JP2008250244A - Multilayer optical film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a multilayer optical film which hardly degrades a near-infrared ray absorption function and an electro-magnetic wave shielding function and does not change haze even when being retained at a high temperature and a high humidity for a long period of time. <P>SOLUTION: The multilayer optical film comprises: a near-infrared ray absorbing pressure-sensitive adhesive layer which includes an acrylic polymer (A) of a weight-average molecular weight 1,200,000 to 1,500,000 prepared by polymerizing acrylic alkyl ester and/or methacrylic alkyl ester (a-1) 82 to 96 pts.mass, carboxylic group-containing monomer (a-2) 4 to 8 pts.mass and other monomer (a-3) 0 to 10 pts.mass, capable of copolymerization with the (a-1) and/or (a-2), (where the total amount of (a-1) to (a-3) is 100 pts.mass), and a diimonium type pigment (B1), wherein solubility of the diimonium type pigment (B1) at 25°C for ethyl acetate 1g is 0.6 mg or more and the diimonium type pigment (B1) is included by 1 to 10 pts.mass to the acrylic polymer (A) 100 pts.mass; an antireflection layer; an electro-magnetic wave shielding layer; and a transparent resin substrate. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a multilayer optical film. Specifically, it is related with the multilayer optical film arrange | positioned in the front surface of a plasma display panel (PDP).

  PDP is known to emit near-infrared rays (wavelength of about 800 to 1100 nm), and since this near-infrared rays may adversely affect peripheral electronic devices, it is necessary to block them.

  In order to absorb near infrared rays emitted from the PDP, near infrared absorbing films have been used. A near-infrared absorbing film is generally bonded to a front plate together with an electromagnetic wave shielding film and an antireflection film to form a panel. However, in order to laminate these functional films, a separate pressure-sensitive adhesive sheet is required, which causes a problem that the haze value of the panel increases and the manufacturing process increases, resulting in high costs.

  Therefore, attempts have been made to solve the above problems by using an adhesive sheet containing a near-infrared adsorbing dye and an adhesive (for example, Patent Documents 1 to 9). However, when any pressure-sensitive adhesive sheet was exposed to a humid and heat environment for a long time, a decrease in near-infrared cut function and an increase in haze were recognized, which were far from practical use. This is because haze is increased due to the deposition of near-infrared adsorbing dye on the pressure-sensitive adhesive layer, or active species such as radicals are generated due to the cleavage of the pressure-sensitive adhesive molecule, resulting in deterioration of the near-infrared adsorbing dye. Conceivable.

In addition, in order to shield electromagnetic waves leaking from the front side of a display unit such as a CRT or PDP, an electromagnetic wave shielding plate formed with a conductive or magnetic pattern on a base is mounted on the front side of the display. Widely used as a front plate. The electromagnetic shielding plate used as the front plate is required not to lower the transparency of the display screen of the display in addition to the function of shielding electromagnetic waves.
JP-A-9-208918 JP 2001-207142 A JP 2003-82302 A JP 2005-62506 A JP 2005-272588 A JP 2006-257223 A JP-T-2006-516357 JP 2007-4098 A JP 2007-16198 A

  An object of the present invention is to provide a multilayer optical film in which a decrease in near-infrared absorption function and an electromagnetic wave shielding function is small and haze does not change even when kept under high temperature and high humidity for a long time.

  As a result of diligent research to solve the above problems, the present inventor polymerized acrylic acid alkyl ester and / or methacrylic acid alkyl ester, carboxyl group-containing monomer, and other copolymerizable monomers as required. A near-infrared absorbing pressure-sensitive adhesive layer comprising an acrylic polymer (A) having a weight average molecular weight of 1,200,000 to 1,500,000 and a diimonium dye (B1), the diimonium dye (B1) at 25 ° C. A near-infrared absorbing pressure-sensitive adhesive layer having a solubility in 1 g of ethyl acetate of 0.6 mg or more and containing 1 to 10 parts by mass of the diimonium dye (B1) with respect to 100 parts by mass of the acrylic polymer (A); The multilayer optical film including the prevention layer; the electromagnetic wave shielding layer; and the transparent resin base material absorbs near infrared rays for a long time even in a humid heat environment. Degradation and haze change of the function and the electromagnetic shielding function have found that extremely small. Based on this knowledge, further studies have been made and the present invention has been completed.

  That is, the present invention relates to the following multilayer optical film.

Item 1. (A-1) acrylic acid alkyl ester and / or methacrylic acid alkyl ester 82-96 parts by mass,
(A-2) 4-8 parts by mass of a carboxyl group-containing monomer, and (a-3) 0-10 parts by mass of other monomers copolymerizable with the above (a-1) and / or (a-2) (provided that The total amount of (a-1) to (a-3) is 100 parts by mass)
A near-infrared absorbing pressure-sensitive adhesive layer comprising an acrylic polymer (A) having a weight average molecular weight of 1,200,000 to 1,500,000 and a diimonium dye (B1), wherein the diimonium dye (B1) Near-infrared absorbing pressure-sensitive adhesive having a solubility in 1 g of ethyl acetate at 25 ° C. of 0.6 mg or more and containing 1 to 10 parts by mass of the diimonium dye (B1) with respect to 100 parts by mass of the acrylic polymer (A) A multilayer optical film comprising: an antireflection layer; an electromagnetic wave shielding layer; and a transparent resin substrate.

