection layer, its transmissivity of wavelength that reflectivity is little must increase.Therefore, if the pigment of look quick type solar cell the reflectivity of the optical wavelength of the wavelength of easy absorption reduce, the transmissivity of this wavelength then raises.In addition, because the energy of the light of short wavelength side is big, therefore by reducing the reflectivity of this wavelength, pigment can absorb more high-octane light.

Common antireflection film is designed to realize the scope of the wavelength of minimum reflectance at 550～600nm.This is because the wavelength that people's visual sensitivity is the highest is 550nm, therefore, make reflectivity minimum under this wavelength.

But look quick type solar cell is according to the difference of pigment and therefore the absorbing wavelength difference must make the design that meets this pigment.

For example, on TAC (" TAC " that the Off イ of Fuji Le system company makes) film, be coated with hard conating successively, high refractive index layer and low-index layer (" Z-7503 " that JSR makes), high refractive index layer is for having added the high refractive index layer (n=1.68) of ITO particulate (" Ei-3 " that big Japanese coating is made), low-index layer be the tetramethylol methane tetraacrylate that comprises hollow silica (" PE-4A " that common prosperity company makes) (n=1.43), reflectivity when changing the thickness of high refractive index layer and low-index layer as shown in figure 44, the reflectivity under the wavelength 400nm is as shown in table 16 below.

[table 16]

No.	High refractive index layer thickness (nm)	Low-index layer thickness (nm)	400nm reflectivity (%)
No.	High refractive index layer thickness (nm)	Low-index layer thickness (nm)	400nm reflectivity (%)	1	81	96	＞4
2	81	73	＜2	1	81	96	＞4
2	81	73	＜2	3	33	96	＜2

By these results as can be known,, can change the wavelength of realizing minimum reflectance, reduce the reflectivity (raising transmissivity) of short wavelength side by reducing the thickness of low-index layer, high refractive index layer.

Claims

1. antireflection film, this antireflection film forms by stack gradually hard conating, high refractive index layer and low-index layer on transparent base film, it is characterized in that,

This low-index layer is by under the atmosphere gas of the oxygen concentration of 0～10000ppm, to the irradiation ultraviolet radiation of filming its curing is formed, and wherein this is filmed and comprises:

The silicon dioxide microparticle of hollow (hereinafter referred to as " hollow silica "),

Polyfunctional group (methyl) acrylic compounds,

Photoepolymerizationinitiater initiater.

2. antireflection film, this antireflection film forms by stack gradually electric conductivity high index of refraction hard conating and low-index layer on transparent base film, it is characterized in that,

Polyfunctional group (methyl) acrylic compounds,

Photoepolymerizationinitiater initiater.

3. antireflection film according to claim 1, it is characterized in that this polyfunctional group (methyl) acrylic compounds is a principal ingredient with following general formula (I) represented 6 functional groups (methyl) acrylic compounds and/or represented 4 functional groups (methyl) acrylic compounds of following general formula (II):

N, m, o, p, q, r represent 0～2 integer independently of one another,

R ¹～R ⁶Represent that independently of one another carbon number is that carbon number that 1～3 alkylidene or one or more hydrogen atoms are replaced by fluorine atom is 1～3 the alkylidene of fluoridizing.)，

S, t, u, v represent 0～2 integer independently of one another,

R ¹¹～R ¹⁴Represent that independently of one another carbon number is that carbon number that 1～3 alkylidene or one or more hydrogen atoms are replaced by fluorine atom is 1～3 the alkylidene of fluoridizing.)。

4. antireflection film according to claim 3, it is characterized in that, this polyfunctional group (methyl) acrylic compounds further comprises represented fluorine-containing difunctional (methyl) acrylic compounds of following general formula (III), and in total polyfunctional group (methyl) acrylic compounds, the ratio of this fluorine-containing difunctional (methyl) acrylic compounds is 5 weight % or more than it

A ^a-O-(CH ₂) _xa-Rf-(CH ₂) _xb-O-A ^b......(III)

(in above-mentioned general formula (III), A ^a, A ^bRepresent acryloyl group, methacryl, α-fluorine acryloyl group or trifluoromethyl acryloyl group independently of one another, Rf represents perfluorinated alkylidene, and xa, xb represent 0～3 integer independently of one another.)。

5. antireflection film according to claim 3, it is characterized in that, this polyfunctional group (methyl) acrylic compounds further comprises and is selected from that to have 6 or more a plurality of fluorine atom and molecular weight in 1 molecule be 1000 or (methyl) acrylic compounds of 3～6 functional groups below it, with a kind or multiple fluorine-containing polyfunctional group (methyl) acrylic compounds in 1 molecular weight, having in (methyl) acrylic compounds that 10 or more a plurality of fluorine atom and molecular weight are 1000～5000 6～15 functional groups, and in total polyfunctional group (methyl) acrylic compounds, the ratio of this fluorine-containing polyfunctional group (methyl) acrylic compounds is 5 weight % or more than it.

