JP5692499B2 - Infrared shielding material fine particle dispersion and coating liquid for forming infrared shielding adhesive film, infrared shielding adhesive film and infrared shielding optical member, multilayer filter for plasma display panel and plasma display panel - Google Patents

Description

The present invention relates to an infrared shielding adhesive film and an infrared shielding optical member containing tungsten oxide fine particles or / and composite tungsten oxide fine particles that are transparent in the visible light region and absorb in the near infrared region, and in particular, tungsten. Infrared shielding adhesive film having excellent moisture and heat resistance characteristics while maintaining high infrared absorption characteristics of oxide fine particles and / or composite tungsten oxide fine particles (infrared here refers to a wavelength region of 800 to 1100 nm) And an infrared shielding optical member, a multilayer filter for a plasma display panel (hereinafter, abbreviated as PDP) and a plasma display panel having the infrared shielding adhesive film and the infrared shielding optical member, and the infrared shielding adhesive film and the infrared ray. infrared shielding material microparticle dispersion liquid for forming a shielding optical member To an improved infrared shielding pressure-sensitive film-forming coating solution.

  In recent years, demand for flat-screen televisions such as PDP televisions and liquid crystal televisions has increased, and since there is a tendency to prefer flat-screen televisions of 50 inches or more, demand for PDP televisions that can be easily made larger than liquid crystal televisions is expected. It is. A general configuration of this PDP will be described with reference to the drawings. FIG. 1 is an enlarged cross-sectional view showing an outline of an AC type (AC type) PDP light emitting unit. In FIG. 1, reference numeral 11 denotes a front glass substrate (front cover plate), and display electrodes 12 are formed on the front glass substrate 11. Further, the front glass substrate 11 on which the display electrodes 12 are formed is covered with a dielectric glass layer 13 and a protective layer 14 made of magnesium oxide (MgO). Reference numeral 15 denotes a rear glass substrate (back plate). On the rear glass substrate 15, address electrodes 16, partition walls 17, and a phosphor layer 18 are provided. Reference numeral 19 encloses a discharge gas. It is a discharge space.

  The light emission principle of the PDP is that a voltage is applied between the display electrode 12 and the address electrode 16 to discharge in the discharge space 19 and excite the mixed gas of xenon and neon introduced into the discharge space. Then, vacuum ultraviolet rays are emitted, and the phosphor layers 18 that emit red, green, and blue (hereinafter abbreviated as RGB) fluorescence are emitted by the vacuum ultraviolet rays, thereby enabling color display. ing.

  However, xenon gas generates near infrared rays in addition to the vacuum ultraviolet rays, and a part of the near infrared rays is emitted forward of the PDP. In particular, infrared rays having a wavelength range of 800 nm to 1100 nm cause malfunction in a cordless phone or a remote control of home appliances, and adversely affect transmission optical communication. Another problem is that the electromagnetic waves that are generated adversely affect the human body. Further, neon gas emits orange light, which has a problem of adversely affecting RGB light emission.

  Therefore, a multilayer filter (laminated body) formed by laminating an infrared shielding film for preventing malfunction of the device due to infrared rays, a neon cut shielding film for shielding orange emission derived from neon gas, and an electromagnetic shielding film on the front surface of the PDP. ) Is provided. Each film such as the infrared shielding film, the neon cut shielding film, and the electromagnetic wave shielding film constituting the multilayer filter (laminate) is generally referred to as a “base material”.

  By the way, although the infrared shielding film in the said multilayer filter (laminated body) is comprised by the membrane | film | coat containing an infrared rays absorption material, in order to ensure sufficient visibility with the said low amount of light emission (energy saving), the said infrared absorption material. In addition, it is required to have such characteristics that light in the visible light region (wavelength region, about 380 nm to 780 nm) is sufficiently transmitted and infrared light in the wavelength region 800 nm to 1100 nm is shielded. Conventionally, organic compounds such as organic dyes and metal complexes have been used as the infrared absorbing material. When an infrared shielding film containing an organic compound such as an organic dye or a metal complex as an infrared absorbing material is formed, the organic compound is contained in a thermosetting or photocurable binder, and this is formed on the substrate. A method of incorporating the cured product into a multilayer filter for PDP is generally performed.

  Here, as infrared absorbing materials such as organic dyes and metal complexes, diimonium compounds, aminium compounds, phthalocyanine compounds, organometallic complexes, cyanine compounds, azo compounds, polymethine compounds, quinone compounds, diphenylmethane compounds , Triphenylmethane compounds, etc., but these are markedly deteriorated over time due to heat and light, so when these organic compounds are used alone, it is difficult to maintain the performance for a long time. There was a problem that there was. In order to suppress degradation of organic compounds such as organic dyes and metal complexes with respect to light, an independent layer (ultraviolet absorption layer) is provided in the vicinity of the viewing surface side surface of the PDP of the infrared shielding film containing the organic compound. Measures to reinforce the light resistance are generally taken. For this reason, there is a limitation on the structure as a multilayer filter (laminated body), which causes a decrease in productivity and an increase in cost due to an increase in the number of layers. As an effective method for reducing the number of stacked layers, there can be considered a method in which an existing base material is combined with an infrared shielding function, a function of shielding neon-derived light emission, and the like. In particular, a method in which an adhesive film that is indispensable for pasting substrates together is a composite functional adhesive film is effective.

  In addition, in order to reduce power consumption (energy saving) in PDP televisions, a reduction in the amount of light emission is required. To ensure the same visibility as conventional PDPs, the visible light transmittance of the PDP front filter is increased. Must be set. However, as a feature of infrared absorbing materials such as the above organic dyes and metal complexes, phthalocyanine compounds have absorption in the visible light region. Therefore, in order to ensure sufficient visibility, it is necessary to increase the amount of luminescence and save energy. It is difficult to realize. Therefore, diimonium compounds with high visible light transmittance are used, but they have good compatibility with thermosetting or photocurable binders, but are generally used as adhesive film-forming binders (meth) acrylic Due to the poor compatibility with the polymer, it was difficult to contain the diimonium compound in the adhesive film. For this reason, it is necessary to install an infrared shielding film containing a diimonium-based compound, and it is difficult to reduce the number of laminated multilayer filters (laminates). The (meth) acrylic polymer generally used as a binder for forming an adhesive film contains a hydroxyl group (—OH) and a carboxy group (—COOH) as crosslinking groups in the polymer skeleton, and has strong adhesiveness. There is an “acid group type” and a “neutral type” that contains only hydroxyl groups in the polymer skeleton and has weak adhesion. And both are properly used depending on the structure of the filter, for example, it can be re-attached in the bonding process of filter manufacture, and the above-mentioned "neutral type" with weak adhesiveness is used when emphasizing improvement in yield. When importance is attached to prevention of peeling in the filter of the product, the above-mentioned “acid group type” having strong adhesiveness is used.

  Under such a technical background, instead of an organic compound having low resistance to heat and light, in Patent Document 1, as the near infrared ray absorbing material (infrared shielding material), a general formula WyOz (W is tungsten, O is oxygen, tungsten oxide fine particles represented by 2.2 ≦ z / y ≦ 2.999), and / or general formula MxWyOz (where M is H, He, alkali metal, alkaline earth metal, Rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn , Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I Element, W is tungsten, O is oxygen, 0. The composite tungsten oxide fine particles represented by 01 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3) are applied, and the particle diameter of the near-infrared shielding material (infrared shielding material) fine particles is 1 nm or more Proposed the near-infrared shielding material (infrared shielding material) fine particle dispersion characterized by being 800 nm or less, and the optical properties, conductivity, manufacturing method, etc. of this near-infrared shielding material (infrared shielding material) fine particle dispersion. In Patent Document 2, a near-infrared shielding (infrared shielding) adhesive film using the tungsten oxide fine particles represented by the general formula WyOz and / or the composite tungsten oxide fine particles represented by the general formula MxWyOz is used. Has proposed a multilayer filter (laminate) for PDP.

  Patent Document 3 discloses a hard coat layer containing a near-infrared shielding material (infrared shielding material) such as a cured resin and a tungsten oxide compound on one surface of a base film and a low refractive index layer containing a cured resin. An antireflection film constituted by sequentially laminating is disclosed, and a PDP multilayer filter (laminated body) is proposed in which the antireflection film is attached to a front panel of a PDP.

  Furthermore, Patent Document 4 discloses an electromagnetic wave shielding adhesive film in which an adhesive layer is laminated on a transparent substrate such as a PDP, and a conductive layer having a geometric figure is embedded in the adhesive layer, and this An electromagnetic wave shielding display in which an electromagnetic wave shielding adhesive film is bonded to a display surface such as a PDP has been proposed.