  Item 2. In the near-infrared absorbing pressure-sensitive adhesive layer, with respect to 100 parts by mass of the acrylic polymer (A), at least one selected from the group consisting of an isocyanate curing agent, an epoxy curing agent, and a metal chelate curing agent. Item 2. The multilayer optical film according to Item 1, comprising 0.001 to 10 parts by mass of the curing agent (C).

  Item 3. Item 1 or 2 wherein the near-infrared absorbing pressure-sensitive adhesive layer contains 1 to 10 parts by mass of the diimonium dye (B1) and the phthalocyanine dye (B2) with respect to 100 parts by mass of the acrylic polymer (A). A multilayer optical film as described in 1.

  Item 4. Any one of Items 1 to 3, wherein the transparent resin base material has a transparent porous layer on one surface, and a conductive portion (electromagnetic wave shielding layer) having a geometric pattern is provided on the surface of the transparent porous layer. The multilayer optical film described.

  Item 5. The electromagnetic wave shielding layer is formed by screen-printing a conductive paste containing particulate silver oxide, tertiary fatty acid silver and a solvent in a geometric pattern on the transparent porous layer surface of the transparent resin substrate, and then printing the transparent Item 5. The multilayer optical film according to Item 4, which is a layer obtained by heat-treating a conductive resin substrate.

  Item 6. Item 6. The multilayer optical film according to Item 4 or 5, wherein the transparent resin substrate has an antireflection layer on the surface opposite to the electromagnetic wave shielding layer.

  Item 7. Item 7. The multilayer optical film according to any one of Items 1 to 6, wherein the multilayer optical film is laminated in the order of antireflection layer / transparent resin substrate / electromagnetic wave shield layer / near infrared absorbing pressure-sensitive adhesive layer.

  Item 8. Furthermore, the multilayer optical film in any one of claim | item 1 -7 containing a neon absorption layer.

Item 9. The layer structure of the multilayer optical film is
Antireflection layer / transparent resin substrate / electromagnetic wave shielding layer / near infrared absorbing pressure-sensitive adhesive layer / neon absorbing layer,
Antireflection layer / transparent resin substrate / near infrared absorbing pressure-sensitive adhesive layer / electromagnetic wave shield layer / transparent resin substrate / neon absorption layer,
Antireflection layer / Transparent substrate / Near infrared absorbing pressure-sensitive adhesive layer / Transparent resin substrate / Electromagnetic wave shield layer / Neon absorption layer or Antireflection layer / Transparent resin substrate / Neon absorption layer / Transparent resin substrate / Electromagnetic wave shielding layer / near infrared absorbing adhesive layer,
Item 9. The multilayer optical film according to Item 8, which is laminated in the order of.

Item 10. (A-1) acrylic acid alkyl ester and / or methacrylic acid alkyl ester 82-96 parts by mass,
(A-2) 4-8 parts by mass of a carboxyl group-containing monomer, and (a-3) 0-10 parts by mass of other monomers copolymerizable with the above (a-1) and / or (a-2) (provided that The total amount of (a-1) to (a-3) is 100 parts by mass)
A near-infrared and neon-absorbing pressure-sensitive adhesive layer containing an acrylic polymer (A) having a weight average molecular weight of 1,200,000 to 1,500,000, a diimonium dye (B1), and a neon cut dye (D). The solubility of the diimonium dye (B1) in 1 g of ethyl acetate at 25 ° C. is 0.6 mg or more, and the diimonium dye (B1) is added in an amount of 1 to 10 with respect to 100 parts by mass of the acrylic polymer (A). A multilayer optical film comprising a near-infrared and neon-absorbing pressure-sensitive adhesive layer containing 0.001 part by mass or more of neon-cut dye (D); an antireflection layer; an electromagnetic wave shielding layer; and a transparent resin substrate.

  Item 11. At least 1 selected from the group consisting of an isocyanate curing agent, an epoxy curing agent and a metal chelate curing agent with respect to 100 parts by mass of the acrylic polymer (A) in the near infrared and neon absorbing pressure-sensitive adhesive layer. Item 11. The multilayer optical film according to Item 10, comprising 0.001 to 10 parts by mass of the seed curing agent (C).

  Item 12. Item 10 wherein the near infrared and neon absorbing pressure-sensitive adhesive layer contains 1 to 10 parts by mass of the diimonium dye (B1) and the phthalocyanine dye (B2) with respect to 100 parts by mass of the acrylic polymer (A). Or the multilayer optical film of 11.