6. antireflection film according to claim 1, it is characterized in that, above-mentioned hollow silica has been carried out acrylic acid modified (methyl) the acrylic acid modified hollow silica of end group (methyl) for by represented end group (methyl) the acrylic silane coupling agent of following general formula (IV) to the surface

R ²³～R ²⁵Represent that independently of one another hydrogen atom or carbon number are 1～4 alkyl.)。

7. antireflection film according to claim 6, it is characterized in that, above-mentioned hollow silica be by with 100～150 ℃ of above-mentioned end group (methyl) acrylic silane coupling agent under hydro-thermal reaction or the reaction under microwave irradiation, acrylic acid modified (methyl) the acrylic acid modified hollow silica of end group (methyl) has been carried out on the surface.

8. antireflection film according to claim 1, it is characterized in that, above-mentioned hollow silica is for passing through the represented end group fluorinated alkyl silane coupling agent of following general formula (V), the fluorinated alkyl modification hollow silica of the surface having been carried out the modification of end group fluorinated alkyl

(in above-mentioned general formula (V), R ³¹～R ³³Represent that independently of one another hydrogen atom or carbon number are 1～4 alkyl, ya represents 1～8 integer, and yb represents 1～3 integer.)。

9. antireflection film according to claim 8, it is characterized in that, above-mentioned hollow silica be by with 100～150 ℃ of above-mentioned end group fluorinated alkyl silane coupling agent under hydro-thermal reaction or the reaction under microwave irradiation, the fluorinated alkyl modification hollow silica of the surface having been carried out the modification of end group fluorinated alkyl.

10. antireflection film, this antireflection film forms by stack gradually hard conating, transparency conducting layer, light absorbing zone and low-index layer on transparent base film, it is characterized in that,

Polyfunctional group (methyl) acrylic compounds,

Photoepolymerizationinitiater initiater,

And, the minimum reflectance of this antireflection film be 0.5% or its transmissivity following, wavelength 550nm be 70% or its reflectivity above, wavelength 400nm be 2% or below it.

11. an antireflection film, this antireflection film forms by stack gradually hard conating, electric conductivity light absorbing zone and low-index layer on transparent base film, it is characterized in that,

Polyfunctional group (methyl) acrylic compounds,

Photoepolymerizationinitiater initiater,

12. antireflection film according to claim 10 is characterized in that, is provided with easy adhesive layer on this transparent base film, is provided with hard conating on this easy adhesive layer,

The refractive index of this hard conating is 1.48～1.55,

If refractive index that will this easy adhesive layer is designated as n _a, the refractive index of this transparent base film is designated as n _b, the refractive index of this hard conating is designated as n _HC, then

(n _b+n _HC)/2-0.03≤n _a≤(n _b+n _HC)/2+0.03

The thickness T of this easy adhesive layer satisfies:

(550/4)×(1/n _a)-10nm≤T≤(550/4)×(1/n _a)+10nm。

13. antireflection film according to claim 12 is characterized in that, this easy adhesive layer is formed on this transparent base film when being shaped this transparent base film.

14. antireflection film according to claim 10, it is characterized in that this polyfunctional group (methyl) acrylic compounds is a principal ingredient with following general formula (I) represented 6 functional groups (methyl) acrylic compounds and/or represented 4 functional groups (methyl) acrylic compounds of following general formula (II):

N, m, o, p, q, r represent 0～2 integer independently of one another,

S, t, u, v represent 0～2 integer independently of one another,

15. antireflection film according to claim 10, it is characterized in that, above-mentioned hollow silica be by with 100～150 ℃ of represented end group (methyl) the acrylic silane coupling agent of following general formula (IV) under hydro-thermal reaction or the reaction under microwave irradiation, acrylic acid modified (methyl) the acrylic acid modified hollow silica of end group (methyl) has been carried out on the surface

16. antireflection film according to claim 10, it is characterized in that, above-mentioned hollow silica be by with 100～150 ℃ of the represented end group fluorinated alkyl silane coupling agent of following general formula (V) under hydro-thermal reaction or the reaction under microwave irradiation, the surface has been carried out the fluorinated alkyl modification hollow silica of end group fluorinated alkyl modification

17. antireflection film according to claim 10 is characterized in that, above-mentioned transparency conducting layer is to be selected from ATO, ZnO, Sb with (methyl) acrylic compounds bond resin solidification ₂O ₅, SnO ₂, ITO and In ₂O ₃In at least a particulate form, and its thickness is 80～200nm.