  Further, along with the increase in the size of the display, it is required to further reduce the weight and thickness of the PDP, and the improvement of the impact resistance of the panel has become an important issue, so the above-described infrared shielding film and electromagnetic wave shielding (electromagnetic wave shielding) ) In addition to the layer and the like, Patent Document 5 proposes a pressure-sensitive adhesive layer excellent in impact relaxation property that relaxes against an impact from the viewing surface side.

International Publication No. WO2005 / 037932 JP 2006-154516 A JP 2006-201443 A JP 2000-323891 A JP 2005-023133 A

  By the way, a multilayer for PDP in which tungsten oxide fine particles and / or composite tungsten oxide fine particles (infrared shielding material fine particles) having resistance to heat and light as compared with organic compounds such as organic dyes and metal complexes described above are used. In the infrared shielding adhesive film of the filter (laminate), when a (meth) acrylic polymer is applied as a material component for forming an adhesive film, the tungsten oxide fine particles and / or composite tungsten in the infrared shielding adhesive film Recent experiments have revealed that the moisture and heat resistance characteristics of oxide fine particles are equivalent to or inferior to those of organic compounds such as organic dyes and metal complexes. Regarding the infrared shielding adhesive film of the multilayer filter (laminate) for PDP There was a need to improve its heat and humidity resistance.

The present invention has been made paying attention to such problems, and the problem is that infrared shielding that exhibits excellent resistance to wet heat while maintaining high visible light transmittance and infrared shielding properties. Provided are an adhesive film and an infrared shielding optical member, and a multilayer filter for a plasma display panel having the infrared shielding adhesive film and the infrared shielding optical member, and a plasma display panel. An object of the present invention is to provide an infrared shielding material fine particle dispersion that forms a member and a coating liquid for forming an infrared shielding adhesive film.

  Therefore, the present inventors have conducted the following technical studies in order to solve the above problems.

  First, a resin such as (meth) acrylic polymer that constitutes an infrared shielding adhesive film contains a small amount of radical initiator and unreacted monomer, and the polymer is cut by heat, oxygen, and moisture in a humid heat environment. , Causing haze accompanied by yellowing of the resin and deterioration of transparency due to chain decomposition by radicals generated at the time of cutting. “Primary antioxidants” such as hindered phenols that trap radicals may be added to prevent degradation of this polymer, but degradation of inorganic compounds filled in resins such as (meth) acrylic polymers It is not added for the purpose of preventing. Other antioxidants include salicylic acid or its derivatives, but the additive itself absorbs light energy (ultraviolet rays) to prevent photodegradation of the resin. The type is different. In addition, metal deactivators (generally classified as antioxidants) are those that capture heavy metal ions such as copper, iron, cobalt, manganese, and chromium, which have a catalytic action that significantly accelerates oxidative degradation of polymers. In the infrared shielding pressure-sensitive adhesive film to which the tungsten oxide fine particles or / and the composite tungsten oxide fine particles not containing the catalytic ions are applied, it is considered that there is no effect by addition.

  When radicals involved in polymer degradation are involved in the degradation of inorganic compounds or metals (that is, tungsten oxide or composite tungsten oxide) that have completely different bonding states (covalent bonds for organic compounds and ionic bonds for inorganic compounds). Is hard to think. Therefore, even if a hindered phenol-based antioxidant, which is a “primary antioxidant” for scavenging radicals, is added to the infrared shielding adhesive film, an effect of suppressing the deterioration of the inorganic compound cannot be expected.

  However, the tungsten oxide fine particles and / or composite tungsten oxide fine particles as the near infrared absorbing material (infrared absorbing material) applied to the above-described infrared shielding adhesive film have a particle size of nano-order, and from the conventional milli-order. The present inventors have predicted that a deterioration mechanism that cannot be predicted with micro-order metal powders is exhibited.

  Therefore, the present inventors have further studied the cause of deterioration of the moisture and heat resistance characteristics, taking into account the effects of the radicals, which have not been considered in the past, and as a result, “secondary antioxidants that decompose organic peroxides” It was found that the wet heat deterioration of the tungsten oxide fine particles and / or the composite tungsten oxide fine particles, which are nano-order fine particles, was improved by adding the antioxidant as "to the infrared shielding adhesive film.

  By the way, it is considered that the mechanism for producing a large amount of the organic peroxide is a phenomenon peculiar to the case where fine particles are contained in an adhesive polymer. In general, when the adhesive layer is bonded to a metal plate, the functional groups such as carboxyl, hydroxyl, and amino groups contained in the polymer that constitutes the main component of the adhesive layer are adhered by a covalent bond with the metal or van der Waals force. And the adhesive layer is bonded to the metal plate. It is known that this adhesion decreases due to water and peeling occurs, and the mechanism is considered to be that the covalent bond is physically broken when water penetrates the metal surface and the adhesive layer interface. It has been. Accordingly, in the infrared shielding adhesive film in which the tungsten oxide fine particles or / and the composite tungsten oxide fine particles are uniformly present in the infrared shielding adhesive film, a large number of the tears are locally generated, and radicals are generated along with the tearing. It is thought that organic peroxide is generated.

  As a result of these studies by the present inventors, a “primary antioxidant” that traps radicals is added to the infrared shielding adhesive film containing the tungsten oxide fine particles or / and the composite tungsten oxide fine particles. However, the suppression of deterioration is not improved, and it has been found that deterioration can be suppressed for the first time by adding a “secondary antioxidant” that decomposes the organic oxide, and in the above “secondary antioxidant” There are two types of phosphoric antioxidants and sulfur-based antioxidants. In (meth) acrylic polymers that are adhesive film forming materials, the addition of phosphorous antioxidants as the first countermeasure In addition, the inventors have found that the above-mentioned wet heat resistance can be improved.

  In addition, in the infrared shielding adhesive film to which tungsten oxide fine particles and / or composite tungsten oxide fine particles are applied as the infrared absorbing material, the reason why the shielding effect in the infrared region is reduced in a humid heat environment is that the surface of the fine particles is deteriorated. Cause. In general, oxidative degradation due to residual chlorine or water is suspected as a substance that degrades inorganic compounds or metals, but in a humid heat environment, water vapor (water) that has penetrated into the resin (infrared shielding adhesive) oxidizes the fine particles. It can be considered to deteriorate. Therefore, as a second countermeasure, it is considered that a method for suppressing the permeation of water vapor is effective for suppressing deterioration (improvement of the moisture and heat resistance characteristics).

  Furthermore, as a third countermeasure, it was considered effective to form stronger bonds in order to suppress the breakage of bonds that are radical generating elements. The bond considered here indicates a bond between the functional group for crosslinking (organic material) of the (meth) acrylic polymer and the tungsten oxide fine particles or / and the composite tungsten oxide fine particles (inorganic material). Addition of a silane coupling agent, alkoxide, or metal chelate is effective as a material to supplement this bond. However, when the (acid) type (meth) acrylic polymer is used, the alkoxide or metal having a high reaction rate is used. A coating solution for forming an infrared shielding adhesive film to which a necessary amount of chelate is added has a problem that a crosslinking reaction proceeds simultaneously with mixing with a (meth) acrylic polymer and the form of the coating solution cannot be maintained. Therefore, it has been found that by adding a silane coupling agent having a relatively slow reaction rate, it is possible to maintain the coating solution viscosity in a coatable state and to improve the wet heat resistance. As the silane coupling agent, those having a functional group X of the following general formula (IV) having a vinyl group, an epoxy group, a mercapto group, or an isocyanate group are effective. Those having amino groups have been found to have poor compatibility with (meth) acrylic polymers and adversely affect the transparency of the infrared shielding adhesive film.

  Furthermore, for the purpose of accelerating the crosslinking reaction of the (meth) acrylic polymer, it has been found that the resistance to moist heat is improved by adding zinc oxide having a catalytic action. However, the addition amount of zinc oxide is limited to about 100 ppm of the (meth) acrylic polymer, and if it is added, the crosslinking reaction proceeds immediately after the addition due to its catalytic action, and the form of the coating solution for forming an infrared shielding adhesive film Can not keep.

  As described above, it has been found that the above-mentioned moist heat resistance can be improved by the first countermeasure containing a phosphorus-based antioxidant, and further, the second countermeasure containing a clay mineral and a silane coupling agent. Further, it was found that the above-mentioned wet heat resistance can be further improved by using a third countermeasure containing zinc oxide and zinc oxide together. The present invention has been completed by such technical examination and technical discovery.

That is, the invention according to claim 1
An infrared shielding material fine particle dispersion in which infrared shielding material fine particles are dispersed in a solvent , and a (meth) acrylic polymer and a cross-linking agent, which are film forming materials not included in the dispersion, are added to the dispersion Infrared shielding material fine particle dispersion constituting a coating liquid for forming an infrared shielding adhesive film,
Tungsten oxide fine particles represented by the general formula WyOz (W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999), general formula MxWyOz (where M is H, He, alkali metal) , Alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl , Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I 1 or more elements selected, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3) The infrared shielding material fine particles are composed of more than one kind of oxide fine particles. And the phosphorus-based antioxidant is contained in the solvent, and the phosphorus-based antioxidant is 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-ditridecyl). It is characterized by comprising at least one phosphorous antioxidant selected from phosphite, diphenyloctyl phosphite, and trisisodecyl phosphite .

