KR20070017132A - Transparent laminate - Google Patents

Abstract

A transparent laminate having excellent antireflection, near infrared and electromagnetic shielding properties, durability, visibility, and light weight, and useful as an optical filter includes a first laminate including a first transparent substrate, an antireflection layer formed on its front and back surfaces, and a near infrared shielding layer, respectively. And a second laminate including a second transparent substrate and an electromagnetic wave shielding layer formed on the surface thereof are integrated by bonding the near-infrared shielding layer and the electromagnetic wave shielding layer such as a metal mesh layer through an adhesive layer.

Reflection, near-infrared, shielding, mesh, metal, transparent, substrate, electromagnetic wave, lamination, adhesive, bonding, visual recognition.

Description

Transparent laminate {TRANSPARENT LAMINATE}

The present invention relates to a transparent laminate, and more particularly, to a transparent laminate useful as an optical filter on a display surface of a display device such as a plasma display.

Plasma display devices (hereinafter referred to as PDPs) include a front glass substrate having a display electrode, a bus electrode, a dielectric layer, and a protective layer, and a rear glass substrate having a phosphor layer on the data electrode, the dielectric layer, and the stripe barrier rib. A cell is formed by bonding so that it may cross orthogonally, and it is comprised by discharging discharge gas, such as xenon, in this cell. The light emission of the plasma display device is caused by the discharge of xenon due to the application of a voltage between the data electrode and the display electrode, and generates ultraviolet rays when the xenon ions in the plasma state return to the ground state. R) Green (G) and blue (B) light is emitted. In the process of emitting these visible lights, near infrared rays and electromagnetic waves are generated in addition to these visible lights. Therefore, the plasma display device is generally provided with an antireflection film, a near infrared absorbing film, and a filter provided with an electromagnetic wave shielding function on the entire surface of the plasma display light emitting part based on the glass.

Plasma display devices are considered to be useful as thin display devices with small installation spaces and wall-mounted display devices. However, in the above-described plasma display device, as described in Japanese Patent Application Laid-open No. Hei 10-319859 (Patent Document 1), on the PDP apparatus including the light emitting means, there are several layers on the glass with a certain space spaced therefrom. Since the optical filter means comprised by laminating | stacking the film laminated body which laminated | stacked the applied film is provided, it cannot be said that sufficient weight reduction is achieved, and in order to actually hang it on the wall in a normal house, the wall needs to be strong enough. It may be necessary to perform reinforcement work on the wall itself beforehand. In addition, there is a drawback that external light appears twice on the display surface by reflection of the front glass part of the PDP, the front surface and the back surface of the optical filter. In general, the main thing of the electromagnetic shielding film used in the optical filter is an etched metal (copper) mesh, or because the metal (copper) is exposed on the etched end surface, the reflection color peculiar to the metal (copper) is changed to the display image. It is giving a problem to a hue.

[Patent Document 1] Japanese Patent Application Laid-Open No. 10-319859

The present invention has excellent anti-reflective property, near-infrared shielding, and electromagnetic shielding properties, has excellent durability and visibility, is lightweight, easy to manufacture and handle, and can be used as an optical filter on a display surface of a display device such as a plasma display device. It is to provide a transparent laminate.

The transparent laminated body of this invention was formed on the 1st laminated part, the 2nd transparent base material, and the 1st laminated part containing a 1st transparent base material, the reflection prevention layer formed on the one surface, and the near-infrared shielding layer formed on the other surface. It has a 2nd laminated part which consists of an electromagnetic wave shielding layer, the near-infrared shielding layer of a said 1st laminated part, and the adhesive bond layer which joins the said 2nd laminated part, It is characterized by the above-mentioned.

In the transparent laminate of the present invention, it is preferable that the electromagnetic wave shielding layer is a metal mesh layer.

In the transparent laminated body of this invention, it is preferable that the near-infrared shielding layer of a said 1st laminated part and the electromagnetic wave shielding layer of a said 2nd laminated part are joined.

In the transparent laminated body of this invention, the said 2nd laminated part may further have a back adhesive layer formed on the other surface of the said 2nd transparent base material.

In the transparent laminated body of this invention, it is preferable that the adhesive strength of the back surface adhesive layer of a said 2nd laminated part is 1-20N / 25mm.

In the transparent laminate of the present invention, the near-infrared shielding layer of the first laminate portion has an absorption maximum in a region of the first near-infrared absorbing dye made of at least one near-infrared absorptive dimonium-based compound, and in the region of the near-infrared wavelength of 750 to 950 nm. And a transparent resin comprising a second near-infrared absorbing dye comprising the dimonium-based compound and at least one kind of dye compound, and a polymer of at least one type of ethylenically unsaturated monomer, wherein the polymer for transparent resin At least 30% by mass of the ethylenically unsaturated monomer constituting the compound represented by the following general formula (2):

[In the above formula (2), R represents a hydrogen atom or a methyl group, and X represents a cyclic hydrocarbon group having 6 to 25 carbon atoms.

In the transparent laminate of the present invention, the near-infrared absorptive dimonium compound for the first near-infrared absorbing dye contained in the near-infrared shielding layer of the first laminate comprises a dimonium compound cation and the following formula (1);

_{(CF 3 SO 2) 2 N} - (1)

It is preferable that it is comprised by the counter anion represented by

In the transparent laminate of the present invention, the near-infrared absorptive dimonium compound for the first near-infrared absorbing dye contained in the near-infrared shielding layer of the first laminate part is represented by the following general formula (3):

It is preferable that it is a compound represented by.

In the transparent laminated body of this invention, the said transparent resin contained in the near-infrared shielding layer of a said 1st laminated part has the glass transition temperature of 60-120 degreeC, the number average molecular weight of 20,000-80,000, and the weight average molecular weight of 200,000-400,000. It is preferable.

In the transparent laminate of the present invention, the anti-reflection layer of the first laminate part includes a hard coating layer, a conductive medium refractive index layer laminated on the hard coating layer, a high refractive index layer laminated on the conductive medium refractive index layer, and It is preferable that it is comprised from the low refractive index layer laminated | stacked on the high refractive index layer.

In the transparent laminate of the present invention, the hard coat layer included in the antireflection layer contains oxide fine particles and a binder component, and the content rate of the oxide fine particles is preferably 30% by mass or more.

In the transparent laminated body of this invention, it is preferable that the said metal mesh layer contained in a said 2nd laminated part contains the metal mesh which has the surface blackened by the electroplating of black metal.

In the transparent laminate of the present invention, the electromagnetic wave shielding layer preferably has a thickness of 1 to 15 µm.

In the transparent laminated body of this invention, it is preferable that a shock absorbing layer is further contained between the near-infrared shielding layer of the said 1st laminated part, and the said adhesive bond layer.

In the manufacturing method of the transparent laminated body of this invention, an anti-reflective layer is formed on one surface of a 1st transparent base material, a near-infrared shielding layer is formed on the other surface of a 1st transparent base material, and a 1st laminated part is formed separately, A metal mesh layer is formed on one surface of the second transparent substrate to form a second laminate, and the near infrared shielding layer of the first laminate and the metal mesh layer of the second laminate are bonded to each other through an adhesive layer to form a laminate. It is characterized by.

In the manufacturing method of the transparent laminated body of this invention, in order to form the metal mesh layer of the said 2nd laminated part, the image which has a desired mesh pattern is printed by ink containing a catalyst on one surface of a 2nd transparent base material, It is preferable to perform electroless metal plating and / or electrolytic metal plating on the printed surface to deposit metal along the pattern of the catalyst-containing ink image and to fix it on the second transparent substrate.

(Effects of the Invention)

The transparent laminate of the present invention is excellent in anti-reflection, near-infrared shielding, electromagnetic shielding, durability, visual observation of images, and is light and easy to manufacture and handle, for example, to display various display devices such as plasma display devices. It is practically useful as a surface optical filter.

1 is a cross-sectional explanatory view of an example of a transparent laminate of the present invention,

2 is a cross-sectional explanatory view of another example of the transparent laminate of the present invention,

3 is a cross-sectional explanatory view of an antireflection layer of the transparent laminate of the present invention,

4 is an explanatory front view of the transparent laminate of the present invention,

5 is an explanatory view of a partial cross section when the transparent laminate of the present invention is mounted on a PDP.

As shown in FIG. 1, the transparent laminated body 1 of this invention is the 1st transparent base material 11, the antireflection layer 12 formed in the one surface, and the near-infrared shielding layer 13 formed in the other surface. ), The first laminated portion 61 having the first laminated portion 61, the second transparent substrate 21, the second laminated portion 62 having the electromagnetic shielding layer 22 formed on one surface thereof, and the first laminated portion 61; And an adhesive layer 31 for bonding the second laminate part 62 to each other.

In the conventional transparent laminated body for optical filters, each functional layer mentioned above was formed on a separate transparent base material, and the transparent base material which supports these functional layers was formed by laminating | stacking with a glass panel through an adhesive layer.