18. antireflection film according to claim 10 is characterized in that, above-mentioned light absorbing zone comprises carbon black particle and titanium nitride particulate, and, if the complex index of refraction of this light absorbing zone is designated as n+ik, then

n＝1.45～1.75、

k＝0.1～0.35。

19. antireflection film according to claim 11 is characterized in that, above-mentioned electric conductivity light absorbing zone comprises carbon black particle, and, if the complex index of refraction of this electric conductivity light absorbing zone is designated as n+ik, then

n＝1.45～1.75、

k＝0.1～0.35。

20. antireflection film according to claim 10 is characterized in that, this transparent base film is the PET film, and above-mentioned hard conating one side of this PET film is formed with, and refractive index is 1.55～1.61, thickness is the easy adhesive layer of 75～95nm.

21. an antireflection film, this antireflection film forms by stack gradually easy adhesive layer, hard conating, high refractive index layer and low-index layer on transparent base film, it is characterized in that,

Polyfunctional group (methyl) acrylic compounds,

Photoepolymerizationinitiater initiater.

22. an antireflection film, this antireflection film forms by stack gradually easy adhesive layer, high index of refraction hard conating and low-index layer on transparent base film, it is characterized in that,

Polyfunctional group (methyl) acrylic compounds,

Photoepolymerizationinitiater initiater.

23. antireflection film according to claim 21 is characterized in that, the refractive index of this hard conating is 1.48～1.55,

(n _b+n _HC)/2-0.03≤n _a≤(n _b+n _HC)/2+0.03

The thickness T of this easy adhesive layer satisfies:

(550/4)×(1/n _a)-10nm≤T≤(550/4)×(1/n _a)+10nm。

24. antireflection film according to claim 21 is characterized in that, this easy adhesive layer is formed on this transparent base film when being shaped this transparent base film.

25. antireflection film according to claim 21 is characterized in that, the refractive index of above-mentioned high refractive index layer is 1.68 or more than it, and this high refractive index layer comprises and is selected from SnO ₂The electric conductivity high index of refraction particulate and the TiO that are formed with ITO ₂, ZrO ₂And CeO ₂At least a kind of high index of refraction particulate in the particulate group that the superelevation refractive index particulate of being formed is formed and with the bond composition of represented 6 functional groups (methyl) acrylic compounds of following general formula (VI) as principal ingredient,

(in above-mentioned general formula (VI), A ⁴¹～A ⁴⁶Represent acryloyl group, methacryl, α-fluorinated acrylamide acyl group or trifluoromethyl acryloyl group independently of one another.)。

26. antireflection film according to claim 25 is characterized in that, the average primary particle diameter of above-mentioned high index of refraction particulate is 10～150nm.

27. antireflection film according to claim 25, it is characterized in that, the average primary particle diameter of above-mentioned high index of refraction particulate is 30～40nm, and in total particulate, primary particle size be the accumulation number of the following particulate of 30nm or its be 20% or it is above, primary particle size is 45nm or its above particulate accumulation number be 20% or more than it.

28. antireflection film according to claim 25, it is characterized in that, above-mentioned high index of refraction particulate is for covering the high index of refraction particulate that the ITO particulate is made on the anatase titanium dioxide particulate, and the average primary particle diameter of titanium dioxide fine particles is that cover thickness that 5～80nm, ITO particulate form is 5nm or more than it.

29. antireflection film according to claim 25, it is characterized in that, above-mentioned high index of refraction particulate is for covering the high index of refraction particulate that the ITO particulate is made on the rutile titanium dioxide particulate, and the cover thickness that the aspect ratio of titanium dioxide fine particles is 2～10, the ITO particulate forms is 5nm or more than it.