The invention according to claim 2
In the infrared shielding material fine particle dispersion according to the invention of claim 1,
It is characterized by containing clay minerals,
The invention according to claim 3
In the infrared shielding material fine particle dispersion according to the invention of claim 2,
The clay mineral includes bentonite selected from quartz, cristopalite, feldspar, mica, zeolite, and / or smectite selected from montmorillonite, beidellite, nontronite, saponite, hectorite, saconite, stevensite. It is characterized by
The invention according to claim 4
In the infrared shielding material fine particle dispersion according to the invention of claim 2 or 3,
It contains a silane coupling agent,
The invention according to claim 5
In the infrared shielding material fine particle dispersion according to the invention of claim 4,
The silane coupling agent is composed of one or more silane coupling agents selected from the following general formula (IV).

［但し、式（IV）中、Ｒは、メチル基、エチル基、プロピル基から選択される直鎖アルキル基を表し、Ｘは、ビニル基、エポキシ基、ウレイド基、メルカプト基、スルフィド基、イソシアネート基から選択される官能基を表す。］

[In the formula (IV), R represents a linear alkyl group selected from a methyl group, an ethyl group, and a propyl group, and X represents a vinyl group, an epoxy group, a ureido group, a mercapto group, a sulfide group, and an isocyanate group. Represents a functional group selected from the group. ]

Next, the invention according to claim 6 is:
In the infrared shielding material fine particle dispersion according to any one of claims 1, 2, and 4,
The tungsten oxide fine particles or / and the composite tungsten oxide fine particles have a composition phase represented by the general formula WyOz (where W is tungsten, O is oxygen, 2.45 ≦ z / y ≦ 2.999). Including,
The invention according to claim 7 provides:
In the infrared shielding material fine particle dispersion according to any one of claims 1, 2, and 4,
The composite tungsten oxide fine particles represented by the general formula MxWyOz includes one or more of hexagonal, tetragonal, or cubic crystal structures,
The invention according to claim 8 provides:
In the infrared shielding material fine particle dispersion according to the invention of claim 7,
The M element includes one or more of Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn and has a hexagonal crystal structure.

The invention according to claim 9 is
In the coating liquid for forming the infrared shielding adhesive film,
The infrared shielding material fine particle dispersion according to any one of claims 1 to 8, wherein at least one selected from a (meth) acrylic polymer, an epoxy-based crosslinking agent, a metal chelate-based crosslinking agent, and an isocyanate-based crosslinking agent. It is characterized by comprising a crosslinking agent,
The invention according to claim 10 is:
In the coating liquid for forming an infrared shielding adhesive film according to the invention of claim 9,
It is characterized by containing zinc oxide,
The invention according to claim 11 is:
In the coating liquid for forming an infrared shielding adhesive film according to the invention of claim 9 or 10,
The (meth) acrylic polymer is
(A-1) composed of acrylic acid alkyl ester and / or methacrylic acid alkyl ester, or
(A-2) It is characterized by comprising a polymer obtained by polymerizing another monomer copolymerizable with the above (a-1).

Next, the invention according to claim 12 is:
In infrared shielding adhesive film,
A coating film is formed by applying the coating liquid for forming an infrared shielding adhesive film according to any one of claims 9 to 11 on a first substrate surface or a plasma display panel surface of a multilayer filter for a plasma display panel, And it is obtained by aging treatment of the coating film,
The invention according to claim 13 is:
In the infrared shielding optical member,
The first base material and the infrared shielding adhesive film according to claim 12 formed on the first base material surface,
The invention according to claim 14 is:
In multilayer filters for plasma display panels,
The infrared shielding optical member according to claim 13 is incorporated,
The invention according to claim 15 is
In plasma display panels,
The multilayer filter for plasma display panels of Claim 14 is provided, It is characterized by the above-mentioned.

An infrared shielding material fine particle dispersion in which infrared shielding material fine particles are dispersed in a solvent , and a (meth) acrylic polymer and a cross-linking agent, which are film forming materials not included in the dispersion, are added to the dispersion The infrared shielding material fine particle dispersion according to claim 1 of the present invention constituting the coating liquid for forming an infrared shielding adhesive film is a tungsten oxide fine particle represented by the general formula WyOz, a general formula 4. It is composed of one or more kinds of oxide fine particles selected from composite tungsten oxide fine particles represented by MxWyOz, and the phosphorus-based antioxidant is contained in the solvent, and the phosphorus-based antioxidant is 4 , 4′-butylidene-bis (3-methyl-6-tert-butylphenyl-ditridecyl) phosphite, diphenyloctyl phosphite, and tris And characterized in that it is composed of one or more phosphorus-based antioxidant selected from the source-decyl phosphite, infrared shielding material microparticle dispersion liquid according to claim 2 of the present invention, in addition to the phosphorus-based antioxidant In addition, the infrared shielding material fine particle dispersion according to claim 4 of the present invention contains a viscosity mineral and a silane coupling agent in addition to the phosphorous antioxidant. It is characterized by being.

The infrared ray shielding material fine particle dispersion is added with (meth) acrylic polymer and at least one cross-linking agent selected from an epoxy cross-linking agent, a metal chelate cross-linking agent and an isocyanate cross-linking agent. According to the infrared shielding adhesive film of the present invention formed using the infrared shielding adhesive film-forming coating liquid according to claim 10 to which the infrared shielding adhesive film-forming coating liquid according to item 9 or zinc oxide is further added. Infrared shielding material fine particles are composed of one or more kinds of oxide fine particles selected from tungsten oxide fine particles represented by the general formula WyOz and composite tungsten oxide fine particles represented by the general formula MxWyOz, and phosphorus-based oxidation prevention Incorporating any of the above agents or phosphorus antioxidants and viscosity minerals, silane coupling agents, or zinc oxide. It is possible to exhibit while excellent wet heat resistance wet heat resistance maintaining high visible light transmittance and near infrared absorptive been improved shielding material fine particles.

  Similarly, in the multilayer filter for a plasma display panel and the plasma display panel according to the present invention using the infrared shielding adhesive film and the infrared shielding optical member of the present invention provided with the infrared shielding adhesive film, high visible light transmission is similarly applied. It is possible to exhibit excellent heat and humidity resistance while maintaining the rate and near infrared absorption.

It is schematic structure explanatory drawing of a plasma display panel.

  Hereinafter, embodiments of the present invention will be described in detail.

First, an infrared shielding material fine particle dispersion in which infrared shielding material fine particles are dispersed in a solvent, and a (meth) acrylic polymer and a crosslinking agent, which are film forming materials not contained in the dispersion, Infrared shielding material fine particle dispersion comprising the coating liquid for forming an infrared shielding adhesive film is added to the tungsten oxide fine particles represented by the general formula WyOz, the composite tungsten oxide represented by the general formula MxWyOz An infrared shielding pressure-sensitive adhesive film-forming coating according to the present invention, characterized in that an infrared shielding material fine particle composed of one or more oxide fine particles selected from fine particles and a phosphorus-based antioxidant are contained in a solvent. liquor, in the infrared shielding material microparticle dispersion liquid, (meth) acrylic-based polymer, epoxy-based crosslinking agents, metal chelate-based crosslinking agents, isocyanate-based Is characterized in that at least one crosslinking agent is selected from the bridge agent is formed by addition.

  In addition, the infrared shielding adhesive film according to the present invention is formed by applying the coating liquid for forming the infrared shielding adhesive film on the first substrate surface or the plasma display panel surface of the multilayer filter for plasma display panel. In addition, the infrared shielding optical member according to the present invention is obtained by aging the coating film, and the infrared shielding optical film according to the present invention is formed on the first substrate and the infrared shielding adhesive film formed on the first substrate surface. It is comprised by these.

  Next, a multilayer filter for a plasma display panel according to the present invention is characterized in that the infrared shielding optical member is incorporated, and the plasma display panel according to the present invention is provided with a multilayer filter for a plasma display panel. It is characterized by this.

  Hereinafter, description will be made sequentially.

1. Infrared shielding material fine particle dispersion Adhesive film forming material (meth) acrylic polymer and a crosslinking agent are added to form an infrared shielding adhesive film forming coating solution, and the infrared shielding material fine particle dispersion according to the present invention is 4 10 to 80 composed of ˜89 parts by weight of solvent and one or more oxide fine particles selected from tungsten oxide fine particles represented by the general formula WyOz and composite tungsten oxide fine particles represented by the general formula MxWyOz It contains a part by weight of infrared shielding material fine particles and a phosphorus-based antioxidant, and the content of the phosphorus-based antioxidant can be appropriately selected. The average dispersed particle size of the tungsten oxide fine particles and composite tungsten oxide fine particles is desirably 800 nm or less, and more preferably the average dispersed particle size is 100 nm or less.