In the transparent laminate of the present invention, since the antireflection layer is formed on one surface of the first transparent substrate and the near-infrared shielding layer is formed on the other surface, the number of the transparent substrate and the adhesive layer is reduced, and high transmittance and low haze are achieved. In this way, improved optical characteristics can be obtained.

Since the transparent laminated body of this invention has the structure mentioned above, it does not contribute to each function, and is equipped with the various functions in combination, reducing the number of base materials and adhesive layers which may adversely affect in some cases. The integral transparent laminated body is comprised. In addition, since the number of bonding steps is required once, the number of manufacturing steps is reduced, the production yield is improved, the performance of the product is stabilized, and the reliability is also improved. In addition, since the antireflection layer forms the outermost layer of the transparent laminate, an excellent antireflection effect is obtained.

Moreover, the transparent laminated body of this invention is a agent which has a 1st laminated base material which has a 1st transparent base material, the reflection prevention layer formed in each surface, and the near-infrared shielding layer, a 2nd transparent base material, and the electromagnetic wave shielding layer formed in the one surface. It is preferable that 2 laminated parts are laminated | stacked and bonded together the near-infrared shielding layer side of a 1st laminated part, and the electromagnetic wave shielding layer side of a 2nd laminated part through an adhesive bond layer. In this case, since the near-infrared shielding layer and the electromagnetic wave shielding layer are sandwiched and protected between the first and second transparent substrates, they are excellent in durability and weather resistance of the performance and excellent in reliability. Moreover, when using a metal mesh layer as an electromagnetic wave shielding layer, an adhesive bond layer fills the space | gap part of the metal mesh of a metal mesh layer, and the transparent laminated body which has no space | gap part is obtained.

(1st and 2nd transparent base material)

As long as it is a transparent material, a 1st transparent base material and a 2nd transparent base material do not have a limitation in the kind, composition, etc. The material constituting the first and second transparent substrates is generally selected from transparent plastic materials, and for example, polyester-based substrates in the form of plates or sheets or films, triacetylcellulose substrates, polycarbonate substrates, polyethers A sulfone substrate, a polyacrylate substrate, a norbornene-based substrate, an amorphous polyolefin-based substrate, or the like can be appropriately selected, and the thickness thereof is not particularly limited, and a film or plate form of about 50 μm to 10 mm can be used. As a polyester base material, the polyethylene terephthalate (henceforth PET) base material is especially used preferably because it is excellent in the point of durability, solvent resistance, productivity, etc. In addition, you may use the colored thing for the 1st transparent base material and the 2nd transparent base material in order to adjust color tone and transmittance | permeability.

The transparent laminate of the present invention is excellent in the antireflection effect, the near infrared shielding effect, and the electromagnetic wave shielding effect required for the plasma display. Therefore, an optical filter having excellent characteristics on the display surface of the plasma display can be formed by adhering the transparent laminate to a panel such as glass or plastic, or directly to the display surface of the plasma display. In particular, when the transparent plastic substrate in the form of a film is used as the first transparent substrate and the second transparent substrate, the transparent laminate of the present invention including such a substrate is composed of a plasma because a transparent laminate having a light weight and flexibility can be constituted. It is particularly suitable for the case of direct adhesion to the display surface of the display.

(About ultraviolet shielding property of a 1st transparent base material)

Moreover, in the transparent laminated body of this invention, it is preferable to use the material which has ultraviolet-ray shielding property as a 1st transparent base material. This is because the near-infrared absorbing dye used for a near-infrared shielding layer is generally low in ultraviolet resistance, and can suppress deterioration of a near-infrared absorbing dye by using the material which has an ultraviolet shielding property as a 1st transparent base material. For example, the transparent base material which has ultraviolet-shielding property can be obtained by containing a ultraviolet absorber in the 1st transparent base material which consists of a material mentioned above. As a ultraviolet absorber, ultraviolet absorbing compounds, such as a benzophenone series, a benzotriazole type, a paraamino benzoic acid type, and a salicylic acid type, are mentioned, for example. Usually, a sufficient effect will not be acquired if a ultraviolet absorber is not used in any added amount or more. When adding a ultraviolet absorber to a thin coating layer, there is a limit to the amount of ultraviolet absorber that can be contained in the coating layer, it is difficult to obtain the required ultraviolet shielding effect. However, in the transparent laminate of the present invention, since the near-infrared shielding layer is located inside the first transparent substrate, the ultraviolet absorber is contained in the first transparent substrate itself having a larger thickness than the coating layer so that a sufficient amount of the ultraviolet absorber is contained. Therefore, deterioration of a near-infrared absorbing pigment can be suppressed and the outstanding near-infrared absorption performance can be maintained by it. As ultraviolet-ray shielding performance of a 1st transparent base material, it is preferable that an ultraviolet transmittance is 2% or less in the ultraviolet region of 380 nm or less.

(Near infrared shielding layer)

In the transparent laminate of the present invention, the near-infrared shielding layer preferably has a shielding property against near-infrared rays in the region of 800 to 1100 nm, and preferably contains a near-infrared absorbing dye in the resin matrix. The near-infrared absorbing dye is not particularly limited as long as it has a near-infrared shielding property in the range of 800 to 1100 nm. Examples thereof include dimonium compounds, aluminum compounds, phthalocyanine compounds, organometallic complex compounds, cyanine compounds, azo compounds, and polymethines. A compound, a quinone compound, a diphenylmethane compound, a triphenylmethane compound, a mercaptonnaphthol compound, etc. can be used, These may be used by a single species, or may be used in combination of 2 or more types suitably. good.

The dimonium compound has a strong absorptivity with a molar extinction coefficient of about 100,000 in the near infrared region having a wavelength of 850 to 1100 nm, and thus is excellent in the near infrared shielding property. The dimonium-based compound has a slight absorption in the visible light region having a wavelength of 400 to 500 um and forms a yellowish-brown transmission color. However, the near-infrared absorbing pigment used in the transparent laminate of the present invention because the visible light transmittance is superior to other near-infrared absorbing pigments. It is preferable that at least 1 type of dimonium type compound is contained in it.

A near-infrared ray shielding layer, a near infrared absorbent di aunt nyumgye used in the transparent laminate of the present invention compound is the diimonium compound cation in the general formula _{(1): (CF 3 SO} 2) 2 N - by a counter anion represented by The compound comprised is used preferably, It is preferable to use the compound of the said General formula (3) as such a near-infrared absorptive dimonium type compound.

In order for a near-infrared shielding layer to express practically sufficient near-infrared shielding property, it is preferable that the transmittance | permeability of the near-infrared wavelength of 900-1000 nm is 20% or less. The preferred blending amount of the near-infrared absorbing pigment in the near-infrared shielding layer varies depending on the thickness of the near-infrared shielding layer. When using a dimonium-based compound and designing the thickness of the near-infrared shielding layer to about 5 to 50 µm, it is transparent. It is preferable that the compounding quantity of a near-infrared absorptive dye compound is about 0.5-5.0 mass parts with respect to 100 mass parts of resin. When the compounding quantity of a near-infrared absorbing dye compound with respect to 100 mass parts of transparent matrix resin exceeds 5 mass parts, it may cause segregation of a pigment in a near-infrared shielding layer obtained, a fall of visible light transparency, etc. can be caused.

In addition, when using a dimonium type compound, in order to give practically sufficient durability to the near-infrared shielding layer obtained, it is preferable to use what has a melting point of 190 degreeC or more as said dimonium type compound. A melting point lower than 190 ° C. is easy to deteriorate under high temperature, high humidity. However, a melting point of 190 ° C. or higher can provide a near-infrared shielding layer having a practically good durability in addition to selecting a suitable matrix resin type described later.

In addition, in order to express practically sufficient near-infrared shielding property in a near-infrared shielding layer, it is preferable to use the near-infrared absorptive pigment | dye whose near-infrared transmittance with a wavelength of 850-900 nm is 20% or less. For this purpose, for example, when a dimonium-based compound is used, at least one dye having an absorption maximum at 750 to 900 nm as the second near infrared absorbing dye and having no substantial absorption in the visible region, for example, the absorption coefficient at the absorption maximum wavelength and It is preferable to use one or two or more near-infrared absorbing dyes in which the ratios of the respective absorption coefficients at wavelengths of 450 nm (center wavelength of blue light), 525 nm (center wavelength of green light), and 620 nm (center wavelength of red light) are all 5.0 or more, It is more preferable that the ratio of the said extinction coefficient is 8.0 or more. When any one of the ratios of the extinction coefficients is less than 5.0, when the average transmittance of 850 to 900 nm, which is practically necessary, is 20% or less, wavelengths 450 nm (center wavelength of blue light), 525 nm (center wavelength of green light), and 620 nm (center wavelength of red light) Any one of the visible light transmittances at) becomes less than 60%, and the transmittance in the visible light region may become insufficient practically.