30. antireflection film according to claim 21, it is characterized in that this polyfunctional group (methyl) acrylic compounds is a principal ingredient with following general formula (I) represented 6 functional groups (methyl) acrylic compounds and/or represented 4 functional groups (methyl) acrylic compounds of following general formula (II):

N, m, o, p, q, r represent 0～2 integer independently of one another,

S, t, u, v represent 0～2 integer independently of one another,

31. antireflection film according to claim 30, it is characterized in that, this polyfunctional group (methyl) acrylic compounds further comprises represented fluorine-containing difunctional (methyl) acrylic compounds of following general formula (III), and in total polyfunctional group (methyl) acrylic compounds, the ratio of this fluorine-containing difunctional (methyl) acrylic compounds is 5 weight % or more than it.

A ^a-O-(CH ₂) _xa-Rf-(CH ₂) _xb-O-A ^b......(III)

32. antireflection film according to claim 30, it is characterized in that, this polyfunctional group (methyl) acrylic compounds further comprises and is selected from that to have 6 or more a plurality of fluorine atom and molecular weight in 1 molecule be 1000 or (methyl) acrylic compounds of 3～6 functional groups below it, with a kind or multiple fluorine-containing polyfunctional group (methyl) acrylic compounds in 1 molecular weight, having in (methyl) acrylic compounds that 10 or more a plurality of fluorine atom and molecular weight are 1000～5000 6～15 functional groups, and in total polyfunctional group (methyl) acrylic compounds, the ratio of this fluorine-containing polyfunctional group (methyl) acrylic compounds is 5 weight % or more than it.

33. antireflection film according to claim 21, it is characterized in that, above-mentioned hollow silica has been carried out acrylic acid modified (methyl) the acrylic acid modified hollow silica of end group (methyl) for by represented end group (methyl) the acrylic silane coupling agent of following general formula (IV) to the surface

34. antireflection film according to claim 33, it is characterized in that, above-mentioned hollow silica be by with 100～150 ℃ of above-mentioned end group (methyl) acrylic silane coupling agent under hydro-thermal reaction or the reaction under microwave irradiation, (methyl) acrylic acid modified (methyl) acrylic acid modified hollow silica has been carried out on the surface.

35. antireflection film according to claim 21, it is characterized in that, above-mentioned hollow silica is for passing through the represented end group fluorinated alkyl silane coupling agent of following general formula (V), the fluorinated alkyl modification hollow silica of the surface having been carried out the modification of end group fluorinated alkyl

36. antireflection film according to claim 35, it is characterized in that, above-mentioned hollow silica be by with 100～150 ℃ of above-mentioned end group fluorinated alkyl silane coupling agent under hydro-thermal reaction or the reaction under microwave irradiation, the fluorinated alkyl modification hollow silica of the surface having been carried out the modification of end group fluorinated alkyl.

37. an electromagnetic wave shielding transmitance window material, this window material is characterized in that by forming to major general's electro-magnetic screen layer and transparency carrier, the stacked integration of outermost anti-reflection layer,

This anti-reflection layer has high refractive index layer and the low-index layer that is arranged on this high refractive index layer,

This low-index layer is filmed by photocuring and is formed, and described filming comprises:

Polyfunctional group (methyl) acrylic compounds,

Photoepolymerizationinitiater initiater.

38. according to the described electromagnetic wave shielding transmitance of claim 37 window material, it is characterized in that this polyfunctional group (methyl) acrylic compounds is a principal ingredient with following general formula (I) represented 6 functional groups (methyl) acrylic compounds and/or represented 4 functional groups (methyl) acrylic compounds of following general formula (II):

N, m, o, p, q, r represent 0～2 integer independently of one another,

S, t, u, v represent 0～2 integer independently of one another,

39. according to the described electromagnetic wave shielding transmitance of claim 38 window material, it is characterized in that, this polyfunctional group (methyl) acrylic compounds further comprises represented fluorine-containing difunctional (methyl) acrylic compounds of following general formula (III), and in total polyfunctional group (methyl) acrylic compounds, the ratio of this fluorine-containing difunctional (methyl) acrylic compounds is 5 weight % or more than it

A ^a-O-(CH ₂) _xa-Rf-(CH ₂) _xb-O-A ^b......(III)

40. according to the described electromagnetic wave shielding transmitance of claim 38 window material, it is characterized in that, this polyfunctional group (methyl) acrylic compounds further comprises and is selected from that to have 6 or more a plurality of fluorine atom and molecular weight in 1 molecule be 1000 or (methyl) acrylic compounds of 3～6 functional groups below it, with a kind or multiple fluorine-containing polyfunctional group (methyl) acrylic compounds in 1 molecular weight, having in (methyl) acrylic compounds that 10 or more a plurality of fluorine atom and molecular weight are 1000～5000 6～15 functional groups, and in total polyfunctional group (methyl) acrylic compounds, the ratio of this fluorine-containing polyfunctional group (methyl) acrylic compounds is 5 weight % or more than it.