  Item 13. Any one of Items 10 to 12, wherein the transparent resin base material has a transparent porous layer on one surface, and a conductive portion (electromagnetic wave shielding layer) having a geometric pattern is provided on the surface of the transparent porous layer. The multilayer optical film described.

  Item 14. The electromagnetic wave shielding layer is formed by screen-printing a conductive paste containing particulate silver oxide, tertiary fatty acid silver and a solvent in a geometric pattern on the transparent porous layer surface of the transparent resin substrate, and then printing the transparent Item 14. The multilayer optical film according to Item 13, which is a layer obtained by heat-treating a conductive resin substrate.

  Item 15. Item 15. The multilayer optical film according to any one of Items 10 to 14, wherein the transparent resin base material has an antireflection layer on a surface opposite to the electromagnetic wave shielding layer.

  Item 16. Item 16. The multilayer optical device according to any one of Items 10 to 15, wherein the multilayer optical film is laminated in the order of an antireflection layer / transparent resin substrate / electromagnetic shielding layer / near infrared and neon absorbing pressure-sensitive adhesive layer. the film.

Item 17. The layer structure of the multilayer optical film is an antireflection layer / transparent resin substrate / electromagnetic wave shielding layer / near infrared and neon absorbing pressure-sensitive adhesive layer,
Antireflection layer / transparent resin substrate / infrared and neon absorbing adhesive layer / electromagnetic wave shielding layer / transparent resin substrate, or antireflection layer / transparent resin substrate / infrared and neon absorbing adhesive layer / transparent Resin base material / electromagnetic wave shielding layer,
Item 17. The multilayer optical film according to any one of Items 10 to 16, which is laminated in this order.

  Even if the multilayer optical film of the present invention is kept at high temperature and high humidity for a long time, the near-infrared absorption function and the electromagnetic wave shielding function are hardly deteriorated and the haze does not change. Therefore, it is suitably used as an optical film for PDP.

The multilayer optical film of the present invention comprises at least a near-infrared absorbing pressure-sensitive adhesive layer, an antireflection layer, an electromagnetic wave shielding layer, and a transparent resin substrate, and each layer is laminated. Hereinafter, each layer will be described.
[Near-infrared (NIR) absorbing adhesive layer]
Acrylic polymer (A)
The acrylic polymer (A) contained in the near-infrared absorbing pressure-sensitive adhesive layer comprises (a-1) 82 to 96 parts by mass of acrylic acid alkyl ester and / or methacrylic acid alkyl ester, (a-2) carboxyl group-containing monomer 4 To 8 parts by mass, and (a-3) 0 to 10 parts by mass of other monomers copolymerizable with (a-1) and / or (a-2) above (however, (a-1) to (a- 3) is a polymer having a weight average molecular weight of 1,200,000 to 1,500,000.

  Examples of the acrylic acid alkyl ester in the acrylic acid alkyl ester and / or methacrylic acid alkyl ester represented by the above (a-1) include C1-15 linear, branched or cyclic alkyl esters of acrylic acid. For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, n-pentyl acrylate, isoamyl acrylate, acrylic acid Examples include n-hexyl, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, isobornyl acrylate, cyclohexyl acrylate, and the like.

  Examples of the alkyl methacrylate include C1-15 linear, branched or cyclic alkyl esters of methacrylic acid, such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, and n methacrylate. -Butyl, sec-butyl methacrylate, tert-butyl methacrylate, n-pentyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, methacryl Examples include acid nonyl, decyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate and the like.

  Among them, it is preferable to use an alkyl acrylate ester having 4 to 8 carbon atoms in the alkyl group, since the adhesive strength and flexibility of the resulting pressure-sensitive adhesive are improved. Particularly, n-butyl acrylate, 2-ethylhexyl acrylate are preferable. Is preferred.

  Such (a-1) monomer is contained in 82 to 96 parts by mass, preferably 87 to 95.9 parts by mass, in 100 parts by mass of the total amount of monomers (a-1) to (a-3). .

  Examples of the carboxyl group-containing monomer represented by (a-2) include compounds having an unsaturated bond (double bond) having one or more carboxyl groups in the molecule. For example, acrylic acid, methacrylic acid, β-carboxyethyl acrylate, β-carboxyethyl methacrylate, 5-carboxypentyl acrylate, 5-carboxypentyl methacrylate, monoacryloyloxyethyl succinate, monomethacryloyloxyethyl succinate Examples thereof include esters, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, itaconic acid, crotonic acid, fumaric acid, maleic acid and the like.

  Among them, it is preferable to use an acrylic monomer or a methacrylic monomer having good copolymerizability with (a-1), and it is particularly preferable to use acrylic acid or methacrylic acid having good transparency of the resulting adhesive.

  Such a monomer (a-2) is contained in 4 to 8 parts by mass in 100 parts by mass of the total amount of monomers (a-1) to (a-3).

  By copolymerizing the carboxyl group-containing monomer at the above-mentioned use amount, (B) a near-infrared absorbing dye, which will be described later, is stabilized, deterioration is suppressed, and the near-infrared cut function is reduced or haze is maintained even in a long-time humid heat environment. Can be suppressed.