Absorbance maximum at 750-900 nm, the absorption coefficient at the absorption maximum wavelength and the respective absorption coefficients at wavelength 450 nm (center wavelength of blue light), 525 nm (center wavelength of green light) and 620 nm (center wavelength of red light). Examples of the second near infrared absorbing dye compound having a ratio of 5.0 or more include dithiol nickel complex compounds, indoleum compounds, phthalocyanine compounds, naphthalocyanine compounds, and the like. In particular, the phthalocyanine-based compound and the naphthalocyanine-based compound are generally excellent in durability and can be suitably used. Since the naphthalocyanine-based compound is more expensive, the phthalocyanine-based compound is more suitably used in practice.

Furthermore, in the transparent laminate of the present invention, it is preferable that the transmittance of visible light having a wavelength of 590 nm is 10% or less lower than that of visible light at wavelengths of 450 nm, 525 nm, and 620 nm, respectively. In this case, when the transparent laminate of the present invention is used as an optical filter, the contrast of a display such as a plasma display is improved, and the color tone correction function is increased. In order to make the transmittance | permeability of visible light of wavelength 590nm of the transparent laminated body of this invention 10% or more lower than the transmittance | permeability of visible light in wavelength 450nm, 525nm, and 620nm, respectively, it is preferable to contain a selective absorbing color material in a near-infrared shielding layer. The colorant which selectively absorbs visible light having a wavelength of 590 nm is not particularly limited as long as it does not adversely affect the deterioration in the composition of the dimonium compound. For example, a quinacridone pigment, an azomethine compound, a cyanine compound, a porphyrin compound, and the like. It is preferable to use.

As a near-infrared absorbing dye matrix resin, acrylic resin, methacrylic resin, etc. can be used, for example, It is preferable to use the transparent resin whose glass transition point is 60 degreeC or more, As such a transparent resin, Acrylic resin, methacrylic resin It is preferable that either one. If the glass transition point of the transparent resin is less than 60 ° C., the resin softens when exposed to high temperature of 60 ° C. or more for a long time, and at the same time, the pigment in the near-infrared shielding layer is particularly susceptible to deterioration, and thus the transparent laminate The long-term stability of the color balance may be impaired or the shielding property of the near infrared rays may be degraded. On the other hand, when a glass transition point is 60 degreeC or more, thermal alteration of a pigment | dye, especially the pigment | dye which consists of a dimonium type compound can be suppressed in the near-infrared shielding layer obtained. In addition, by using the above resin, it is possible to prevent deterioration of the pigment in the near infrared shielding layer, distortion of the near infrared shielding layer, peeling, and the like when the near infrared shielding layer is laminated and bonded to the electromagnetic shielding layer through the adhesive layer. Examples of the resin that satisfies the above requirements include polyester resins, acrylic resins, methacryl resins, and the like, and acrylic resins and / or methacryls having excellent dyeing property (adhesiveness) of dimonium compounds, which are alkaline dyes. It is suitable to use a system resin.

As a formation method of a near-infrared shielding layer, the formation method of dissolving or disperse | distributing said near-infrared absorbing dye and matrix resin in a solvent, apply | coating the obtained solution or dispersion on one surface of a 1st transparent base material, and drying a solvent is known. have. As a coating method, the normal coating layer formation method may be sufficient, For example, the coating method using coating apparatuses, such as a bar coater, a gravure reverse coater, and a slit die coater, can be used.

Examples of the solvent of the coating solution for forming the near-infrared shielding layer include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetone, acetonitrile, dichloromethane, dimethylformamide, butyl acetate, toluene, and the like. It may be used alone or in combination.

(Reflective layer)

In the transparent laminated body of this invention, there is no limitation in the structure, composition, etc. of the antireflection layer formed on the other surface of a 1st transparent base material, and may have a single layer structure, or may have multiple structures. Moreover, you may further form the thin film layer which has functions, such as an electrically conductive layer, such as an antistatic layer, and / or an anti-glare layer, on an antireflection layer.

(Electromagnetic shielding layer)

In the transparent laminate of the present invention, there is no limitation on the configuration, composition, and the like of the electromagnetic shielding layer formed on one surface of the second transparent substrate of the second laminate, and may be formed so as to have electromagnetic shielding properties and image transmittance, for example, a metal mesh. A layer, a transparent conductive film containing a conductive material, and the like can be used.

For example, the metal mesh layer may be obtained by bonding a metal mesh to a second transparent substrate, and laminating a metal foil such as copper foil on the second transparent substrate, or etching a metal layer formed by plating a metal such as copper to form a mesh pattern. What was formed in the form of etc. can be used. Here, as a metal mesh adhere | attached to the 2nd transparent base material, what adhere | attached the metal plated mesh on the surface of the metal mesh or the fiber is used. As the transparent conductive film layer, for example, a conductive material such as silver formed by vapor deposition, sputtering, or the like is used.

In addition, it is preferable that it is 1-15 micrometers, and, as for the thickness of an electromagnetic wave shielding layer, it is more preferable that it is 1-10 micrometers. When using a metal mesh layer as an electromagnetic shielding layer, when the thickness of a metal mesh layer is thicker than 15 micrometers, a viewing angle will become narrow and visibility will fall. Furthermore, even when the surface is blackened, when visually recognized in an oblique direction, the depth direction of the metal mesh is hardly blackened, and the color tone of the metal is exposed, thereby causing a problem in color tone of the screen.

In addition, as shown in FIG. 1, in the second laminated portion 62 of the transparent laminate 1 of the present invention, an electromagnetic wave shielding layer 22 is formed on one surface of the second transparent substrate 21. The back adhesive layer 41 may be formed on the other surface. This backside adhesive layer allows the transparent laminate of the present invention to be adhered to a panel such as glass or plastic, or directly to the display surface of the plasma display, whereby an optical filter having excellent characteristics on the display surface of the plasma display can be obtained. Can be fixed In addition, when the 2nd transparent base material 21 is in contact with the adhesive bond layer 31, and the electromagnetic wave shielding layer 22 is formed in the opposite side to the adhesive bond layer 31, the back surface adhesive layer (on the electromagnetic wave shielding layer 22 41) may be formed. It is preferable that the adhesive (adhesive) strength of this back surface adhesive layer is 1-20 N / 25 mm (1-20 N / 1 inch) at the initial stage of adhesion, More preferably, it is 1-15 N / 25 mm, More preferably, Is 1-10 N / 25 mm, More preferably, it is 4-8 N / 25 mm. This is because when the transparent laminate of the present invention is directly adhered to the display surface of the plasma display as an optical filter, it may be necessary to peel off again after the adhesion. In order to reuse the module by peeling the optical filter, for example, when the bonding position is not appropriate or when the optical filter is damaged after the adhesion, the adhesive strength of the backing adhesive layer is preferably some weak adhesion. . More suitably, it is preferable that the said adhesive (adhesion) strength rises with time, and when it reaches an equilibrium, the adhesive strength is 5-25 N / 25 mm, More preferable Preferably it is 10-15N / 25mm. Thus, by forming the adhesive layer with a relatively low adhesive strength on the back surface of the said 2nd laminated part of the transparent laminated body of this invention, peeling operation of the transparent laminated body in case of emergency is made easy, and the expensive module main body It can make it possible to reuse.

(Specific example of near infrared shielding layer)

In the transparent laminate of the present invention, the near-infrared shielding layer is a first near-infrared ray composed of at least one near-infrared absorptive dimonium compound composed of a dimonium compound cation and a counter anion represented by the formula (1). A second near-infrared absorbing pigment which has an absorption maximum, an absorption maximum in the region of 750-950 nm of near-infrared wavelength, and consists of the said dimonium type compound and at least 1 sort (s) of heterogeneous pigment compound, and at least 1 type of ethylenically unsaturated It is preferable that 30 mass% or more of the said at least 1 sort (s) of ethylenically unsaturated monomer is included in the monomer represented by the said General formula (2) including transparency resin containing the polymer of a monomer.

As mentioned above, it is suitable to use a dimonium compound as a near-infrared absorbing dye, However, when it is left to stand for a long time in a high temperature, high-humidity atmosphere, a dimonium compound has a problem that a change in composition cannot be avoided.

The present inventors have studied the mechanism of deterioration of a dimonium compound under a high temperature and high humidity atmosphere. As a result, the deterioration is caused by the decomposition of the counter anion in the dimonium compound by the intervening moisture in the resin composition coating film and the thermal energy by heating. Was found to be due. Moreover, this inventor is a dimonium type cationic compound which has a specific counter anion of General formula (1), and is heterogeneous with a 1st near-infrared absorption pigment | dye, has an absorption maximum in a near-infrared region, and does not show absorption substantially in a visible region. The near-infrared shielding layer containing the second near-infrared absorbing dye and the transparent resin made of a monomer containing 30% by mass or more of the specific monomer compound represented by the general formula (2) has a change in chromaticity under a high temperature, high humidity atmosphere and a long exposure of external light. Less, having a high transmittance in the visible region and a high near-infrared shielding region in the 850-1000 nm region, and without degrading the characteristics of the near-infrared shielding layer by heating, pressurization and contact with the adhesive layer, and furthermore, It was discovered that lamination can be bonded to the mesh layer.