41. according to the described electromagnetic wave shielding transmitance of claim 37 window material, it is characterized in that, above-mentioned hollow silica be by with 100～150 ℃ of represented end group (methyl) the acrylic silane coupling agent of following general formula (IV) under hydro-thermal reaction or the reaction under microwave irradiation, (methyl) acrylic acid modified (methyl) acrylic acid modified hollow silica has been carried out on the surface

42. according to the described electromagnetic wave shielding transmitance of claim 37 window material, it is characterized in that, above-mentioned hollow silica be by with 100～150 ℃ of the represented end group fluorinated alkyl silane coupling agent of following general formula (V) under hydro-thermal reaction or the reaction under microwave irradiation, the surface has been carried out the fluorinated alkyl modification hollow silica of end group fluorinated alkyl modification

43., it is characterized in that above-mentioned high refractive index layer comprises the high index of refraction particulate and has the bond composition of aryl according to the described electromagnetic wave shielding transmitance of claim 37 window material.

44., it is characterized in that above-mentioned anti-reflection layer directly is formed on the above-mentioned transparency carrier according to the described electromagnetic wave shielding transmitance of claim 37 window material.

45. according to the described electromagnetic wave shielding transmitance of claim 37 window material, it is characterized in that, above-mentioned anti-reflection layer is the antireflection film that sticks on the outermost surface, and this antireflection film forms by stack gradually hard conating, high refractive index layer and low-index layer on transparent base film.

46. according to the described electromagnetic wave shielding transmitance of claim 37 window material, it is characterized in that, it is arranged in the illuminant colour on the front surface of red more weak luminescent panel, and by increasing the thickness of above-mentioned high refractive index layer or low-index layer, the wavelength of minimum reflectance that makes this electromagnetic wave shielding transmitance window material is to the displacement of long wave direction, and reaches red light wavelength by the wavelength that makes this minimum reflectance and improve red transmissivity.

47. according to the described electromagnetic wave shielding transmitance of claim 37 window material, it is characterized in that, it is arranged on the front surface of the more weak luminescent panel of illuminant colour Smalt, and by reducing the thickness of above-mentioned high refractive index layer or low-index layer, the wavelength of minimum reflectance that makes this electromagnetic wave shielding transmitance window material is to the displacement of shortwave direction, and reaches blue light wavelength by the wavelength that makes this minimum reflectance and improve blue transmissivity.

48. a gas discharge type luminescent panel, it is by luminescent panel body, the electro-magnetic screen layer and the stacked integration of outermost anti-reflection layer that are arranged on the front surface of this luminescent panel body being formed, it is characterized in that,

This anti-reflection layer possesses high refractive index layer and the low-index layer that is arranged on this high refractive index layer,

Polyfunctional group (methyl) acrylic compounds,

Photoepolymerizationinitiater initiater.

49. according to the described gas discharge type luminescent panel of claim 48, it is characterized in that this polyfunctional group (methyl) acrylic compounds is a principal ingredient with following general formula (I) represented 6 functional groups (methyl) acrylic compounds and/or represented 4 functional groups (methyl) acrylic compounds of following general formula (II):

N, m, o, p, q, r represent 0～2 integer independently of one another,

S, t, u, v represent 0～2 integer independently of one another,

50. according to the described gas discharge type luminescent panel of claim 49, it is characterized in that, this polyfunctional group (methyl) acrylic compounds further comprises represented fluorine-containing difunctional (methyl) acrylic compounds of following general formula (III), and in total polyfunctional group (methyl) acrylic compounds, the ratio of this fluorine-containing difunctional (methyl) acrylic compounds is 5 weight % or more than it

A ^a-O-(CH ₂) _xa-Rf-(CH ₂) _xb-O-A ^b ......(III)

51. according to the described gas discharge type luminescent panel of claim 49, it is characterized in that, this polyfunctional group (methyl) acrylic compounds further comprises and is selected from that to have 6 or more a plurality of fluorine atom and molecular weight in 1 molecule be 1000 or (methyl) acrylic compounds of 3～6 functional groups below it, with a kind or multiple fluorine-containing polyfunctional group (methyl) acrylic compounds in 1 molecular weight, having in (methyl) acrylic compounds that 10 or more a plurality of fluorine atom and molecular weight are 1000～5000 6～15 functional groups, and in total polyfunctional group (methyl) acrylic compounds, the ratio of this fluorine-containing polyfunctional group (methyl) acrylic compounds is 5 weight % or more than it.