  Examples of other monomers copolymerizable with (a-1) and / or (a-2) represented by (a-3) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylic 2-hydroxypropyl acid, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2-hydroxy-3-chloroacrylate Hydroxyl-containing monomers such as propyl, 2-hydroxy-3-chloropropyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate; 2-methoxyethyl acrylate, acrylic acid 2 -Ethoxyethyl, acrylic acid 2- Acrylic acid alkoxy esters such as toxipropyl, 3-methoxypropyl acrylate, 2-methoxybutyl acrylate, 4-methoxybutyl acrylate; 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-methoxypropyl methacrylate , Methacrylic acid alkoxyesters such as 3-methoxypropyl methacrylate, 2-methoxybutyl methacrylate, 4-methoxybutyl methacrylate; acrylics such as ethylene glycol acrylate, polyethylene glycol acrylate, propylene glycol acrylate, polypropylene glycol acrylate, etc. Acid alkylene glycol; ethylene glycol methacrylate, polyethylene glycol methacrylate, propylene glycol methacrylate, polypropylene methacrylate Alkylene glycol methacrylates such as recall; aryl acrylates such as benzyl acrylate, phenoxyethyl acrylate, and phenyl acrylate; aryl methacrylates such as benzyl methacrylate, phenoxyethyl methacrylate, and phenyl methacrylate; vinyl acetate, styrene, α -Methylstyrene, allyl acetate, etc. are mentioned.

  Such (a-3) monomer is contained in 0 to 10 parts by mass, preferably 0.1 to 5 parts by mass, in 100 parts by mass of the total amount of monomers (a-1) to (a-3).

  Among these, a hydroxyl group-containing monomer is preferable because it acts as a crosslinking point when an isocyanate curing agent is used, and the adhesive physical properties of the obtained adhesive can be adjusted within a suitable range. In particular, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate are copolymerizable with (a-1) and / or (a-2). It is preferable because it is good and has good reactivity with the curing agent. It is preferable that the usage-amount of this hydroxyl-containing monomer shall be 0.1-2 mass parts in 100 mass parts of total amounts of the monomer of (a-1)-(a-3).

  In addition, it is preferable not to use the monomer which has nitrogen-containing functional groups, such as an amino group and an amide group, as (a-3) monomer, since it has the effect | action which accelerates | stimulates the fading of a diimonium dye (B).

  It is important that the acrylic polymer (A) obtained by copolymerizing the above (a-1) to (a-3) has a weight average molecular weight (Mw) of 1,200,000 to 1,500,000. When the molecular weight is less than 1,200,000, the durability of the diimonium dye (B1) is lowered or precipitated, and a sufficient effect cannot be obtained. Even if the molecular weight is larger than 1,500,000, the durability of the diimonium dye (B1) or the phthalocyanine dye (B2) deteriorates or precipitates, and a sufficient near-infrared cut effect cannot be obtained. In addition, a weight average molecular weight is the value of polystyrene conversion measured by GPC method.

  Such an acrylic polymer (A) can be obtained by a known polymerization method. Among them, a solution polymerization method is preferable because the molecular weight can be easily adjusted and impurities can be reduced. Suitable conditions for adjusting the weight average molecular weight (Mw) in the range of 1,200,000 to 1,500,000 include, for example, ethyl acetate, toluene, methyl ethyl ketone and the like as a solvent, and a polymerization initiator of 0.01 to 100 parts by mass with respect to 100 parts by mass of the monomer. It can be obtained by adding 0.5 parts by mass and reacting at a reaction temperature of 40 to 80 ° C. for 2 to 20 hours in a nitrogen atmosphere while adding a solvent as appropriate.

  The glass transition temperature of the acrylic polymer (A) used in the present invention is 0 ° C. or lower, preferably −20 ° C. or lower. When the glass transition temperature is higher than 0 ° C., the adhesiveness of the obtained pressure-sensitive adhesive to the base material and the flexibility of the pressure-sensitive adhesive layer are lowered, and there is a risk of peeling or floating from the base material.

  The glass transition temperature in the present invention is calculated by the following FOX formula (1) from the glass transition temperature of the homopolymer.

1 / Tg = Wa / Tga + Wb / Tgb + (1)
Tg: Glass transition temperature of copolymer Tga, Tgb,...: Glass transition temperature of homopolymer of monomer a, monomer b,... Wa, Wb. Weight fraction of body b ...
Infrared absorbing dye (B)
The near-infrared absorbing dye (B) contained in the near-infrared absorbing pressure-sensitive adhesive layer may be a dye having a maximum absorption wavelength at 800 nm to 1100 nm, and examples thereof include a diimonium dye (B1) and a phthalocyanine dye (B2). . You may use these both individually or in combination of 2 or more types. Of these, the diimonium dye (B1) is preferable, and the diimonium dye (B1) is essential in the present invention. These dyes should have high solubility in a solvent or the like. Specifically, the solubility in 1 g of ethyl acetate at 25 ° C. under normal pressure (about 0.1 MPa) is 0.6 mg or more, preferably 0.8 to 300 mg, more preferably 1 to 200 mg. Here, ethyl acetate was used as a reference solvent because the solubility parameter value (SP value) of ethyl acetate approximates that of acrylic polymer (A).