(A) Solvent
The solvent used in the infrared shielding material fine particle dispersion is required not to inhibit the crosslinking reaction of the (meth) acrylic polymer. The (meth) acrylic polymer having a carboxyl group or / and a hydroxyl group as a crosslinkable group is an epoxy crosslinker, a metal chelate crosslinker or an isocyanate crosslinker as a crosslinkable group in the (meth) acrylic polymer skeleton. It reacts with a carboxyl group or / and a hydroxyl group, and a crosslinking reaction for crosslinking (meth) acrylic polymers proceeds.

  The solvent has a carboxyl group (COOH group) or a hydroxyl group (OH group) that reacts with the crosslinking agent in a rate-determining manner and inhibits the reaction between the crosslinking group and the crosslinking agent contained in the (meth) acrylic polymer. One or more kinds selected from ketones, esters, hydrocarbons, and ethers that are not contained are preferable. Typical examples include ketones such as methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; toluene, xylene, etc. And hydrocarbons such as ethyl ether and isopropyl ether. Of these, ketones and esters are more preferable because they are low in danger and toxicity and are easy to handle. In addition, in the isocyanate type crosslinking agent, when a blocked isocyanate or the like that does not inactivate by side reaction with alcohols is used, it is not a problem to use alcohols. Representative examples include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, and tert-butanol.

(B) Tungsten oxide fine particles and composite tungsten oxide fine particles Infrared shielding material fine particles applied in the present invention have the general formula WyOz (W is tungsten, O is oxygen, and 2.2 ≦ z / y as described above. ≦ 2.999), tungsten oxide fine particles represented by general formula MxWyOz (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, One or more elements selected from Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, W is tungsten, O is oxygen, 0.001 ≦ x / Y ≦ 1, 2.2 ≦ / Y ≦ 3) constituted by one or more oxide particles are selected from the composite tungsten oxide fine particles expressed by.

Examples of the tungsten oxide fine particles represented by the general formula WyOz (2.2 ≦ z / y ≦ 2.999) include W ₁₈ O ₄₉ , W ₂₀ O ₅₈ , and W ₄ O ₁₁ . If the value of z / y is 2.2 or more, it is possible to completely avoid the appearance of an undesired WO ₂ crystal phase in the infrared shielding material and to obtain the chemical stability of the material. Can do. On the other hand, if the value of z / y is 2.999 or less, a sufficient amount of free electrons is generated and an efficient infrared shielding material is obtained. And the WyOz compound whose range of z / y is 2.45 <= z / y <= 2.999 is a compound called what is called a Magneli phase, and is excellent in durability.

The composite tungsten oxide fine particles represented by the general formula MxWyOz (0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3) have hexagonal, tetragonal, and cubic crystal structures. Since it has excellent durability when it has, it preferably has one or more crystal structures selected from hexagonal crystals, tetragonal crystals, and cubic crystals. For example, in the case of composite tungsten oxide fine particles having a hexagonal crystal structure, preferable M elements include Cs, Rb, K, Ti, In, Ba, Li, Ca, Sr, Fe, and Sn. Examples thereof include composite tungsten oxide fine particles containing one or more selected elements. The addition amount x of the M element added at this time is preferably 0.001 or more and 1 or less in x / y, and more preferably around 0.33. This is because the value of x / y calculated theoretically from the hexagonal crystal structure is 0.33, and preferable optical characteristics can be obtained with the addition amount before and after this. On the other hand, the abundance z of oxygen is preferably 2.2 or more and 3 or less in z / y. Typical examples include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _3, etc., but useful if x, y and z are within the above ranges. Infrared shielding characteristics can be obtained.

  These tungsten oxide fine particles and composite tungsten oxide fine particles may be used alone or in combination.

When at least one selected from the tungsten oxide fine particles and the composite tungsten oxide fine particles is used in the infrared shielding material fine particle dispersion , the average dispersed particle size is preferably 800 nm or less, more preferably 200 nm or less, Preferably it is 100 nm or less. When the average dispersed particle diameter of the tungsten oxide or composite tungsten oxide exceeds 800 nm, the geometrical scattering or Mie scattering, since the result in scattered light in the visible light region of wavelengths 380 nm to 780 nm, the infrared shielding material The appearance of the infrared shielding adhesive film in the multilayer filter for PDP produced using the fine particle dispersion becomes like frosted glass, and a clear screen display cannot be obtained, which is not preferable. When the average dispersed particle size is 200 nm or less, geometric scattering or Mie scattering is reduced, and a Rayleigh scattering region is obtained. In the Rayleigh scattering region, the scattered light is reduced in inverse proportion to the sixth power of the average dispersed particle size, so that visible light scattering is reduced and a clear screen display is possible. Further, it is preferable that the average dispersed particle diameter is 100 nm or less because scattered light is extremely reduced.

(C) Antioxidant The antioxidant applied in the present invention is not particularly limited in chemical structure as long as it acts as an organic peroxide decomposer and decomposes into an inactive compound.

  Antioxidants that decompose organic peroxides into inactive compounds are referred to as “secondary antioxidants” as described above, and include phosphorus antioxidants and sulfur antioxidants.

The antioxidant as the “secondary antioxidant” applied in the present invention is required to be a phosphorus antioxidant, and includes the following general formula (I), general formula (II), and general formula (III). It is necessary to comprise at least one phosphorus-based antioxidant selected from

［但し、式（Ｉ）中、Ｒ_１〜Ｒ_３は、直鎖アルキル基、分岐アルキル基、環状アルキル基、フェニル基、または、上記アルキル基内の一部水素原子がフェニル基に置換された官能基を表すと共に、ｐ、ｑ、ｒはそれぞれ独立して０〜３の整数を表し、かつ、ｐ＋ｑ＋ｒ＝３である。］

[In the formula (I), R _{1 to} R ₃ are each a linear alkyl group, a branched alkyl group, a cyclic alkyl group, a phenyl group, or a partial hydrogen atom in the alkyl group is substituted with a phenyl group. While representing a functional group, p, q, and r each independently represent an integer of 0 to 3, and p + q + r = 3. ]

［但し、式（II）中、Ｒ_１〜Ｒ_５は、直鎖アルキル基、分岐アルキル基、環状アルキル基、フェニル基、または、上記アルキル基内の一部水素原子がフェニル基に置換された官能基を表すと共に、ｐ、ｑ、ｒ、ｓはそれぞれ独立して０〜４の整数を表し、かつ、ｐ＋ｑ＋ｒ＋ｓ＝４である。］

[However, in the formula (II), R _{1 to} R ₅ are a linear alkyl group, a branched alkyl group, a cyclic alkyl group, a phenyl group, or a partial hydrogen atom in the alkyl group is substituted with a phenyl group. While representing a functional group, p, q, r, and s each independently represent an integer of 0 to 4, and p + q + r + s = 4. ]

［但し、式（III）中、Ｒ_１〜Ｒ₇は、直鎖アルキル基、分岐アルキル基、環状アルキル基、フェニル基、または、上記アルキル基内の一部水素原子がフェニル基に置換された官能基を表すと共に、ｐ、ｑ、ｒ、ｓ、ｔ、ｕはそれぞれ独立して０〜６の整数を表し、かつ、ｐ＋ｑ＋ｒ＋ｓ＋ｔ＋ｕ＝６である。］

[In the formula (III), R _{1 to} R ₇ are a linear alkyl group, a branched alkyl group, a cyclic alkyl group, a phenyl group, or a partial hydrogen atom in the alkyl group is substituted with a phenyl group. In addition to representing a functional group, p, q, r, s, t, and u each independently represent an integer of 0 to 6, and p + q + r + s + t + u = 6. ]

  Specific examples of the phosphorus antioxidant include, for example, triphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, diphenyloctyl phosphite, diphenylisodecyl phosphite, phenyldiisodecyl phosphite, Tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene phosphite, trisisodecyl phosphite, trisnonylphenyl phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol Diphosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol Diphosphite, bis (2,4-dicum Phenyl) pentaerythritol-diphosphite, tetrakis (2,4-di-t-butylphenyl) (1,1-biphenyl) -4,4′-diylbisphosphite, di-t-butyl-m-cresyl-phosphonite, Distearyl pentaerythritol diphosphite, di (2,6-di-t-butylphenyl) -pentaerythritol diphosphite, di (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol diphos Phyto, 4,4′-butylidene-bis (3-methyl-6-t-butylphenyl-ditridecyl) phosphite, cyclic neopentanetetrayl (octadecyl phosphite), diisodecyl pentaerythritol diphosphite, 2,2- Methylenebis (4,6-di-t-butylphenyl) octylphosphine Bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, hydrogenated bisphenol A pentaerythritol phosphite polymer, hydrogenated bisphenol A phosphite polymer, tetraphenyltetra (tridecyl) pentaerythritol tetra Examples thereof include phosphite, tetra (tridecyl) -4,4′-isopropylidene diphenyl phosphite, tetraphenyl dipropylene glycol diphosphite and the like.