(First Near Infrared Absorption Dye)

In the transparent laminate of the present invention, a compound composed of a counter anion and a dimonium compound cation of the formula (1) is preferably used as the first near infrared absorbing dye. Since the dimonium-based cationic compound has a specific counter anion represented by the formula (1), when it is included in the near infrared shielding layer, the counter anion of the formula (1) is decomposed by thermal energy by intervening moisture and heating. It exhibits strong resistance to, and can thereby suppress the deterioration of the composition of the first dye.

In the near-infrared shielding film formed by using the near-infrared shielding paint, it is preferable to control the average transmittance of wavelength 850nm to 900nm to 20% or less in order to express practically sufficient near-infrared shielding property. When only the dimonium compound is contained in the near-infrared shielding film, sufficient near-infrared shielding cannot be obtained in the wavelength region, and when the first near-infrared absorbing dye is contained in an excessive content in order to improve the near-infrared shielding, the chromaticity before and after each test ( It is not preferable because the amount of change in X and Y) is large.

Therefore, it is preferable to add the 2nd near-infrared absorbing pigment which has absorption maximum in wavelength 750-950nm, but is substantially absorptive to visible region to the near-infrared shielding layer formation paint of this invention. By containing a 1st near-infrared absorbing dye and a 2nd near-infrared absorbing dye, the obtained near-infrared shielding layer can form the coating film which has the outstanding near-infrared shielding property in the near-infrared region of 850 nm-1000 nm, and also the outstanding transmittance also in a visible light part.

(2nd near infrared absorption pigment)

The second near-infrared absorbing dye used in the present invention is applied to the respective extinction coefficients at wavelength 450 nm (central wavelength of blue light), 525 nm (central wavelength of green light), and 620 nm (central wavelength of red light) of the extinction coefficient at the absorption maximum wavelength. It is preferable that all the ratios are 5.0 or more, and it is more preferable that it is 8.0 or more. When the ratio with respect to the extinction coefficient of any one of said wavelengths is less than 5.0, when the average transmittance of wavelength 850nm-900nm is 20% or less, wavelength 450nm (center wavelength of blue light), 525nm (center wavelength of green light), and 620nm (center wavelength of red light) Any one of the visible light transmittances at) becomes less than 60%, and the transmittance in the visible light region may be insufficient.

As a 2nd near-infrared absorption pigment | dye used for this invention, a dithiol metal complex type compound, a phthalocyanine type compound, a naphthalocyanine type compound, a cyanine type compound, etc. are mentioned, for example. In particular, phthalocyanine-based compounds are suitably used because of their excellent solubility in organic solvents.

Recently, many phthalocyanine-based compounds having an absorption maximum in the near-infrared region have been proposed by introducing conjugated π-electron substituents such as phenyl groups or a plurality of electron-donating substituents such as alkoxy groups to the phthalocyanine skeleton. The phthalocyanine-based compound represented by) can be suitably used in the present invention because the ratio of the extinction coefficient is 5.0 or more, respectively.

[In Formula (4), eight α's each independently represent one selected from -SR ¹ , -0R ^2, and -NHR ³ groups and halogen atoms, provided that at least one α represents a -NHR ³ group , 8 β each independently represent at least one selected from —SR ¹ , —0R ² and a halogen atom, provided that at least one β represents a —SR ¹ or —0R ² group, and the eight α and 8 At least one of β represents a halogen atom and a -0R ² group,

R ¹ , R ² and R ³ each independently represent one selected from a phenyl group having or without a substituent, an alkyl group having 1 to 20 carbon atoms and an aralkyl group having 7 to 20 carbon atoms,

M represents one selected from one metal atom, one or more hydrogen atoms, one metal oxide and a metal halide]

Moreover, 2 or more types of near-infrared absorbing dye compounds may be respectively used as a 1st near-infrared absorbing dye and a 2nd near-infrared absorbing dye, and further other pigment | dye may be added as needed. Moreover, it is preferable that the compounding mass ratio of a 1st near-infrared absorbing dye and a 2nd near-infrared absorbing dye is 3: 2-29: 1, More preferably, it is 2: 1-9: 1. If the blending ratio is less than 3/2, the transmittance of the visible ray light may become insufficient, and if it exceeds 29/1, the amount of chromaticity change before and after various reliability tests may increase.

(Transparent Resin for Near Infrared Shielding Layer)

The transparency resin used for the paint for forming the near-infrared shielding layer of the present invention includes at least one selected from polymers of at least one ethylenically unsaturated monomer, and includes at least 30% by mass of the ethylenically unsaturated monomers forming the polymer, Preferably, 50-100 mass% is a monomer compound of the said General formula (2). The transparency resin having the above-described structure shows high solubility in various organic solvents (for example, toluene, xylene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, mesoisobutyl ketone, cyclohexane and tetrahydrofuran) and high A coating film having moisture permeability and ultraviolet resistance can be formed. In the monomer represented by General formula (2), it is preferable that they are C6-C25 cyclic hydrocarbon group represented by X, for example, a cyclohexyl group, a methylcyclohexyl group, a cyclododecyl group, a carbonyl group, an isobornyl group.

As transparency resin formed by superposing | polymerizing the monomer component containing 30 mass% or more of monomer compounds represented by General formula (2), it is preferable that it is methacrylate resin which has X = C6-C25 cyclic hydrocarbon group. Thermoplastic coatings formed of paints in which the first and second near-infrared absorbing pigments are dispersed in other general methacrylate resins such as methyl methacrylate resins, due to the influence of moisture in the environment when they are exposed for a long time under high temperature and high humidity Deterioration of the resin coating film occurs, thereby causing a problem that the chromaticity of the coating film is greatly changed due to the deterioration of the first near infrared absorbing dye. On the other hand, by using the polymer containing the monomer represented by the said General formula (2) as an essential monomer component as transparency resin, the durability under the high temperature, high humidity of the said 1st near-infrared absorbing dye improves, and also the durability to ultraviolet irradiation Can also be improved.

Moreover, in this invention, it is preferable that the transparency resin for a near-infrared shielding layer is thermoplastic methacrylate type resin. When another thermosetting resin, an ultraviolet curable resin, or an electron beam curable resin is used, the reaction activator contained in the resin and the dimonium compound for the first near-infrared absorbing dye easily react with each other to form a pigment in the resin composition or during the film formation process. May cause degeneration.

It is preferable that content with respect to the monomer whole quantity of the monomer compound represented by the said General formula (2) is 30 mass% or more with respect to the gross mass of all the monomers used for polymer formation. When it is less than 30%, the chromaticity change of the coating film by the deterioration of the dimonium type compound for 1st near-infrared absorption pigment | dye may not be fully suppressed. Content of the monomer compound of General formula (2) becomes like this. Preferably it is 50 mass% or more, More preferably, it is 80-100 mass% or more.

The thermoplastic methacrylate resin containing the monomer compound represented by the general formula (2) as an essential polymerization component can be easily synthesized by solution polymerization in a general organic solvent such as toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, and the like. Can be. Moreover, the solubility of the 1st dimonium type compound for near-infrared absorbing dyes and transparency resin itself in paint is sufficiently high, and a stable resin composition can be obtained as a paint.

In the transparency resin obtained by superposing | polymerizing the monomer containing 30 mass% or more of monomer compounds represented by General formula (2), it is preferable that the glass transition point is 60 degreeC or more and 120 degrees C or less, and it is more preferable that it is 80-100 degreeC. Do. If the glass transition point is less than 60 ° C., the resin softens when the coating film is exposed to high temperature of 80 ° C. or more for a long time, and at the same time, the dimonium compound for near-infrared absorbing dye in the coating film is easily deteriorated, and the chromaticity of the coating film is greatly changed or The near-infrared shielding property of a coating film may fall, and long-term heat resistance may fall. However, when the glass transition point of a transparent resin is 60 degreeC or more, the deterioration of the 1st and 2nd near-infrared absorbing dye, especially a dimonium type compound by heat can be suppressed. On the other hand, when a glass transition temperature exceeds 120 degreeC, the coating film obtained will be hard and it will be easy to be broken, and practical problems may arise, for example, to generate | occur | produce a crack easily by fall of bending resistance, handling, etc.

It is preferable that the transparency resin used for this invention is a thermoplastic methacrylate type resin whose glass transition point is 60 degreeC or more and 120 degrees C or less.