52. according to the described gas discharge type luminescent panel of claim 48, it is characterized in that, above-mentioned hollow silica be by with 100～150 ℃ of represented end group (methyl) the acrylic silane coupling agent of following general formula (IV) under hydro-thermal reaction or the reaction under microwave irradiation, (methyl) acrylic acid modified (methyl) acrylic acid modified hollow silica has been carried out on the surface

53. according to the described gas discharge type luminescent panel of claim 48, it is characterized in that, above-mentioned hollow silica be by with 100～150 ℃ of the represented end group fluorinated alkyl silane coupling agent of following general formula (V) under hydro-thermal reaction or the reaction under microwave irradiation, the surface has been carried out the fluorinated alkyl modification hollow silica of end group fluorinated alkyl modification

54., it is characterized in that above-mentioned high refractive index layer comprises the high index of refraction particulate and has the bond composition of aryl according to the described gas discharge type luminescent panel of claim 48.

55., it is characterized in that be provided with transparency carrier in front surface one side of above-mentioned luminescent panel body, above-mentioned anti-reflection layer directly is formed on this transparency carrier according to the described gas discharge type luminescent panel of claim 48.

56. according to the described gas discharge type luminescent panel of claim 48, it is characterized in that, above-mentioned anti-reflection layer is the antireflection film that sticks on the outermost surface, and this antireflection film forms by stack gradually hard conating, high refractive index layer and low-index layer on transparent base film.

57. according to the described gas discharge type luminescent panel of claim 48, it is characterized in that, this luminescent panel body is a red more weak luminescent panel body in the color development light, and by increasing the thickness of above-mentioned high refractive index layer or low-index layer, make this anti-reflection layer the wavelength of minimum reflectance to the displacement of long wave direction, and reach red light wavelength by the wavelength that makes this minimum reflectance and improve red transmissivity.

58. according to the described gas discharge type luminescent panel of claim 48, it is characterized in that, this luminescent panel body is the more weak luminescent panel body of illuminant colour Smalt, and by reducing the thickness of above-mentioned high refractive index layer or low-index layer, the wavelength of minimum reflectance that makes this anti-reflection layer is to the displacement of shortwave direction, and reaches blue light wavelength by the wavelength that makes this minimum reflectance and improve blue transmissivity.

59. a panel display board, it is provided with anti-reflection layer from the teeth outwards, and this anti-reflection layer has high refractive index layer and the low-index layer that is arranged on this high refractive index layer, it is characterized in that,

Polyfunctional group (methyl) acrylic compounds,

Photoepolymerizationinitiater initiater.

60. according to the described panel display board of claim 59, it is characterized in that this polyfunctional group (methyl) acrylic compounds is a principal ingredient with following general formula (I) represented 6 functional groups (methyl) acrylic compounds and/or represented 4 functional groups (methyl) acrylic compounds of following general formula (II):

N, m, o, p, q, r represent 0～2 integer independently of one another,

S, t, u, v represent 0～2 integer independently of one another,

61. according to the described panel display board of claim 60, it is characterized in that, this polyfunctional group (methyl) acrylic compounds further comprises represented fluorine-containing difunctional (methyl) acrylic compounds of following general formula (III), and in total polyfunctional group (methyl) acrylic compounds, the ratio of this fluorine-containing difunctional (methyl) acrylic compounds is 5 weight % or more than it

A ^a-O-(CH ₂) _xa-Rf-(CH ₂) _xb-O-A ^b ......(III)

62. according to the described panel display board of claim 60, it is characterized in that, this polyfunctional group (methyl) acrylic compounds further comprises and is selected from that to have 6 or more a plurality of fluorine atom and molecular weight in 1 molecule be 1000 or (methyl) acrylic compounds of 3～6 functional groups below it, with a kind or multiple fluorine-containing polyfunctional group (methyl) acrylic compounds in 1 molecular weight, having in (methyl) acrylic compounds that 10 or more a plurality of fluorine atom and molecular weight are 1000～5000 6～15 functional groups, and in total polyfunctional group (methyl) acrylic compounds, the ratio of this fluorine-containing polyfunctional group (methyl) acrylic compounds is 5 weight % or more than it.