Among these, in the present invention, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-ditridecyl) phosphite, diphenyloctyl phosphite, and tris, which are liquid at room temperature, are used. It must be a phosphorous antioxidant selected from isodecyl phosphite .

(D) Clay mineral As described above, the infrared shielding material fine particle dispersion according to the present invention preferably contains a clay mineral.

  The clay mineral is selected from bentonite selected from quartz, cristopalite, feldspar, mica, zeolite, and / or montmorillonite, beidellite, nontronite, saponite, hectorite, soconite, stevensite. It is desirable to include a smectite. Among them, clay minerals in which a plate-like crystal has a laminated structure (layered structure) with interlayer ions such as sodium ions and potassium ions are suitable, such as hectorite and montmorillonite.

The clay mineral is preferably a clay mineral that is easily dissolved in a water-insoluble solvent and has improved compatibility with the resin by substituting the interlayer ions with a quaternary ammonium cation or the like. Here, the quaternary ammonium cation preferably includes four carbon chains having 1 to 50 carbon atoms and 3 to 101 hydrogen atoms centering on N +. The carbon chain may have a linear structure, a branched structure, or a cyclic structure. The clay mineral in which the interlayer ion is replaced with a quaternary ammonium cation, etc. is subjected to vibration treatment, stirring treatment, ultrasonication in one or more solvents selected from ketones, esters, hydrocarbons, ethers, and alcohols. It is most preferable to disperse by treatment and use it as a dispersion of transparent infrared shielding material fine particles because it does not adversely affect the haze of the obtained infrared shielding adhesive film.

  By adding the viscosity mineral, water (water vapor) can be prevented from penetrating into the infrared shielding adhesive film. By using a viscosity mineral in combination with the antioxidant, it is effective for further suppressing the wet heat resistance deterioration of the tungsten oxide fine particles and / or the composite tungsten oxide fine particles.

(E) Silane Coupling Agent The infrared shielding material fine particle dispersion according to the present invention preferably contains a silane coupling agent in addition to the clay mineral as described above.

The silane coupling agent applied in the present invention is a compound composed of an organic substance and silicon, and includes a reactive group that chemically bonds with an inorganic material in a molecule and a reactive group that chemically bonds with an organic material. Has two or more different reactive groups. For this reason, it acts as an intermediary between the organic material and the inorganic material which are usually very difficult to bond. The reactive group bonded to the inorganic material includes a methoxy group (—OCH ₃ ) and an ethoxy group (—OC ₂ H ₅ ), which becomes a silanol by hydrolysis and forms a chemical bond with the inorganic surface. Examples of the reactive group that binds to the organic material include a vinyl group, an epoxy group, a ureido group, a mercapto group, a sulfide group, an isocyanate group, a styryl group, a methacryloxy group, an acryloxy group, and an amino group.

  The silane coupling agent is generally used for improving mechanical strength, water resistance, adhesion, resin modification, surface modification, and the like of composite materials. As specific examples of the silane coupling agent, for example, vinyltrimethoxysilane and vinyltriethoxysilane whose organic functional groups are vinyl groups, and 2- (3,4-epoxy whose organic functional groups are epoxy groups. Cyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltri, whose organic functional group is a styryl group Methoxysilane, 3-methacryloxypropyltridimethoxysilane whose organic functional group is methacryloxy group, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, organic functionality The group is active 3-acryloxypropyltrimethoxysilane which is a roxy group, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane whose organic functional group is an amino group, N-2- (aminoethyl) -3-amino Propyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3 -Dimethyl-bitylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, 3 whose organic functional group is a ureido group -Ureidopropyltriethoxysilane, the organic functional group is a mercapto group Lucaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide whose organic functional group is a sulfide group, 3-isocyanatopropyltriethoxysilane whose organic functional group is an isocyanate group, etc. Can be mentioned. Among them, a silane coupling agent having an organic functional group having a vinyl group, an epoxy group, a mercapto group, or an isocyanate group has good reactivity with a (meth) acrylic polymer and / or an acrylic dispersant, and tungsten oxide fine particles or / and It is desirable because the composite tungsten oxide fine particles have a high effect of suppressing heat and heat resistance deterioration. In addition, the addition amount of the silane coupling agent is preferably 10 to 20 parts by weight with respect to the weight of the tungsten oxide fine particles and / or the composite tungsten oxide fine particles.

  On the other hand, a silane coupling agent having an organic functional group having a styryl group, a methacryloxy group, or an acryloxy group may have a weak effect of suppressing the heat-and-moisture resistance deterioration due to the addition. This causes a problem that the coating liquid for forming an adhesive film becomes cloudy and loses transparency.

  And as a silane coupling agent applied in this invention, the silane coupling agent shown by the following general formula (IV) is desirable.

［但し、式（IV）中、Ｒは、メチル基、エチル基、プロピル基から選択される直鎖アルキル基を表し、Ｘは、ビニル基、エポキシ基、ウレイド基、メルカプト基、スルフィド基、イソシアネート基から選択される官能基を表す。］

[In the formula (IV), R represents a linear alkyl group selected from a methyl group, an ethyl group, and a propyl group, and X represents a vinyl group, an epoxy group, a ureido group, a mercapto group, a sulfide group, and an isocyanate group. Represents a functional group selected from the group. ]

2. Infrared shielding adhesive film forming coating solution Next, the infrared shielding adhesive film forming coating solution according to the present invention is obtained by adding (meth) acrylic polymer, epoxy crosslinking agent, metal chelate to the above-described infrared shielding material fine particle dispersion. It is characterized in that at least one kind of crosslinking agent selected from a system crosslinking agent and an isocyanate-based crosslinking agent is added, and further zinc oxide is added in addition to the above-mentioned crosslinking agent.

(A) (Meth) acrylic polymer As the (meth) acrylic polymer, (a-1) acrylic acid alkyl ester and / or methacrylic acid alkyl ester, or (a-2) (a-1) above and Examples thereof include a polymer obtained by polymerizing other copolymerizable monomers.

(A-1) Acrylic acid alkyl ester or / and methacrylic acid alkyl ester Examples of the acrylic acid alkyl ester include C1-15 linear, branched or cyclic alkyl esters of acrylic acid. For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, tert-butyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, n-acrylate -Pentyl, isoamyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, isobonyl acrylate, acrylic acid Examples include cyclohexyl.

  Examples of the alkyl methacrylate include C1-15 linear, branched or cyclic alkyl esters of methacrylic acid. Examples thereof include methyl methacrylate, ethyl methacrylate, -n-propyl methacrylate, and isopropyl methacrylate. , Methacrylate-n-butyl, methacrylate-sec-butyl, methacrylate-t-butyl, methacrylate-n-pentyl, isoamyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, and the like.

  Among them, it is preferable to use an alkyl acrylate ester having an alkyl group having 4 to 8 carbon atoms because the adhesive strength and flexibility of the obtained adhesive are improved. Particularly, n-butyl acrylate, acrylate-2- Ethylhexyl is preferred.

(A-2) Polymer obtained by polymerizing other monomer copolymerizable with (a-1) As the other monomer copolymerizable with (a-1), for example, one or more carboxyl groups are molecules Examples thereof include compounds having an unsaturated bond. For example, acrylic acid, methacrylic acid, acrylic-β-carboxyethyl, methacrylic acid-β-carboxyethyl, acrylic acid-5-carboxypentyl, methacrylic acid-5-carboxypentyl, succinic acid monoacryloyloxyethyl ester, ω-carboxyl Carboxyl group-containing monomers such as polycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, itaconic acid, crotonic acid, fumaric acid, maleic acid; acrylic acid-2-hydroxyethyl, methacrylic acid-2-hydroxyethyl, acrylic acid- 2-hydroxypropyl, 2-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 2-hydroxy-3-chloropropyl acrylate, methacrylate Hydroxyl-containing monomers such as 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-hydroxy-3-phenoxypropyl methacrylate; 2-methoxyethyl acrylate, acrylic Acrylic acid alkoxy esters such as 2-ethoxyethyl acid, 2-methoxypropyl acrylate, 3-methoxypropyl acrylate, 2-methoxybutyl acrylate, 4-methoxybutyl acrylate, methacrylic acid-2- Methacrylic acid alkoxyesters such as methoxyethyl, methacrylic acid-2-ethoxyethyl, methacrylic acid-2-methoxypropyl, methacrylic acid-3-methoxypropyl, methacrylic acid-2-methoxybutyl, methacrylic acid-4-methoxybutyl; Ethylene glycol acrylate Acrylic glycol acrylates such as polyethylene glycol acrylate, propylene glycol acrylate, polypropylene glycol acrylate; alkylene glycol methacrylates such as ethylene glycol methacrylate, polyethylene glycol methacrylate, propylene glycol methacrylate, polypropylene glycol methacrylate; acrylic Aryl acrylates such as benzyl acid, phenoxyethyl acrylate, and phenyl acrylate, aryl methacrylates such as benzyl methacrylate, phenoxyethyl methacrylate, and phenyl methacrylate; vinyl acetate, styrene, α-methylstyrene, allyl acetate, and the like It is done.