Furthermore, in the present invention, the molecular weight of the transparent resin used for the near-infrared shielding layer is preferably a number average molecular weight of 20,000 or more and 80,000 or less, and a weight average molecular weight of 200,000 or more and 400,000 or less. In addition, a number and a weight average molecular weight are the measured values obtained using polystyrene standard GPC. When the weight average molecular weight is less than 200,000, the flexibility of the near-infrared shielding film to be formed may be insufficient, the bending resistance may be inferior, and the chemical resistance may be inferior. In addition, when the weight average molecular weight exceeds 400,000, it may become difficult to solution polymerize the polymer itself. On the other hand, when the number average molecular weight is less than 20,000 or more than 80,000, the chemical resistance of the polymer obtained may be insufficient.

Moreover, when the 1st transparent base material is polyester resin, it is preferable that the transparency resin for near-infrared shielding layers used for this invention has a suitable acid value derived from the monomer containing a carboxyl group. Thereby, adhesiveness with a polyester resin film can be improved. This also improves long-term stability and prevents deterioration of characteristics such as peeling off during lamination. It is preferable that the said suitable acid value is 1 mgKOH or more and 20 mgKOH or less with respect to resin solid content. If the acid value is less than 1 mgKOH, sufficient adhesion between the coating film and the substrate may not be obtained, while if it exceeds 20 mgKOH, it may adversely affect the stability of the dimonium compound for the first near infrared absorbing dye under high temperature.

In addition, when using the said polyester-type resin as a 1st base material, in order to improve the practical adhesiveness with a near-infrared shielding layer, it is preferable to form the adhesive improvement layer which consists of organic resin components on a base material. In the case where the adhesion improving layer is not formed, the near-infrared shielding layer may be easily peeled off at the interface between the polyester resin film and the near-infrared shielding layer.

Although the adhesive improvement layer which can be used for this invention contains an organic resin component as a main component, in order to suppress the color change in use of a near-infrared shielding laminated body, it is preferable that a reactive hardening | curing agent is not included.

There is no restriction | limiting in particular about the organic resin component in the said adhesion | attachment improvement layer, as long as practically sufficient adhesiveness is obtained between the said near-infrared shielding layer and polyester-type resin, For example, acrylic resin, acryl- melanin copolymer resin, acryl- polyester copolymer, poly Ester resin etc. can be used individually or these 2 or more types of mixtures can be used. Moreover, in order to improve the winding property of a film in a coating process, and to prevent blocking and a generation of a scratch, you may contain microparticles | fine-particles, such as a silica fine particle and talc, suitably in an adhesion improving layer.

When reactive adhesives, such as an isocyanate compound and a block isocyanate compound, are contained in the said adhesive improvement layer, when it is exposed to high temperature of 80 degreeC or more for a long time, the 1st near-infrared absorbing dimonium type compound for near-infrared absorbing dye will react with these reactive hardening agents, It is liable to be deteriorated, and the chromaticity of the near-infrared shielding layer is greatly changed, and / or the near-infrared shielding is deteriorated, and the long-term heat resistance can be adversely affected.

In the paint for forming the near-infrared shielding layer used in the present invention, it is preferable that the dry solid mass ratio of the total mass of the first and second near-infrared absorbing dyes to the transparent resin is in the range of 1:99 to 1: 4, More preferably, it is 1: 49-1: 24. If this mass ratio is less than 1/99, it may be necessary to thicken the dry film thickness of the near infrared shielding layer to 20 μm or more in order to obtain a high near infrared shielding rate, but the formation of such a thick film may be difficult, and it also exceeds 1/4 In the process of forming the near-infrared shielding coating film, problems such as deterioration of shielding performance and increase of haze value due to segregation of the infrared absorbing dye may occur.

Moreover, the transparent laminated body of this invention is the degradation acceleration test of 1,000 hours in the high humidity atmosphere of 60 degreeC and 90% of a relative humidity, the degradation acceleration test of 1,000 hours in the high temperature dry atmosphere of 80 degreeC and 50% of relative humidity, Near-infrared shielding lamination before and after the test in each of the 48 hour deterioration accelerated test in a high temperature, high humidity atmosphere with a temperature of 80 ° C. and a relative humidity of 95% and the 48 hour deteriorated accelerated weathering test by irradiation of a xenon lamp of 550 W / m ² of irradiance. It is preferable that it is 0.005 or less, and, as for the amount of change of chromaticity (X and Y) of a sieve, it is more preferable that it is 0-0.003. With such characteristics, when the laminate of the present invention is used in various displays such as a plasma display, its characteristics such as near-infrared shielding properties, visible light transmittance, color tone, etc., can be changed over a long period of time with temperature changes, moisture, and even light irradiation from the outside. It is possible to display a stable image for a long time without deterioration.

(Formation method of near-infrared shielding layer)

In the near-infrared shielding layer of the transparent laminate of the present invention, the first near-infrared absorbing dye, the second near-infrared absorbing dye, and the transparent resin are dissolved or dispersed in the solvent, and the resulting solution or dispersion is applied to one side on the first transparent substrate. The solvent can be formed by drying evaporation. As a coating method, the method normally used may be sufficient, for example, it can apply | coat using coating devices, such as a bar coater, a gravure reverse coater, and a slit die coater.

(Shock absorbing layer)

Furthermore, in the transparent laminated body of this invention, it is preferable that the shock absorbing layer is arrange | positioned between a 1st laminated part and a 2nd laminated part. For example, as shown in FIG. 2, the shock absorbing layer 32 formed by shock absorption is laminated between the near-infrared shielding layer 13 and the adhesive bond layer 31 of the 1st laminated part 61, and a shock absorbing layer as needed. (32) and the near-infrared shielding layer 13 may be further bonded through the intermediate adhesive layer 31a. Alternatively, the shock absorbing material may be contained in the adhesive layer 31 between the near infrared ray shielding layer 13 and the electromagnetic wave shielding layer 22. This is to prevent the impact strength from being lowered as much as excluding glass, when the transparent laminate of the present invention is directly adhered to the display surface of the plasma display, as compared with the optical filter with a conventional glass panel. As the shock absorber, silicone rubber, urethane rubber, styrene butadiene rubber, nitrile rubber, chloroprene rubber, ethylene-propylene rubber, butyl rubber, fluorine rubber, elastomer materials of these copolymers, resins such as polyethylene, polyolefin, cellulose, etc. A film etc. can be used.

In order to use for an optical filter, when the transmittance | permeability and haze are considered, it is preferable that the thickness of the said shock absorption layer 32 is 0.1-1.5 mm. Moreover, as a characteristic of the said shock absorber, it is preferable that tensile strength is 6-10 Mpa, and elongation at the time of cutting | disconnection is 150 to 400%.

(Explanation of Anti-reflective Layer)

In the transparent laminate of the present invention, as shown in FIG. 3, the anti-reflection layer 12 formed on the first laminate and the first transparent substrate 11 includes a hard coat layer 51 and the hard coat layer 51. ), The high refractive index layer 53 laminated on the conductive medium refractive index layer 52, and the low refractive index layer 54 laminated on the high refractive index layer 53. It is preferable that it consists of).

The antireflection layer having such a structure is an antireflection layer having conductivity, and can prevent adhesion of dust due to static electricity and the like. In addition, since the conductive medium refractive layer has the function of the medium refractive index layer, it is possible to form an antireflection film formed by three layers of medium refractive, high refractive index, and low refractive index, thereby obtaining an excellent antireflection effect.

(Hard Coating Layer of Anti-Reflection Layer)

Although the hard-coat layer laminated | stacked on a 1st transparent base material is formed by the resin component, it is preferable to contain an oxide fine particle. By containing an oxide fine particle, adhesiveness with a 1st transparent base material improves. Adhesiveness is especially important so that the antireflection layer in this invention does not peel or damage at the time of adhesion | attachment of a 1st transparent base material and a 2nd transparent base material.

It is preferable that content of oxide fine particles in a hard coat layer is 30 mass%-80 mass%. When content of oxide fine powder is less than 30 mass%, adhesiveness between a 1st transparent base material and a medium refractive index layer will fall, and film hardness, such as the target pencil hardness and steel wool strength, will not be obtained. When the content of the oxide fine powder is more than 80% by mass, the content of the oxide fine powder is excessive, the film strength of the obtained hard coating layer is reduced, or the whitening phenomenon is observed in the obtained hard coating layer, or the flexibility of the film after curing is reduced, so that cracks are formed. Problems such as being easy to occur occur.

Moreover, it is preferable to design so that the refractive index of a hard-coat layer may become the same value as the surface average refractive index of a 1st transparent base material. This is because the so-called "surface rainbow color unevenness" can be made inconspicuous by reducing the difference between the amplitude of the reflectance caused by the difference in the refractive index of the hard coat layer and the surface average refractive index of the first transparent substrate. However, when using a PET film with an adhesive layer as the first transparent base material, it is preferable that the refractive index of the hard coat layer is equal to or close to the refractive index calculated by the following formula.