63. according to the described panel display board of claim 59, it is characterized in that, above-mentioned hollow silica be by with 100～150 ℃ the hydro-thermal reaction or the reaction under microwave irradiation of represented end group (methyl) the acrylic silane coupling agent of following general formula (IV), acrylic acid modified (methyl) the acrylic acid modified hollow silica of end group (methyl) has been carried out on the surface

64. according to the described panel display board of claim 59, it is characterized in that, above-mentioned hollow silica be by with 100～150 ℃ of the represented end group fluorinated alkyl silane coupling agent of following general formula (V) under hydro-thermal reaction or the reaction under microwave irradiation, the surface has been carried out the fluorinated alkyl modification hollow silica of end group fluorinated alkyl modification

65., it is characterized in that above-mentioned high refractive index layer comprises the high index of refraction particulate and has the bond composition of aryl according to the described panel display board of claim 59.

66., it is characterized in that it has transparency carrier in a surperficial side, and above-mentioned anti-reflection layer directly is formed on this transparency carrier according to the described panel display board of claim 59.

67. according to the described panel display board of claim 59, it is characterized in that, above-mentioned anti-reflection layer is the antireflection film that sticks on the outermost surface, and this antireflection film forms by stack gradually hard conating, high refractive index layer and low-index layer on transparent base film.

68. according to the described panel display board of claim 59, it is characterized in that, by under the condition of the wavelength of the minimum reflectance that does not change above-mentioned anti-reflection layer, increasing above-mentioned high refractive index layer thickness and reducing the thickness of above-mentioned low-index layer, reflectivity under the wavelength of this minimum reflectance is increased, and reduce the average reflectance of visible-range, thereby the surface reflection look that makes display is near neutral color.

69. a show window material, it is provided with anti-reflection layer from the teeth outwards, and this anti-reflection layer has high refractive index layer and the low-index layer that is arranged on this high refractive index layer, it is characterized in that,

Polyfunctional group (methyl) acrylic compounds,

Photoepolymerizationinitiater initiater.

70. according to the described show window material of claim 69, it is characterized in that this polyfunctional group (methyl) acrylic compounds is a principal ingredient with following general formula (I) represented 6 functional groups (methyl) acrylic compounds and/or represented 4 functional groups (methyl) acrylic compounds of following general formula (II):

N, m, o, p, q, r represent 0～2 integer independently of one another,

S, t, u, v represent 0～2 integer independently of one another,

71. according to the described show window material of claim 70, it is characterized in that, this polyfunctional group (methyl) acrylic compounds further comprises represented fluorine-containing difunctional (methyl) acrylic compounds of following general formula (III), and in total polyfunctional group (methyl) acrylic compounds, the ratio of this fluorine-containing difunctional (methyl) acrylic compounds is 5 weight % or more than it

A ^a-O-(CH ₂) _xa-Rf-(CH ₂) _xb-O-A ^b......(III)

72. according to the described show window material of claim 70, it is characterized in that, this polyfunctional group (methyl) acrylic compounds further comprises and is selected from that to have 6 or more a plurality of fluorine atom and molecular weight in 1 molecule be 1000 or (methyl) acrylic compounds of 3～6 functional groups below it, with a kind or multiple fluorine-containing polyfunctional group (methyl) acrylic compounds in 1 molecular weight, having in (methyl) acrylic compounds that 10 or more a plurality of fluorine atom and molecular weight are 1000～5000 6～15 functional groups, and in total polyfunctional group (methyl) acrylic compounds, the ratio of this fluorine-containing polyfunctional group (methyl) acrylic compounds is 5 weight % or more than it.

73. according to the described show window material of claim 69, it is characterized in that, above-mentioned hollow silica be by with 100～150 ℃ of represented end group (methyl) the acrylic silane coupling agent of following general formula (IV) under hydro-thermal reaction or the reaction under microwave irradiation, acrylic acid modified (methyl) the acrylic acid modified hollow silica of end group (methyl) has been carried out on the surface

74. according to the described show window material of claim 69, it is characterized in that, above-mentioned hollow silica be by with 100～150 ℃ of the represented end group fluorinated alkyl silane coupling agent of following general formula (V) under hydro-thermal reaction or the reaction under microwave irradiation, the surface has been carried out the fluorinated alkyl modification hollow silica of end group fluorinated alkyl modification

75., it is characterized in that above-mentioned high refractive index layer comprises the high index of refraction particulate and has the bond composition of aryl according to the described show window material of claim 69.