(B) Crosslinking agent Examples of the crosslinking agent include the above-mentioned isocyanate crosslinking agents, epoxy crosslinking agents, and metal chelate crosslinking agents. Among them, isocyanate crosslinking agents are preferable, and particularly, isocyanate crosslinking agents and metal chelate crosslinking agents. It is preferable to use together.

The isocyanate crosslinking agent, tolylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, chlorpheniramine diisocyanate, hexamethylene f Ji diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetra Merrill xylylene Polyisocyanate compounds having two or more isocyanate groups in the molecule such as diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate; addition of these with polyhydric alcohols such as trimethylolpropane and pentaerythritol Compounds of these compounds and polyisocyanate compounds Type compounds and isocyanurate compounds; these polyisocyanate compounds and known polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols and the like in addition to two or more in the urethane prepolymer type molecule. Examples include compounds having an isocyanate group.

  Examples of the epoxy crosslinking agent include bisphenol A epichlorohydrin type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, Trimethylolpropane triglycidyl ether, diglycidyl aniline, diamine glycidyl amine, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N′-diamine glycidylaminomethyl) Examples thereof include compounds having two or more epoxy groups in the molecule such as octhexane.

  Examples of the metal chelate crosslinking agent include acetylene and ethyl acetoacetate coordinated to polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium. Compounds.

(C) a zinc oxide used in combination with zinc oxide the crosslinking agent, the transparency of the infrared-shielding pressure-sensitive film-forming coating solution, particularly the shape Without affecting the coating properties are not specified, an infrared shielding material microparticle dispersion liquid It is desirable to make fine particles with the same acrylic dispersant and solvent. Since it is added in order to promote the crosslinking reaction of the (meth) acrylic polymer, the addition amount is preferably 1 to 100 ppm of the weight of the (meth) acrylic polymer. If, for example, 1000 ppm is added in excess of 100 ppm, the crosslinking reaction proceeds simultaneously with the addition of zinc oxide, and the viscosity increases rapidly or hardens, which may adversely affect the coatability.

3. Infrared shielding adhesive film and infrared shielding optical member The coating liquid for forming an infrared shielding adhesive film according to the present invention includes a (meth) acrylic polymer, an epoxy-based crosslinking agent, and a metal chelate-based crosslinking in the infrared shielding material fine particle dispersion described above. In addition, an infrared shielding adhesive film according to the present invention is configured by adding at least one kind of crosslinking agent selected from an agent and an isocyanate-based crosslinking agent, or by adding zinc oxide in addition to the crosslinking agent. The coating solution for forming the infrared shielding adhesive film is applied on the first substrate surface or the plasma display panel surface of the multilayer filter for plasma display panel to form a coating film, and the coating film is obtained by aging treatment. The infrared shielding pressure-sensitive adhesive film may further contain a neon cut dye or a color tone correction dye. The first substrate of the multilayer filter for a plasma display panel is an arbitrary film body such as an electromagnetic wave shielding film other than the infrared shielding adhesive film, an external force absorbing layer described later, or an infrared shielding adhesive film that constitutes the multilayer filter. Film formation body on which the main body is formed (in this case, the infrared shielding adhesive film main body and the film formation body constitute an infrared shielding adhesive film in the multilayer filter. In the case where it is provided, these film forming bodies also become constituent elements of each film). The first base material may be an arbitrary base material (a base material exposed on the surface) of a multilayer filter directly provided on the surface of the plasma display panel, or may be attached to the surface of the plasma display panel. It may be an arbitrary base material of the multilayer filter before being processed.

  The film-formed body to which the coating liquid for forming the infrared shielding adhesive film is applied may be a film or a board, and the shape is not limited. As transparent film-forming materials, polyethylenes such as polyethylene terephthalate (hereinafter sometimes referred to as PET), acrylics, urethanes, polycarbonates, ethylene vinyl acetate copolymers, polyvinyl chloride, fluorine resins, etc. are used for various purposes. It can be used accordingly. Moreover, glass other than resin can be used.

  In addition, as a method of applying the coating liquid for forming the infrared shielding adhesive film, it is not particularly limited as long as the coating film can be uniformly formed on the first base material surface or the plasma display panel surface of the multilayer filter for a plasma display panel. Examples include a doctor blade method, a bar coating method, a gravure coating method, a dip coating method, and a slit coating method.

  In addition, since one or more kinds of oxide fine particles selected from the tungsten oxide fine particles and composite tungsten oxide fine particles contained in the infrared shielding adhesive film are uniformly dispersed in a material rich in transparency, It can be used without impairing the design property even if it is installed on the surface. In the infrared shielding adhesive film, the (meth) acrylic polymer that is a film-forming material is preferably used when different materials such as a glass substrate and a PET substrate are bonded to each other in the PDP panel. This is because it has good transparency with high visible light transmittance.

  Then, a (meth) acrylic polymer [below] used for an infrared shielding adhesive film containing at least a phosphorus-based antioxidant or containing a clay mineral, a silane coupling agent, and zinc oxide in addition to the phosphorus-based antioxidant The functional group contained in the adhesive resin or PSA (Pressure Sensitive Adhesive) may be an “acid group type” that contains many carboxyl groups that improve the adhesiveness of the infrared shielding film in addition to the hydroxyl groups described above. There is no limitation as long as the tungsten oxide fine particles and the composite tungsten oxide fine particles can be dispersed without agglomeration.

  Next, the infrared shielding optical member according to the present invention includes a first base material to which an infrared shielding adhesive film-forming coating solution is applied and an infrared shielding adhesive film formed on the first base material surface. .

  And since it becomes possible to stick the said infrared shielding optical member directly on the 2nd base material surface of a multilayer filter by the effect | action of an infrared shielding adhesive film, since the adhesive film has an infrared shielding function, the manufacturing cost is reduced. There is an effect that can be achieved. The second base material of the multilayer filter corresponds to any film such as an electromagnetic wave shielding film or an external force absorbing layer other than the infrared shielding adhesive film that constitutes the multilayer filter.

4). The multilayer filter for plasma display panels and the plasma display panel The multilayer filter for plasma display panels according to the present invention is a multilayer filter that is applied to the plasma display panel and that incorporates the infrared shielding optical member according to the present invention. In addition, the multilayer filter is configured by laminating a plurality of base materials (including the above-described first base material, second base material, etc.) such as an infrared shielding adhesive film, an electromagnetic wave shielding film, an external force absorption layer, When the infrared shielding adhesive film, the electromagnetic shielding film, the external force absorbing layer, etc. are provided with a film-forming body, the infrared shielding adhesive film body and the infrared shielding adhesive film comprising the film-forming body, the electromagnetic wave shielding film body and the substrate are formed. An electromagnetic wave shielding film made of a film body, an external force absorbing layer main body, an external force absorbing layer made of a film formation body, and the like are included. The multilayer filter (laminated body) composed of a plurality of base materials is formed by directly applying a coating solution containing the constituent materials of each base material on the surface of the plasma display panel. When forming the multilayer filter (laminate), a separate multilayer filter (laminate) composed of a plurality of substrates is prepared in advance, and this multilayer filter (laminate) is pasted on the surface of the plasma display panel. ), Or a multilayer filter (laminated body) may be formed by appropriately combining these methods.

  On the other hand, the plasma display panel according to the present invention is a plasma display panel in which the multilayer filter for a plasma display panel according to the present invention is incorporated.

  In addition, about the said infrared shielding adhesive film, according to the electromagnetic shielding function, it is made into the structure where the mesh which has an electromagnetic wave shielding function in the infrared shielding adhesive film, and / or the fibrous metal layer or the metal containing layer was embedded. This is preferable because it can achieve three types of functions of an infrared shielding function, an electromagnetic wave function, and an adhesion function in one layer.

  About the said mesh-shaped electromagnetic wave shielding member, if it has electromagnetic wave shielding ability, the kind etc. will not be limited. Typical examples include Cu, Fe, Ni, Cr, Al, Au, Ag, W, Ti, or metal foils made of these alloys processed into a mesh shape, and conductivity such as carbon black, Cu, and Ni. Examples include inks in which fine particles are dispersed in a binder resin and printed in a mesh pattern.