  In the present invention, the content of the diimonium dye (B1) is 1 to 10 parts by weight, preferably 1.2 parts per 100 parts by weight of the acrylic polymer (A) having a weight average molecular weight of 1,200,000 to 1,500,000. It is -8 mass parts, More preferably, it is 1.5-6 mass parts.

  By using it in the above-mentioned amount, the diimonium dye is stabilized by the acrylic polymer, and it is possible to suppress a decrease in transmittance and an increase in haze in a wet heat environment.

  Further, in addition to the diimonium dye (B1), a phthalocyanine dye (B2) may be used in combination. In that case, the total amount of the diimonium dye (B1) and the phthalocyanine dye (B2) is 1 to 10 parts by weight, preferably 1.2 to 8 parts by weight with respect to 100 parts by weight of the acrylic polymer (A). Part, more preferably 1.5 to 6 parts by mass. The content ratio (mass ratio) of the diimonium dye (B1) and the phthalocyanine dye (B2) is, for example, 100: 1 to 1: 1, preferably 20: 1 to 5: 4.

  The predetermined amount of the above-mentioned predetermined pigment is used because the pigment is often precipitated in the pressure-sensitive adhesive when the amount of the pigment is small, and the transmittance in the visible region decreases when the amount is large. Because.

  As the diimonium dye (B1), the general formula (I):

The compound which has the partial structure represented by these is mentioned. Specifically, the general formula (Ia):

(In the formula, R ^{1 to} R ⁸ are independently a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aralkyl group which may have a substituent, and a substituent. An aryl group that may have a group, a hydroxy group, an aryloxy group that may have a substituent, an alkoxy group that may have a substituent, or an acyloxy group, and X ⁻ represents an anion. ).

  Examples of the alkyl group of the alkyl group which may have a substituent include a linear, branched, or cyclic alkyl group having 1 to 20, preferably 4 to 8, more preferably 4 to 6 carbon atoms. It is done. When the carbon number is 4 or more, the solubility in an organic solvent is good, and when the carbon number is 8 or less, the heat resistance is good. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a t-butyl group, and a 3-methyl-butyl group. N-pentyl group, iso-pentyl group, neo-pentyl group, cyclopentyl group, 1,2-dimethylpropyl group, n-hexyl group, cyclohexyl group, 1,3-dimethylbutyl group, 1-iso-propylpropyl group 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 2-methyl-1-iso-propylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2- Ethylhexyl group, 3-methyl 1-iso-propylbutyl group, 2-methyl-1-iso-propyl group, 1-t-butyl-2-methylpropyl group, n Nonyl, 3,5,5-trimethyl hexyl group.

  The alkyl group may have a substituent such as a hydroxyl group, a halogen atom, an amino group, an alkylamino group, an alkoxycarbonyl group, an acyl group, a sulfo group, or a carboxyl group.

Examples of the alkenyl group of the alkenyl group that may have a substituent include linear, branched, or cyclic alkenyl groups having 2 to 20, preferably 4 to 8, more preferably 4 to 6 carbon atoms. It is done. As the alkenyl group, for example, vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, or octenyl group.

  The alkenyl group may have a substituent such as a hydroxyl group, a halogen atom, an amino group, an alkylamino group, an alkoxycarbonyl group, an acyl group, a sulfo group, or a carboxyl group.

  Examples of the aralkyl group of the aralkyl group which may have a substituent include a benzyl group, a p-chlorobenzyl group, a p-methylbenzyl group, a 2-phenylethyl group, a 2-phenylpropyl group, and a 3-phenylpropyl group. , A naphthylmethyl group, or a 2-naphthylethyl group.

  The aralkyl group may have a substituent such as a hydroxyl group, a halogen atom, an amino group, an alkylamino group, an alkoxycarbonyl group, an acyl group, a sulfo group, or a carboxyl group on the aromatic ring.

  Examples of the aryl group of the aryl group which may have a substituent include a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group, a naphthyl group, and a biphenyl group.

  The aryl group may have a substituent such as a hydroxyl group, a halogen atom, an amino group, an alkylamino group, an alkoxycarbonyl group, an acyl group, a sulfo group, or a carboxyl group.

  Examples of the aryloxy group of the aryloxy group which may have a substituent include a monocyclic or bicyclic aryloxy group, such as a phenyloxy group, a naphthyloxy group, and a biphenyloxy group.

  The aryloxy group may have a substituent such as a hydroxyl group, a halogen atom, an amino group, an alkylamino group, an alkoxycarbonyl group, an acyl group, a sulfo group, or a carboxyl group.