N = Np-(Ns-Np) / 2

N: refractive index of the transparent hard coating layer

Np: refractive index of PET easy adhesive layer

Ns: surface average refractive index of PET substrate

Further, as the oxide fine particles used in the hard coating layer, silicon oxide, aluminum oxide, antimony oxide, tin oxide, zirconium oxide, tantalum oxide, cerium oxide, titanium oxide and the like can form a hard coating layer having excellent transparency without coloring the hard coating layer. It may be used more appropriately for reasons such as. It is preferable that it is 100 nm or less as a particle diameter of this oxide fine particle. It is because in the fine particle oxide powder of more than 100 nm, the hard coating layer obtained scatters light remarkably by Rayleigh scattering and becomes white and transparency falls.

Examples of the resin component include an ultraviolet curable resin, an electron beam curable resin, a cationic polymerization resin, and the like. Among these, the ultraviolet curable resin is suitably used because it is inexpensive and has excellent adhesiveness with a transparent plastic film. What is necessary is just the photosensitive resin used for the coating method (wet coating method) to ultraviolet curable resin, for example, acrylic resin, an acrylic urethane resin, silicone resin, epoxy resin etc. are suitable for the reason that the dispersibility of the said oxide fine powder is not impaired. Is used.

In the present invention, the hard coat layer in the antireflection layer is formed by applying, drying and irradiating UV light a hard coating layer-forming paint containing at least an organic resin component, oxide fine particles and an organic solvent on a first transparent substrate.

The transparent hard coat layer-forming paint can be obtained, for example, as an organic solvent-based paint in which the oxide fine particles and the resin component are mixed and dispersed in an organic solvent by a conventional method using ultrasonic dispersion, homogenizer, sand mill, etc., using a dispersant. . The organic solvents described above can be selected from alcohols, glycols, acetate esters, ketones, and the like, and these may be used as single species or may be used as a mixture of two or more kinds.

Then, the hard coat layer-forming paint is applied to one surface of the first transparent base material, and crosslinked and cured by ultraviolet irradiation or the like to form a hard coat layer. It is preferable that the thickness of this hard coat layer is 0.5 micrometer-20 nm, More preferably, it is 0.5-2 micrometer. If the thickness is 0.5 μm or less, it may not be possible to develop sufficient film hardness, and if it is 20 μm or more, curling of the first transparent substrate may be large.

On the other hand, various coating methods are possible as a coating method, For example, it can select suitably from the bar coating method, the gravure coating method, the slit coater method, the roll coater method, the dipping coating method, etc.

(Conductive medium refractive index layer)

The conductive medium refractive index layer formed on the hard coat layer preferably has conductivity and contains fine particles of medium refractive index and a binder component.

It is preferable that content of the said electroconductive medium refractive index microparticles | fine-particles in an electroconductive medium refractive index layer is 50 mass% or more, and it is more preferable to exist in the range of 70 to 95% especially. When the content of the conductive medium refractive index fine particles is less than 50 mass%, the surface resistance value of the conductive medium refractive index layer 3 increases, the conductivity deteriorates, and at the same time, the filler component can be reduced, and thus the adhesion with the hard coating layer May become insufficient. On the other hand, when the content of the conductive medium refractive index fine particles exceeds 95% by mass, the content of the binder component is relatively decreased, so that a sufficient amount of the conductive medium refractive index fine particles cannot be maintained in the binder matrix, and on the conductive medium refractive index layer, When the other layer is applied, the film is likely to be scratched, which may cause a poor appearance.

As the conductive medium refractive index fine particles, metal particles such as antimony-containing tin oxide (hereinafter referred to as ATO), tin-containing indium oxide (hereinafter referred to as ITO), aluminum-containing zinc oxide, gold, silver, and palladium have transparency and conductivity. It is used more suitably for the reason which can form the outstanding electroconductive medium refractive index layer.

Moreover, it is preferable that the particle diameter of the said electroconductive medium refractive index microparticles is 1-100 nm in average particle diameter. If the average particle diameter is less than 1 nm, it is easy to cause agglomeration at the time of coating, it is difficult to uniformly disperse for coating, and further, the viscosity of the coating may increase, resulting in poor dispersion. In addition, when the average particle diameter of the conductive medium refractive index fine particles exceeds 100 nm, the resultant conductive medium refractive index layer may appear white due to the diffused reflection of light by Rayleigh scattering, resulting in a decrease in transparency.

Preferred binder components are those produced from silicone alkoxides and / or hydrolysis products.

In the transparent laminate of the present invention, the conductive medium refractive index layer is formed on the hard coating layer 51 by using a conductive medium refractive index layer-forming paint containing at least conductive medium refractive index particles, silicon alkoxide and / or a hydrolysis product thereof, and an organic solvent. It can form by apply | coating and drying.

The conductive medium refractive index layer-forming paint includes an ultrasonic dispersion machine, a homogenizer, a sand mill, and the like by using the above-mentioned conductive medium refractive index oxide fine particles, silicon alkoxide and / or hydrolyzate thereof and other particles added in some cases using a dispersant. It can disperse | distribute in the organic solvent by the conventional method used, and can obtain as an organic solvent type coating material.

The silicon alkoxide may be selected from, for example, a tetraalkoxysilane-based compound, an alkyltrialkoxysilane-based compound, and the like, and the organic solvent may be selected from alcohols, glycols, acetate esters, ketones, and the like. A single species may be used or may be used as a mixture of two or more kinds.

And it is preferable to apply | coat the said coating material for electroconductive medium refractive index layer formation on a transparent hard-coat layer, for example, to dry at 70-130 degreeC for 1 minute or more, and to adjust an optical film thickness to the range of 140 +/- 30 nm.

It is not preferable with respect to the drying temperature because it causes thermal deformation depending on the transparent plastic film used. In addition, when it is less than 70 degreeC, hardening rate becomes slow and strength is not expressed. Moreover, when hardening time is less than 1 minute, film strength will run short and it is not preferable.

In addition, as a coating method, it can select suitably from the bar coating method, the gravure coating method, the slit coater method, the roll coater method, the dipping coating method, etc., for example.

(High refractive index layer)

The high refractive index layer formed on the conductive medium refractive index layer contains, for example, oxide fine particles having a high refractive index and a binder component.

It is preferable that content of the high refractive index oxide fine particle in a high refractive index layer is 50 mass% or more, and it is more preferable that it is especially 60-95 mass%. When the content of the high refractive index oxide fine particles is less than 50%, the content of the binder component is relatively increased to cause a decrease in refractive index, and sufficient high refractive index is not obtained, and the reflectance may be excessively increased. When the content of the high refractive index oxide fine particles exceeds 95%, the high refractive index oxide fine particles cannot be sufficiently immobilized by the binder component, and scratches are more likely to occur when another layer is applied on the transparent high refractive index layer. May cause poor appearance.

As the high refractive index oxide fine particles, cerium oxide, zinc oxide, zirconium oxide, titanium oxide, tantalum oxide, and the like can be more suitably used for the reason of forming the high refractive index layer 53 having excellent transparency.

Moreover, it is preferable that the particle diameter of a high refractive index oxide fine powder is 1-100 nm in average particle diameter. If the average particle diameter is less than 1 nm, it is easy to cause agglomeration at the time of coating, it is difficult to uniformly disperse for coating, and the viscosity of the coating may increase and poor dispersion may occur. In addition, when the average particle diameter of the high refractive index oxide fine powder exceeds 100 nm, the resulting high refractive index layer diffuses light remarkably by Rayleigh scattering, making it appear white, resulting in insufficient transparency.

As the binder component, silica derived from silicon alkoxide and / or its hydrolysis product is preferable.

The high refractive index layer of this invention is formed by apply | coating and drying on a conductive medium refractive index layer using the transparent high refractive index formation paint containing at least high refractive index oxide fine particles, a binder component, and an organic solvent.

The high refractive index layer forming paint is a conventional high refractive index oxide powder, silicon alkoxide and / or its hydrolysis products and optionally added particles using a dispersant using an ultrasonic disperser, homogenizer, sand mill, etc. It can disperse in the organic solvent by the method and can obtain it as an organic solvent type coating material.

The silicon alkoxide may be selected from, for example, a tetraalkoxysilane-based compound, an alkyltrialkoxysilane-based compound, and the like, and the organic solvent may be selected from alcohols, glycols, acetate esters, ketones, and the like. A single species may be used or a mixture of two or more kinds thereof may be used.