76., it is characterized in that possessing transparency carrier and directly be formed at the lip-deep anti-reflection layer of this transparency carrier according to the described show window material of claim 69.

77. according to the described show window material of claim 69, it is characterized in that, possess transparency carrier and the lip-deep antireflection film that sticks on this transparency carrier, this antireflection film forms by stack gradually hard conating, high refractive index layer and low-index layer on transparent base film.

78. according to the described panel display board of claim 69, it is characterized in that, by under the condition of the wavelength of the minimum reflectance that does not change above-mentioned anti-reflection layer, increasing the thickness of above-mentioned high refractive index layer and reducing the thickness of above-mentioned low-refraction, reflectivity under the wavelength of this minimum reflectance is increased, and reduce the average reflectance of visible-range, thereby reduce the actual color of display material and the aberration of the color of being seen.

79. a solar module, this solar module are can use battery formed by battery by sealed solar between transparency protected parts of face side and inner surface side guard block, it is characterized in that,

Surface at the transparency protected parts of this face side is formed with anti-reflection layer,

Polyfunctional group (methyl) acrylic compounds,

Photoepolymerizationinitiater initiater.

80. according to the described solar module of claim 79, it is characterized in that this polyfunctional group (methyl) acrylic compounds is a principal ingredient with following general formula (I) represented 6 functional groups (methyl) acrylic compounds and/or represented 4 functional groups (methyl) acrylic compounds of following general formula (II):

N, m, o, p, q, r represent 0～2 integer independently of one another,

S, t, u, v represent 0～2 integer independently of one another,

81. 0 described solar module according to Claim 8, it is characterized in that, this polyfunctional group (methyl) acrylic compounds further comprises represented fluorine-containing difunctional (methyl) acrylic compounds of following general formula (III), and in total polyfunctional group (methyl) acrylic compounds, the ratio of this fluorine-containing difunctional (methyl) acrylic compounds is 5 weight % or more than it

A ^a-O-(CH ₂) _xa-Rf-(CH ₂) _xb-O-A ^b......(III)

82. 0 described solar module according to Claim 8, it is characterized in that, this polyfunctional group (methyl) acrylic compounds further comprises and is selected from that to have 6 or more a plurality of fluorine atom and molecular weight in 1 molecule be 1000 or (methyl) acrylic compounds of 3～6 functional groups below it, with a kind or multiple fluorine-containing polyfunctional group (methyl) acrylic compounds in 1 molecular weight, having in (methyl) acrylic compounds that 10 or more a plurality of fluorine atom and molecular weight are 1000～5000 6～15 functional groups, and in total polyfunctional group (methyl) acrylic compounds, the ratio of this fluorine-containing polyfunctional group (methyl) acrylic compounds is 5 weight % or more than it.

83. according to the described solar module of claim 79, it is characterized in that, above-mentioned hollow silica be by with 100～150 ℃ of represented end group (methyl) the acrylic silane coupling agent of following general formula (IV) under hydro-thermal reaction or the reaction under microwave irradiation, acrylic acid modified (methyl) the acrylic acid modified hollow silica of end group (methyl) has been carried out on the surface

84. according to the described solar module of claim 79, it is characterized in that, above-mentioned hollow silica be by with 100～150 ℃ of the represented end group fluorinated alkyl silane coupling agent of following general formula (V) under hydro-thermal reaction or the reaction under microwave irradiation, the surface has been carried out the fluorinated alkyl modification hollow silica of end group fluorinated alkyl modification

85., it is characterized in that above-mentioned high refractive index layer comprises the high index of refraction particulate and has the bond composition of aryl according to the described solar module of claim 79.

86., it is characterized in that above-mentioned anti-reflection layer directly is formed on the transparency protected parts of above-mentioned face side according to the described solar module of claim 79.

87. according to the described solar module of claim 79; it is characterized in that; above-mentioned anti-reflection layer is the antireflection film that sticks on the transparency protected parts of above-mentioned face side, and this antireflection film is by stacking gradually high refractive index layer and low-index layer forms on transparent base film.

88. 7 described solar modules is characterized in that according to Claim 8, are provided with hard conating between above-mentioned transparent base film and high refractive index layer.

89., it is characterized in that by reducing the thickness of above-mentioned high refractive index layer or low-index layer, the wavelength of minimum reflectance that makes this anti-reflection layer is to the displacement of shortwave direction according to the described solar module of claim 79.