  The alkoxy group of the alkoxy group which may have a substituent includes, for example, a linear, branched, or cyclic alkoxy group having 1 to 20 carbon atoms, preferably 4 to 8 carbon atoms, more preferably 4 to 6 carbon atoms. It is done. When the carbon number is 4 or more, the solubility in an organic solvent is good, and when the carbon number is 8 or less, the heat resistance is good. Examples of the alkoxy group include methoxy group, ethoxy group, n-propyloxy group, iso-propyloxy group, n-butyloxy group, iso-butyloxy group, sec-butyloxy group, t-butyloxy group, 3-methyl- Butyloxy group, n-pentyloxy group, iso-pentyloxy group, neo-pentyloxy group, cyclopentyloxy group, 1,2-dimethylpropyloxy group, n-hexyloxy group, cyclohexyloxy group, 1,3-dimethylbutyl Oxy group, 1-iso-propylpropyloxy group, 1,2-dimethylbutyloxy group, n-heptyloxy group, 1,4-dimethylpentyloxy group, 2-methyl-1-iso-propylpropyloxy group, 1 -Ethyl-3-methylbutyloxy group, n-octyloxy group, -Ethylhexyloxy group, 3-methyl 1-iso-propylbutyloxy group, 2-methyl-1-iso-propyloxy group, 1-t-butyl-2-methylpropyloxy group, n-nonyloxy group, 3,5 , 5-trimethylhexyloxy group and the like.

  The alkoxy group may have a substituent such as a hydroxyl group, a halogen atom, an amino group, an alkylamino group, an alkoxycarbonyl group, an acyl group, a sulfo group, or a carboxyl group.

  Examples of the acyloxy group include C2-10 alkanoyloxy groups such as acetyloxy group, propionyloxy group, and butyryloxy group; and aryloyloxy groups such as benzoyloxy group and naphthoyloxy group.

X ^- is the anion represented by the example, chloride, bromide, iodide, perchlorate ion, periodate ion, nitrate ion, benzenesulfonate ion, P- toluenesulfonic acid ion, methyl sulfate ion, Ethyl sulfate ion, propyl sulfate ion, tetrafluoroborate ion, tetraphenylborate ion, hexafluorate ion, benzenesulfinate ion, acetate ion, trifluoroacetate ion, propionate acetate ion, benzoate ion, oxalate ion Succinate ion, malonate ion, oleate ion, stearate ion, citrate ion, monohydrogen diphosphate ion, dihydrogen monophosphate ion, pentachlorostannate ion, chlorosulfonate ion, fluorosulfonate ion , Trifluoromethanesulfo Acid ions, hexafluoroarsenate ions, hexafluoroantimonate ions, molybdate ions, tungstate ions, titanate ions, zirconate ions, bis (trifluoromethanesulfonyl) imido ions, naphthyl sulfonate ions, etc. .

  Among these anions, perchlorate ion, iodine ion, tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroantimonate ion, trifluoromethanesulfonate ion, bis (trifluoromethanesulfonyl) imido ion, etc. In particular, hexafluoroantimonate ion and bis (trifluoromethanesulfonyl) imido ion are preferable because they are most excellent in thermal stability.

The diimonium dye preferably has a molar extinction coefficient ε around 1000 nm of about 0.8 × 10 ^{4 to} 1.0 × 10 ⁶ . In addition, it is preferable to use a diimonium dye having a purity of 98% or higher, or a diimonium dye having a melting point of 180 ° C. or higher.

  As the phthalocyanine dye (B2), the general formula (II):

And a compound having a maximum absorption wavelength at 800 to 1000 nm. For example, phthalocyanine dyes described in JP-A No. 2001-106658, fluorine-containing phthalocyanine dyes described in JP-A No. 2001-133623, fluorine-containing phthalocyanine dyes described in JP-A No. 2002-822193 Etc. Specifically, EEX COLOR IR-10, eEX COLOR IR-10A, eEX COLOR IR-14, eEX COLOR IR-12, eEX COLOR IR-HA-1, etc. manufactured by Nippon Shokubai Co., Ltd. are used. be able to. Particularly preferred are fluorine-containing phthalocyanine compounds, such as e-color IR-12.

  The central metal M of the phthalocyanine dye is not particularly limited, and metals such as metal-free (hydrogen), iron, copper, zinc, vanadium, titanium, indium and tin, chlorides, bromides, iodines of the metals. Metal halides such as fluoride, metal oxides such as vanadium oxide, titanyl oxide and copper oxide, organic acid metals such as acetate, and complex compounds such as acetylacetonate and metal carbonyls such as carbonyl iron. Of these, metals, metal oxides and metal halides are preferred. More preferred is vanadium oxide.