And the said high refractive index layer forming paint is apply | coated on an electroconductive medium refractive index layer, for example, it is dried at 70-130 degreeC for 1 minute or more, and a high refractive index layer is formed. The thickness is preferably set to 1.2 to 2.5 times the thickness of the optical film of the low refractive index layer. Until now, it is generally known that the thickness design according to the anti-reflection is set to 1/4 of the wavelength (hereinafter referred to as the bottom wavelength) showing the lowest reflectance for the thickness of the high refractive index layer and the low refractive index layer. When the anti-reflection film is produced, the reflectance at the bottom wavelength is the lowest, but the reflectance at the long wavelength side and the low wavelength side is increased, and the reflection color of the portion is stronger, resulting in the deficit reflection color in severe celadon. Furthermore, it leads to the increase of the visibility visibility which is an index of the reflectance to the naked eye. In order to suppress the increase in the reflectance on the long wavelength side and the low wavelength side, studies have been conducted to solve the problem by designing the optical film thickness of the low refractive index layer to be 1.2-2.5 times slightly thicker than the conventional design method. Found.

As for the drying temperature, if it exceeds 130 ° C, depending on the transparent plastic film used, it may cause thermal deformation. In addition, when it is lower than 70 ° C., the curing rate may be slow and sufficient strength may not be expressed. If the curing time is less than 1 minute, the film strength may be insufficient.

In addition, as a coating method, it can select suitably from the bar coating method, the gravure coating method, the slit coater method, the roll coater method, the dipping coating method, etc., for example.

(Low refractive index layer)

The low refractive index layer laminated on the high refractive index layer is formed by applying and drying a low refractive index layer-forming paint containing, for example, silicon alkoxide and / or its hydrolyzate, silicon oil and an organic solvent on the high refractive index layer.

It is preferable that the refractive index of this low refractive index layer is 0.1 or less smaller than the refractive index of a high refractive index layer. The antireflection layer obtained by providing such a transparent low refractive index layer exhibits very excellent antireflection property. As a silicon alkoxide used as this low refractive index layer coating material, it can select suitably from a tetraalkoxy silane type compound, an alkyltrialkoxy silane type compound, etc., and can use.

Moreover, as said silicone oil, it can use suitably from a dialkyl alkoxysilane compound. Moreover, as said organic solvent, it can select suitably from alcohol type, a glycol type, an acetate ester type, and a ketone type, These may be used as a single type, or may mix and use two or more types.

When 0.01-5.0 mass% of silicone oil is contained in the coating material for transparent refractive index layer formation, the contact angle with respect to the water of a coating film will be 90 degrees or more, it will express water repellency and will slide easily, and Membrane strength (particularly steel wool strength) can be improved and antifouling properties can be imparted.

When the content of the silicone oil is less than 0.01% by mass, the silicone oil does not sufficiently bleed to the surface of the transparent low refractive index layer 4, the contact angle to water is less than 90 °, and sufficient water repellency is not obtained, and thus, antistatic and The film strength improvement and antifouling property of the transparent film with an antireflection film may not be obtained. In addition, when the content exceeds 5.0% by mass, the silicone oil becomes excessive on the surface of the transparent low refractive index layer 5, so that the contact angle with water exceeds 90 ° to obtain sufficient water repellency, but silicon alkoxide and / or its hydrolyzate Since the polymerization hardening reaction is inhibited, the film strength of the transparent film with the antistatic and antireflection film can be reduced.

The low refractive index layer is formed by coating the transparent low refractive index layer-forming paint on the transparent high refractive index layer, for example, drying at 70 to 130 ° C. for 1 minute or more to adjust the optical film thickness to 140 nm, and thus the bottom wavelength is about 600 nm. An antistatic and antireflection film can be produced.

When it exceeds 130 degreeC with respect to a drying temperature, heat distortion may be caused, depending on the transparent plastic film used. In addition, if the curing rate is lower than 70 ° C., strength may not be expressed. If the curing time is less than 1 minute, the film strength may be insufficient.

In addition, as a coating method, it can select suitably from the bar coating method, the gravure coating method, the slit coater method, the roll coater method, the dipping coating method, etc., for example.

The antistatic and antireflective films produced by the above method have good antistatic effects and antireflection properties, have a strong film hardness, antifouling properties, and the like. The reason can be considered as follows.

By presenting a large amount of inorganic compound filler in the transparent hard coating layer, the transparent conductive medium refractive index layer and the transparent high refractive index layer, the surface energy of the layer can be increased to remarkably improve the wettability of each paint on the surface of each layer. By the improvement effect, the adhesiveness between layers improves, and the film | membrane strength stronger than before can be obtained by this.

In addition, the transparent low refractive index layer in the outermost layer contains a silicone oil, the contact angle with water exceeds 90 ° can impart water repellency. And even if this waterproof effect is rubbed with a cloth or the like, the effect is sufficiently maintained, and a higher antifouling property can be obtained than before. The reason for the antifouling property is that the silicone oil is contained in the silica matrix and is not easily absorbed.

(Description of Metal Mesh Layer)

In the transparent laminated body of this invention, when the electromagnetic shielding layer of a 2nd laminated part is a metal mesh layer, since this metal mesh layer becomes black, reflection of the surface of a metal mesh is suppressed and visibility is reduced by metal gloss color. You can prevent it.

As a method of blackening, the method of electroplating blackening metals, such as Ni, Sn, Ni-Sn alloy, etc., the method of blackening a metal surface by oxidation or sulfidation, etc. are mentioned.

Moreover, in the transparent laminated body of this invention, it is preferable that the thickness of a metal mesh layer is 1-15 micrometers, More preferably, it is 1-10 micrometers. When the thickness of the metal mesh layer is too thick, the viewing angle may be narrowed and visibility may be reduced.

(General manufacturing method)

In the transparent laminate of the present invention, the antireflection layer is formed on the first transparent substrate by the above-described method, and then the near-infrared shielding layer is formed on the rear surface of the transparent laminate. On the other hand, a metal mesh layer is formed on a 2nd transparent base material by the above-mentioned method. The first laminated portion having the first transparent substrate, the antireflection layer, and the near infrared shielding layer thus obtained, and the second laminated portion including the second transparent substrate and the metal mesh layer are formed on the near infrared shielding layer side and the metal mesh layer side. Lamination bonding through. As a lamination | stacking method, the method normally used for adhesion | attachment of a panel and a film, a film and a film, for example, the method of using a roll laminator, the method of using a sheet laminator, etc. can be used. Moreover, you may heat and pressurize suitably between the said processes. In addition, it is preferable to go through the process of defoaming and transparent after the adhesion. The defoaming method can be carried out by pressurization or reduced pressure, preferably by pressurization. The adhesive layer may contain a coloring material for adjusting the color tone or transmittance.

The metal mesh layer used for the transparent laminate of the present invention may be formed by printing an ink containing a catalyst on a second transparent substrate in a mesh pattern and then electroless plating and / or electroplating a metal on the ink image. desirable. It is preferable to use copper as a metal which precipitates by plating. Moreover, after depositing a metal by electroless plating, it is preferable to again precipitate a metal by electrolytic plating. As a conventionally used method, when a thin film of silver or indium-containing tin oxide (ITO) is formed on a substrate by the sputtering method, the electromagnetic shielding ability of the obtained metal mesh layer is insufficient, thereby propagating an information processing device or the like. Disability Independence It is difficult to clear the Class B criteria set by the VCCI. Although the printing method is not specifically limited, such as the screen printing method and the gravure printing method, A screen printing method is preferable.

As a conventional method of forming a metal mesh, a fiber pattern in which copper is plated with a fiber as a support, a method of laminating a copper foil to a resin film of a substrate, or a mesh patterned sheet by etching a sheet plated with copper on its surface There is an etching mesh forming method, but the former has a problem that the wire diameter of the mesh is about 20 to 50 탆 thick, thereby decreasing the transmittance and causing interference fringes to easily occur. Moreover, since the latter is etching the copper foil which has a thickness of about 10-20 micrometers, the thickness of a metal mesh layer is thick, a viewing angle becomes narrow, and visibility is reduced. Further, even when the surface of the copper foil is blackened, when viewed in an oblique direction, a color tone peculiar to copper is exposed in the depth direction of etching, which causes a problem in color tone of the screen.

The metal mesh layer obtained by the above method of the present invention may have sufficient conductivity even if the thickness is thin. It is especially preferable that it is 1-15 micrometers in thickness, More preferably, it is 1-10 micrometers, and the metal mesh layer which shows the surface resistance of 0.01-0.5 ohm / square and the transmittance | permeability of 70-90% can be obtained in this thickness. Therefore, the metal mesh layer obtained by the above method of the present invention has a wider viewing angle, which improves visibility, and when the surface is blackened, no color tone peculiar to the metal is revealed in the depth direction of the metal mesh, and a problem occurs in the color tone of the screen. Do not give.

By using the transparent laminate of the present invention, it is possible to significantly reduce the weight of the PDP by directly adhering it to the PDP module windshield. The mass of glass used in conventional optical filters is about 4.5 kg for 106.6 cm (42 inch) dimensions and about 5 kg for 127 cm (50 inch) dimensions, so removing glass from these conventional optical filters Realization as an expected wall-mounted TV becomes easy.