  Furthermore, when the infrared shielding adhesive film is composed of an infrared shielding adhesive film having excellent impact relaxation properties, an external force absorbing function is added to alleviate the impact applied to the panel and prevent damage to the PDP. The external force absorbing layer, the infrared shielding adhesive film and the adhesive layer that have been provided separately so far can be achieved by one layer, and further, by embedding the mesh-like electromagnetic shielding member or the like, the electromagnetic shielding ability can be obtained. Since it can match | combine, it is preferable.

  As described above, the infrared shielding adhesive film according to the present invention includes one or more oxide fine particles selected from tungsten oxide fine particles represented by the general formula WyOz and composite tungsten oxide fine particles represented by the general formula MxWyOz. Compared to the case where infrared shielding materials such as organic dyes and metal complexes are applied, it is possible to maintain high near-infrared absorption characteristics over a long period of time because the infrared shielding material fine particles are configured. The film contains at least a phosphorus-based antioxidant, or, in addition to the phosphorus-based antioxidant, a clay mineral, a silane coupling agent, and zinc oxide. The heat-and-moisture resistance characteristics of the fine particles are also dramatically improved.

  Therefore, the plasma display panel in which the multilayer filter having the infrared shielding adhesive film is incorporated is extremely useful industrially because the infrared shielding effect can be maintained for a long time.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these Examples.

[Example 1]
A (meth) acrylic polymer (trade name SK Dyne-2094 manufactured by Soken Chemical Co., Ltd.) to which a mixed solvent of ethyl acetate and methyl ethyl ketone is applied as a solvent is used as a main agent, and diphenyloctyl phosphite is used as a phosphorus antioxidant. Infrared shielding material fine particle dispersion [composite tungsten oxide fine particles Cs _0.33 WO ₃ concentration: 17.4% by weight of Sumitomo Metal Mining Co., Ltd.] in which [trade name ADK STAB C manufactured by ADEKA Corporation] is dissolved YMF-02AA3] and the crosslinking agent listed in Table 1 were mixed with the main agent in the proportions listed in Table 1 to prepare a coating solution for forming an infrared shielding adhesive film according to Example 1. Table 1 shows the composition of the coating solution for forming the infrared shielding adhesive film according to Example 1.

  Next, using a doctor blade on a 50 μm thick PET film, the infrared shielding adhesive film forming coating liquid according to Example 1 was applied and dried at 80 ° C. for 2 minutes, resulting in a coating film thickness of 25 μm. In addition to forming an adhesive layer (infrared shielding adhesive film), the adhesive layer (infrared shielding adhesive film) is bonded to a glass substrate having a thickness of 3 mm to obtain a test sample (infrared shielding optical member) according to Example 1. It was.

[Example 2]
Instead of the phosphorus-based antioxidant (diphenyloctyl phosphite) used in Example 1, 4,4′-butylidene-bis (3-methyl-6-t-butylphenyl-ditridecyl) phosphite [ADEKA Corporation] A test sample (infrared shielding optical member) according to Example 2 was obtained in the same manner as in Example 1 except that the trade name ADK STAB 260 manufactured by the company was used.

[Example 3]
Instead of the phosphorus-based antioxidant (diphenyloctyl phosphite) used in Example 1, trisisodecyl phosphite [trade name Adeka Stub 3010 manufactured by ADEKA Corporation] was used in the same manner as in Example 1. A test sample (infrared shielding optical member) according to Example 3 was obtained.

[Example 4]
A (meth) acrylic polymer (trade name SK Dyne-2094 manufactured by Soken Chemical Co., Ltd.) to which a mixed solvent of ethyl acetate and methyl ethyl ketone is applied as a solvent is used as a main agent, and diphenyloctyl phosphite is used as a phosphorus antioxidant. [Product name ADEKA STAB C manufactured by ADEKA Corporation], polyoxypropylene methylphenyl ammonium (chemical formula: [(CH ₃ ) (C ₂ H ₅ ) ₂ N (CH ₂ CH (CH ₃ ) O) ₂₅ H] + Infrared shielding material fine particle dispersion added with a solution of clay mineral [trade name Lucentite SPN, manufactured by Corp Chemical Co., Ltd.] made of sodium silicate / magnesium (hectorite) surface-treated with methyl isobutyl ketone. [composite tungsten oxide microparticles Cs _0.33 WO ₃ concentration: 17.4% by weight of Sumitomo Metal Mining Co. Manufactured product name YMF-02AA3] and the crosslinking agent described in Table 2 were mixed with the above-mentioned main agent in the ratio described in Table 2 to prepare a coating solution for forming an infrared shielding adhesive film according to Example 4. . Table 2 shows the composition of the coating liquid for forming the infrared shielding adhesive film according to Example 4.

  Next, using a doctor blade on a 50 μm thick PET film, the infrared shielding adhesive film-forming coating solution according to Example 4 was applied and dried at 80 ° C. for 2 minutes to obtain a coating film thickness of 25 μm. In addition to forming an adhesive layer (infrared shielding adhesive film), the adhesive layer (infrared shielding adhesive film) is bonded to a glass substrate having a thickness of 3 mm to obtain a test sample (infrared shielding optical member) according to Example 4. It was.

[Example 5]
Instead of the phosphorus-based antioxidant (diphenyloctyl phosphite) used in Example 4, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-ditridecyl) phosphite [ADEKA Corporation] A test sample (infrared shielding optical member) according to Example 5 was obtained in the same manner as in Example 4 except that the trade name ADK STAB 260 manufactured by the company was used.

[Example 6]
Instead of the phosphorus antioxidant (diphenyloctyl phosphite) used in Example 4, trisisodecyl phosphite [trade name Adeka Stub 3010 manufactured by ADEKA Corporation] was used in the same manner as in Example 4. A test sample (infrared shielding optical member) according to Example 6 was obtained.

[Example 7]
A (meth) acrylic polymer (trade name SK Dyne-2094 manufactured by Soken Chemical Co., Ltd.) to which a mixed solvent of ethyl acetate and methyl ethyl ketone is applied as a solvent is used as a main agent, and diphenyloctyl phosphite is used as a phosphorus antioxidant. [Product name ADEKA STAB C manufactured by ADEKA Corporation], polyoxypropylene methylphenyl ammonium (chemical formula: [(CH ₃ ) (C ₂ H ₅ ) ₂ N (CH ₂ CH (CH ₃ ) O) ₂₅ H] + ) Surface-treated sodium silicate / magnesium (hectorite) clay mineral [trade name Lucentite SPN manufactured by Coop Chemical Co., Ltd.] in methyl isobutyl ketone, and silane coupling agent 3- Isocyanatopropyltriethoxysilane (trade name KBE-9 manufactured by Shin-Etsu Chemical Co., Ltd.) 07) three additives (i.e., the phosphorus-based antioxidant, an infrared shielding material microparticle dispersion liquid clay mineral and a silane coupling agent) was added [composite tungsten oxide microparticles Cs _0.33 WO ₃ concentration: 17. 4% by weight of Sumitomo Metal Mining Co., Ltd., trade name YMF-02AA3], zinc oxide (manufactured by Sumitomo Metal Mining Co., Ltd.) dispersed in toluene using an acrylic dispersant, and listed in Table 3. The crosslinking agent was mixed with the above main agent at a ratio described in Table 3 to prepare a coating solution for forming an infrared shielding adhesive film according to Example 7. Table 3 shows the composition of the coating liquid for forming the infrared shielding adhesive film according to Example 7.

  Next, using a doctor blade on a 50 μm thick PET film, the infrared shielding adhesive film-forming coating solution according to Example 7 was applied and dried at 80 ° C. for 2 minutes to obtain a coating film thickness of 25 μm. In addition to forming an adhesive layer (infrared shielding adhesive film), the adhesive layer (infrared shielding adhesive film) is bonded to a glass substrate having a thickness of 3 mm to obtain a test sample (infrared shielding optical member) according to Example 7. It was.

[Example 8]
A test sample (infrared shielding optical member) according to Example 8 was obtained in the same manner as in Example 7 except that the amount of zinc oxide added in Example 7 was changed to “0.002 parts by weight” shown in Table 4. It was. The proportions of the coating liquid for forming the infrared shielding adhesive film according to Example 8 are shown in Table 4.

[Comparative Example 1]
A test sample (infrared shielding optical member) according to Comparative Example 1 was obtained in the same manner as in Example 1 except that the phosphorus-based antioxidant (diphenyloctyl phosphite) used in Example 1 was not added.