As the phthalocyanine dye, phthalocyanine [CuPc (2,5-C1 ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ ) when Pc is a phthalocyanine nucleus and Ph is a phenyl group. NH) ₄ ] (λmax 807 nm), Pc (2,5-Cl ₂ PhO) ₈ (2,6-Br ₂ -4-CH ₃ PhO) ₄ {Ph (CH ₃ ) CHNH} ₃ F (λmax 835 nm), VOPc ( 2,5-Cl ₂ PhO) ₈ (2,6-Br ₂ -4-CH ₃ PhO) ₄ {PhCH ₂ NH} ₃ F (λmax 840 nm), VOPc (2,5-Cl ₂ PhO) ₈ (2,6 -(CH ₃ ) ₂ PhO) ₄ {Ph (CH ₃ ) CHNH} ₃ F (λmax 834 nm), VOPc (2,6-Cl ₂ PhO) ₈ (2,6- (CH ₃ ) ₂ PhO) ₄ {Ph (CH ₃ ) CHNH} ₃ F (λmax 835 nm), VOPc (4-CNPhO) ₈ (2,6-Br ₂ -4-CH ₃ PhO) ₄ {Ph (CH ₃ ) CHNH} ₃ F (λmax836 nm), VOPc (4-CNPhO) ₈ (2,6- (CH ₃ ) ₂ PhO) ₄ {Ph (CH ₃ ) CHNH} ₃ F (λmax834 nm), and the like. In addition, for those having the maximum absorption wavelength at 850 to 980 nm, [VOPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ ] (λmax 870 nm) , [VOPc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ ] (λmax 912 nm), VOPc (2,5-Cl ₂ PhO) ₄ (2,6- (CH ₃ ) ₂ PhO) ₄ {(C ₂ H ₅ ) ₂ NCH ₂ CH ₂ NH} ₄ (λmax 893 nm). In the present invention, when two kinds of phthalocyanines having a maximum absorption wavelength of more than 800 nm and less than 850 nm and 850 to 980 nm are used as the phthalocyanine (I), the visible light transmittance of the obtained near-infrared absorption filter is increased. Also, it is advantageous in that near infrared light can be cut efficiently.

Neon cut dye (D)
The near-infrared absorbing pressure-sensitive adhesive layer may contain a neon cut pigment (D). The plasma display emits so-called neon orange light centered around 600 nm, and has a drawback that a bright red color cannot be obtained because the orange color is mixed with the red color. By including a neon cut pigment, the above problem can be solved.

  Neon cut dyes are dyes having maximum absorption in the wavelength range of 550 nm to 620 nm, and specifically include cyanine-based, squarylium-based, indole compound-based, azomethine-based, xanthene-based, oxonol-based, azo-based, phthalocyanine. Quinone, azurenium, pyrylium, croconium, dithiol metal complex, pyromethene, azaporphyrin, and the like. These dyes can be used alone or in admixture of two or more. In the present invention, it is preferable to use cyanine dyes, squarylium dyes, and indole compound dyes.

  The neon-cut dye content is adjusted so that the obtained wavelength selective absorption filter has sharp absorption in the wavelength region of 550 nm to 620 nm and the transmittance at the maximum absorption wavelength is 40% or less. It is preferable to do this. It is 0.001 mass part or more with respect to 100 mass parts of said acrylic polymers (A), Preferably it is 0.005-1 mass part, More preferably, it is 0.01-0.5 mass part.

Curing agent (C)
The near-infrared absorbing pressure-sensitive adhesive layer may further contain a curing agent (C). Examples of the curing agent (C) include isocyanate curing agents, epoxy curing agents, metal chelate curing agents, and the like. Of these, isocyanate curing agents are preferable, and it is particularly preferable to use an isocyanate curing agent and a metal chelate curing agent in combination.

  Content of a hardening | curing agent (C) is 0.001-10 mass parts with respect to 100 mass parts of said acrylic polymers (A), Preferably it is 0.01-5 mass parts. In particular, when an isocyanate curing agent and a metal chelate curing agent are used in combination, the content ratio (mass ratio) of the isocyanate curing agent and the metal chelate curing agent is about 100: 1 to 1: 1, preferably 50: 1. It may be about 2: 1.

  Examples of isocyanate curing agents include tolylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethyl. Polyisocyanate compounds having two or more isocyanate groups in the molecule such as xylylene diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate; addition of them with polyhydric alcohols such as trimethylolpropane and pentaerythritol Reacted compounds; these polyisocyanates Compound burette type compounds and isocyanurate compounds; two of these polyisocyanate compounds in a urethane prepolymer type molecule that has undergone addition reaction with known polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols, etc. The compound etc. which have the above isocyanate groups are mentioned.

  Of these, tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and compounds obtained by addition reaction of tetramethylene diisocyanate and trimethylolpropane are preferably used because of their good reactivity.

  When the acrylic polymer has a hydroxyl group, it is preferable to combine an isocyanate curing agent as a crosslinking agent.

  Such an isocyanate curing agent is used in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the acrylic polymer.

  Examples of the epoxy compound 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 tri Molecules such as glycidyl ether, diglycidyl aniline, diamine glycidyl amine, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N′-diamine glycidylaminomethyl) cyclohexane Examples thereof include compounds having two or more epoxy groups.