As shown in FIG. 4, when the transparent laminated body of this invention is used as an optical filter, the 1st laminated part 61 and the 2nd laminated part 62 are the metal mesh layer electrode extraction parts 22a for taking out a ground. It is desirable to stick together like a picture frame to secure).

The structure (partial cross section) at the time of mounting the transparent laminated body of this invention to a PDP is shown in FIG. The transparent laminate 1 of the present invention is directly bonded to the display surface 73 of the PDP module 71. The electromagnetic wave shielding film electrode extracting portion 22a secured by bonding the first stacking portion 61 on the second stacking portion 62 like a picture frame is directly bonded to the case 72 of the module 71, or a clip or clip is placed on the second stacking portion 62. It is mounted by conduction through a lamp or gasket (not shown) or the like. An image formed on the transparent laminate is observed along the arrow direction 75 by the observer 74.

Example

The transparent laminated body of this invention is further demonstrated by the following example.

Example 1

Using a 100 μm-thick PET film as the first transparent substrate, an antireflection layer consisting of a hard coating layer, a conductive medium refractive index layer, a high refractive index layer, and a low refractive index layer was formed on one side thereof, and the opposite side was represented by the formula (1). Dimonium-based pigments and phthalocyanine-based pigments (NIPPON SHOKUBAI CO., LTD., Manufactured by NIPPON SHOKUBAI CO., LTD. The near-infrared shielding layer containing the transparent resin obtained by superposing | polymerizing the monomer component containing 50 weight part was formed, and the 1st laminated part was formed. The dimonium pigment | dye and the phthalocyanine pigment | dye were mix | blended in the weight ratio of 2: 1.

Next, as a second transparent substrate, a palladium-colloid-containing paste was printed on a PET film having a thickness of 125 μm using a screen having a lattice pattern (mesh type) of L / S = 30/270 (μm), which was electroless It was immersed in the copper plating solution, electroless copper plating was performed, electrolytic copper plating was continued, electroplating of Ni-Sn alloy was performed again, and the 2nd laminated part was formed.

Subsequently, a transparent adhesive layer having a thickness of 25 μm was formed on the surface opposite to the near-infrared shielding layer of the first laminated part of the first transparent substrate and on the surface opposite to the electromagnetic shielding layer of the second laminated part of the second transparent substrate, respectively. And the near-infrared shielding layer surface of the first laminated part and the electromagnetic shielding layer of the second laminated part were bonded together, and pressurized for 30 minutes under a pressure of 0.45 MPa to prepare a transparent laminate.

"Total light transmittance", "haze value", "luminous reflectance", "pencil hardness", "steel wool hardness", "adhesiveness", "spectral transmittance (near infrared)" of the obtained transparent laminate, "reliability test (high temperature) Near-infrared transmittance change after 1000 hours at high humidity) "and" electromagnetic shielding property "were evaluated by the following method. The evaluation results are shown in Table 1.

(Assessment Methods)

(1) Total light transmittance: It measured using the haze meter (made by Nippon Denshoku Industries Co., Ltd.).

(2) Luminous reflectance: Measured using a spectrophotometer (V-570 manufactured by JASCO Corporation.).

(3) Pencil Hardness: The surface of the antireflection layer was faced up, and the minimum pencil hardness without scratching was measured under a 1 kg load.

(4) Steel wool strength: The number of scratches generated after reciprocating 10 times while applying the load of 250 g / cm ² to the # 0000 steel wool with the antireflective layer face up was measured.

(5) Adhesion: The surface of the antireflection layer was faced up, and each side of the 1 cm square of the film surface was cut out at 1 mm intervals, and the number of remaining grids after the peeling test three times with the adhesive tape was measured.

(6) Spectral transmittance: The transmittance | permeability in wavelength 850nm, 950nm, 1000nm of each sample was measured using the spectrophotometer (V-570 made by JASCO Corporation.).

(7) reliability

(i) Each sample was put into the thermostat set to 80 degreeC, and the spectral transmittance | permeability after 1000 hours was measured.

(ii) Each sample was put into the constant temperature and humidity test set to 60 degreeC-90% of relative humidity, and the spectral transmittance after 1000 hours was measured.

(8) Electromagnetic wave shielding property: It measured based on KEC method (Kansai Electronics Industry Promotion Center method).

(Test result)

The test result of the Example confirmed that the transparent laminated body of this invention had the outstanding transmittance | permeability, low reflectivity, electromagnetic wave shielding, near-infrared shielding property, and strength, and also excellent durability.

The transparent laminate of the present invention and its manufacturing method are excellent in anti-reflection, near-infrared shielding, electromagnetic shielding properties, excellent in durability, visibility of visible images, light weight, easy to manufacture and handle, for example, display of a plasma display device or the like. It is used as an optical filter of an apparatus, and has high utility.

Claims (16)

A first laminated portion comprising a first transparent substrate, an antireflection layer formed on one surface thereof, and a near infrared shielding layer formed on the other surface thereof; A second laminated portion comprising a second transparent substrate and an electromagnetic shielding layer formed on one surface thereof; and It has a near-infrared shielding layer of a said 1st laminated part, and the adhesive bond layer which joins a said 2nd laminated part, The transparent laminated body characterized by the above-mentioned. The transparent laminate according to claim 1, wherein said electromagnetic shielding layer is a metal mesh layer. The transparent laminate according to claim 1, wherein the near-infrared shielding layer of the first laminate portion and the electromagnetic shielding layer of the second laminate portion are bonded to each other. The transparent laminate according to claim 1, wherein the second laminate further has a back adhesive layer formed on the other side of the second transparent substrate. The adhesive laminate of the back surface adhesive layer of the said 2nd laminated part is 1-20 N / 25mm, The transparent laminated body of Claim 4 characterized by the above-mentioned. The near-infrared shielding layer of claim 1, wherein A first near infrared absorbing dye comprising at least one near infrared absorptive dimonium compound, A second near-infrared absorbing pigment having an absorption maximum in the region of the near-infrared wavelength of 750 to 950 nm and comprising the dimonium compound and at least one kind of a dye compound; A transparency resin comprising a polymer of at least one ethylenically unsaturated monomer, At least 30 mass% of the ethylenically unsaturated monomer which comprises the said polymer for transparency resins is following General formula (2):

[In the formula (2), R represents a hydrogen atom or a methyl group, and X represents a cyclic hydrocarbon group having 6 to 25 carbon atoms.) It is a monomer represented by the transparent laminated body characterized by the above-mentioned. The near-infrared absorptive dimonium compound for said first near-infrared absorbing dye contained in the near-infrared shielding layer of a said 1st lamination | stacking part is a dimonium compound positive ion, and the following general formula (1): _{(CF 3 SO 2) 2 N} - (1) It is comprised by the counter anion represented by the transparent laminated body characterized by the above-mentioned. The near-infrared absorptive dimonium compound for a said 1st near-infrared absorbing dye contained in the near-infrared shielding layer of the said 1st laminated part is a following formula (3):

It is a compound represented by the transparent laminated body characterized by the above-mentioned. 7. The transparent resin included in the near infrared shielding layer of the first laminate part has a glass transition temperature of 60 to 120 ° C, a number average molecular weight of 20,000 to 80,000, and a weight average molecular weight of 200,000 to 400,000. Transparent laminate. 2. The antireflection layer according to claim 1, wherein the antireflection layer of the first laminate part comprises a hard coating layer, a conductive medium refractive index layer laminated on the hard coating layer, a high refractive index layer laminated on the conductive medium refractive index layer, and the high refractive index layer. The transparent laminated body comprised from the low refractive index layer laminated | stacked on the surface. The transparent laminate according to claim 10, wherein the hard coat layer included in the antireflection layer contains oxide fine particles and a binder component, and the content of the oxide fine particles is 30% by mass or more. The transparent laminate according to claim 2, wherein the metal mesh layer included in the second laminate includes a metal mesh having a surface blackened by electroplating of black metal. The transparent laminate according to claim 1, wherein the electromagnetic shielding layer has a thickness of 1 to 15 µm. The transparent laminate according to claim 1, further comprising a shock absorbing layer between the near infrared shielding layer of the first laminate and the adhesive layer. Forming an anti-reflection layer on one surface of the first transparent substrate, and then forming a first laminate by forming a near-infrared shielding layer on the other surface of the first transparent substrate, and separately forming a metal mesh layer on one surface of the second transparent substrate Forming a second laminate, and forming a laminate by bonding the near-infrared shielding layer of the first laminate to the metal mesh layer of the second laminate through an adhesive layer. 16. The method of claim 15, wherein an image having a desired mesh pattern is printed by ink containing a catalyst on one surface of a second transparent substrate to form a metal mesh layer of the second laminate, and on the printed surface. Electroless metal plating and / or electrolytic metal plating are carried out to deposit a metal along the pattern of the catalyst-containing ink image and to fix the metal on the second transparent substrate.

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