[Comparative Example 2]
Instead of the phosphorus-based antioxidant (diphenyloctyl phosphite) used in Example 1, a sulfur-based antioxidant di-tridecyl-thiodipropionate [Adeka Co., Ltd.] which is a “secondary antioxidant” A test sample (infrared shielding adhesive film) according to Comparative Example 2 was obtained in the same manner as in Example 1 except that the product name ADK STAB AO-503] was used.

[Comparative Example 3]
In place of the phosphorus-based antioxidant (diphenyloctyl phosphite) used in Example 1, 4,6-bis (octylthiomethyl) -o-cresol [Ciba A test sample (infrared shielding optical member) according to Comparative Example 3 was obtained in the same manner as in Example 1 except that the trade name “Irganox 1520L” manufactured by Japan Co., Ltd. was used.

[Measurement condition]
Equipment Constant temperature and humidity chamber FX414P [Enomoto Kasei Co., Ltd.]
Spectrophotometer U-4000 [manufactured by Hitachi High-Tech Fielding]

[Moisture and heat resistance test]
The test sample was exposed for 7 days in an environment of 80 ° C. and 95% RH, and the transmittance at a wavelength of 820 nm was measured.

[Transmittance at wavelength 820 nm]
The transmittance at a wavelength of 800 nm to 850 nm was measured to measure the transmittance at 820 nm.

[Test sample evaluation method]
The transmittance at a wavelength of 820 nm was measured for each test example (infrared shielding optical member) according to each Example and each Comparative Example before the test, and this was set to “0 day” to conduct a moisture and heat resistance test.

  The heat and humidity resistance test was performed by storing in a constant temperature and humidity chamber at 80 ° C. and 95% RH for 7 days.

  Transmittance was measured using a spectrophotometer U-4000 [manufactured by Hitachi High-Tech Fielding Co., Ltd.], and the difference in transmittance [ΔT / (%)] between “Day 7” and “Day 0” was calculated. did.

  The results of the wet heat resistance test are shown in Table 5 below.

[Evaluation]
(1) In Examples 1 to 3 and Comparative Example 1, the presence or absence of addition of a phosphorus-based antioxidant is different.

  When these are compared, the change rate (difference in transmittance) [ΔT / (%)] at a wavelength of 820 nm is 7.28 to 7.95 (%) in Examples 1 to 3, but is a comparative example. 1 was 9.57 (%), confirming the superiority of Examples 1 to 3 in which a phosphorus-based antioxidant was added.

(2) Examples 1 to 3 are obtained by changing the type of the phosphorus-based antioxidant that is a “secondary antioxidant”. The effect of addition is confirmed.

(3) In Comparative Example 2, a sulfur-based antioxidant which is a “secondary antioxidant” was added, and unlike the phosphorus-based antioxidant, the effect of adding the antioxidant could not be confirmed.

(4) In Comparative Example 3, a hindered phenolic antioxidant as a “primary antioxidant” that traps radicals was added, and the effect of adding the antioxidant could not be confirmed.

(5) In Examples 4 to 6 and Comparative Example 1, the presence or absence of addition of a phosphorus-based antioxidant and clay mineral is different.

  When these are compared, the change rate (difference in transmittance) [ΔT / (%)] at a wavelength of 820 nm is 6.12 to 6.42 (%) in Examples 4 to 6, but is a comparative example. 1 is 9.57 (%), the superiority of Examples 4 to 6 in which the phosphorus-based antioxidant and the clay mineral were added in combination was confirmed, and the above numerical values were 7.28 to 7. The superiority of Examples 4-6 is confirmed compared with Examples 1-3 which are 95 (%).

(6) In Examples 4 to 6, the type of the clay mineral is not changed, and the type of the phosphorus-based antioxidant that is the “secondary antioxidant” is changed. The effect of adding an antioxidant is confirmed even when the value is changed.

(7) In Examples 7 to 8 and Comparative Example 1, the presence or absence of addition of a phosphorus-based antioxidant, clay mineral, silane coupling agent, and zinc oxide is different.

  When these are compared, the rate of change (difference in transmittance) [ΔT / (%)] at a wavelength of 820 nm is 4.21 to 4.41 (%) in Examples 7 to 8, but is a comparative example. 1 is 9.57 (%), the superiority of Examples 7 to 8 in which four types of phosphorus antioxidant, clay mineral, silane coupling agent, and zinc oxide were added in combination was confirmed. Furthermore, Examples are compared with Examples 1 to 3 in which the numerical value is 7.28 to 7.95 (%) and Examples 4 to 6 in which the numerical value is 6.12 to 6.42 (%). The superiority of 7-8 is confirmed.

(8) In Examples 7 to 8, the addition amount of zinc oxide was changed, and the addition effect was confirmed as the addition amount of zinc oxide was increased.

  According to the infrared shielding adhesive film of the multilayer filter for a plasma display panel according to the present invention, the plasma display panel has excellent resistance to wet heat while maintaining high visible light transmittance and near infrared absorption. It has industrial applicability that is incorporated and applied.

11 Front glass substrate (front cover plate)
12 Display electrode 13 Dielectric glass layer 14 Protective layer made of magnesium oxide (MgO) 15 Back glass substrate (back plate)
16 Address electrode 17 Partition 18 Phosphor layer 19 Discharge space for enclosing discharge gas

Claims (15)

An infrared shielding material fine particle dispersion in which infrared shielding material fine particles are dispersed in a solvent , and a (meth) acrylic polymer and a cross-linking agent, which are film forming materials not included in the dispersion, are added to the dispersion Infrared shielding material fine particle dispersion constituting a coating liquid for forming an infrared shielding adhesive film,
Tungsten oxide fine particles represented by the general formula WyOz (W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999), general formula MxWyOz (where M is H, He, alkali metal) , Alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl , Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I 1 or more elements selected, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3) The infrared shielding material fine particles are composed of more than one kind of oxide fine particles. And the phosphorus-based antioxidant is contained in the solvent, and the phosphorus-based antioxidant is 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-ditridecyl). An infrared shielding material fine particle dispersion comprising at least one phosphorus-based antioxidant selected from phosphite, diphenyloctyl phosphite, and trisisodecyl phosphite . 2. The infrared shielding material fine particle dispersion according to claim 1, wherein clay mineral is contained. The clay mineral includes bentonite selected from quartz, cristopalite, feldspar, mica, zeolite, and / or smectite selected from montmorillonite, beidellite, nontronite, saponite, hectorite, saconite, stevensite. The infrared shielding material fine particle dispersion according to claim 2. 4. The infrared shielding material fine particle dispersion according to claim 2, further comprising a silane coupling agent. The infrared shielding material fine particle dispersion according to claim 4, wherein the silane coupling agent is composed of one or more silane coupling agents selected from the following general formula (IV).

[In the formula (IV), R represents a linear alkyl group selected from a methyl group, an ethyl group, and a propyl group, and X represents a vinyl group, an epoxy group, a ureido group, a mercapto group, a sulfide group, and an isocyanate group. Represents a functional group selected from the group. ] The tungsten oxide fine particles or / and the composite tungsten oxide fine particles have a composition phase represented by the general formula WyOz (where W is tungsten, O is oxygen, 2.45 ≦ z / y ≦ 2.999). The infrared shielding material fine particle dispersion according to any one of claims 1, 2, and 4. 5. The composite tungsten oxide fine particle represented by the general formula MxWyOz includes one or more of hexagonal, tetragonal or cubic crystal structures. An infrared shielding material fine particle dispersion according to claim 1 . The element M includes one or more of Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn and has a hexagonal crystal structure. Item 8. An infrared shielding material fine particle dispersion according to Item 7. The infrared shielding material fine particle dispersion according to any one of claims 1 to 8, wherein at least one selected from a (meth) acrylic polymer, an epoxy-based crosslinking agent, a metal chelate-based crosslinking agent, and an isocyanate-based crosslinking agent. A coating liquid for forming an infrared shielding adhesive film, wherein a crosslinking agent is added.   The coating liquid for forming an infrared shielding adhesive film according to claim 9, comprising zinc oxide. The (meth) acrylic polymer is
(A-1) composed of acrylic acid alkyl ester and / or methacrylic acid alkyl ester, or
(A-2) The coating liquid for forming an infrared shielding adhesive film according to claim 9 or 10, wherein the coating liquid comprises a polymer obtained by polymerizing another monomer copolymerizable with (a-1). .   A coating film is formed by applying the coating liquid for forming an infrared shielding adhesive film according to any one of claims 9 to 11 on a first substrate surface or a plasma display panel surface of a multilayer filter for a plasma display panel, An infrared shielding pressure-sensitive adhesive film obtained by aging the coating film.   An infrared shielding optical member comprising the first substrate and the infrared shielding adhesive film according to claim 12 formed on the first substrate surface.   A multilayer filter for a plasma display panel, wherein the infrared shielding optical member according to claim 13 is incorporated.   A plasma display panel comprising the multilayer filter for a plasma display panel according to claim 14.

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