  Among these, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine is preferably used because of its good reactivity.

  Such an epoxy curing agent is used in an amount of 0.001 to 2 parts by mass, preferably 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the acrylic polymer.

  Examples of the metal chelate curing agent include compounds in which acetylacetone, ethyl acetoacetate, etc. are coordinated to a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium, etc. Is mentioned.

  Among them, a compound in which acetylacetone and ethyl acetoacetate are arranged on aluminum is preferably used because it has an action of suppressing deterioration of the diimonium dye.

  Such a metal chelate curing agent is used in an amount of 0.001 to 2 parts by mass, preferably 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the acrylic polymer.

  As the curing agent (C), it is preferable to use one or more of the above-mentioned compounds. Among them, using an isocyanate curing agent and a metal chelate curing agent in combination shortens the curing time, and the adhesive layer is being cured. It is preferable because preferable adhesive properties can be obtained while suppressing deterioration of the diimonium compound.

  The near-infrared absorbing pressure-sensitive adhesive layer further includes a color correction dye having a maximum absorption wavelength in the range of 300 to 800 nm, a leveling agent, an antistatic agent, a thermal stabilizer, and an antioxidant within a range not impairing the effects of the present invention. An agent, a dispersant, a flame retardant, a lubricant, a plasticizer, or an ultraviolet absorber may be contained.

  The near-infrared absorbing pressure-sensitive adhesive composition obtained by mixing and dispersing the acrylic polymer (A), the near-infrared absorbing dye (B) containing the diimonium-based compound (B1), and, if necessary, the curing agent (C) by a known method. Get things. The mixing and dispersing method is not particularly limited, but it is preferable to use a disperser such as a dissolver, a high speed mixer, a homomixer, a sand mill, an attritor, a homogenizer, or a ball mill.

  The near-infrared-absorbing pressure-sensitive adhesive layer is prepared by, for example, applying a liquid (hereinafter referred to as a coating liquid) in which a near-infrared-absorbing pressure-sensitive adhesive composition is dissolved or dispersed in an organic solvent on a releasable substrate or support film. It can be formed by coating and drying.

  Examples of the organic solvent include aromatics such as toluene and xylene, amides such as N-methyl-2-pyrrolidone, dimethylformamide, and dimethylacetamide, ketones such as methyl ethyl ketone, methyl isobutyl ketone, and acetone, methanol, ethanol, i Examples include alcohols such as propyl alcohol, hydrocarbons such as hexane, tetrahydrofuran, and the like.

  A near-infrared absorptive adhesive layer is formed by coating the near-infrared absorptive adhesive composition on a substrate. Examples of the method include known coating methods such as a doctor blade, a bar coater, a gravure coater, a comma coater, a reverse coater, and a spray method.

  Examples of the substrate include a film-like or sheet-like plastic film and a glass plate. A plastic film is preferable in terms of transparency, cost, and ease of handling. Specific examples include polyesters, acrylics, triacetylcelluloses, polyethylenes, polypropylenes, polyolefins, and polycycloolefins, with polyester films being preferred.

  The coating liquid is applied onto a substrate having a release property. Although it does not specifically limit about the thickness of an adhesive layer, 5 micrometers-50 micrometers, Preferably they are 10 micrometers-40 micrometers, More preferably, 20 micrometers-30 micrometers are good. Furthermore, the base material which gave mold release property is bonded together in the state which a bubble does not generate | occur | produce.

Thus, after providing a near-infrared absorbing pressure-sensitive adhesive layer on a releasable substrate or support film, a release film is further stuck on the near-infrared absorbing pressure-sensitive adhesive layer. From the viewpoint of sex. As the release film, the same as the above-described peelable substrate can be used.
[Electromagnetic wave shielding material]
The electromagnetic shielding material is not particularly limited as long as it shields electromagnetic waves emitted from the plasma display, and the production method thereof is not particularly limited. For example, the electromagnetic wave shielding material is a transparent conductive film, and a transparent resin substrate (plastic film) obtained by depositing a thin film of metal, metal oxide, metal salt or the like is used. The lower the surface resistance of the conductive film, the higher the electromagnetic wave absorption ability, but conversely the visible light transmittance decreases as the vapor deposition layer becomes thicker. In addition, there is a screen-printed conductive paint printed in mesh, or a transparent resin base material (plastic film) that is coated with a conductive metal and etched to form a conductive metal mesh. Can be used.

  Furthermore, you may form an antireflection layer in the opposite surface to the surface in which the electroconductive thin film thru | or electroconductive mesh-like thing of a transparent resin base material is formed.

  The antireflection layer prevents surface reflection, increases visible light transmittance, and at the same time prevents glare, and a known layer can be used. As the formation method, any processing method can be selected, and there is no particular limitation. A method of reducing luminous reflectance by irregularly reflecting external light, for example, forming an antireflection film that causes diffused reflection of light by coating and coating fine particles of silicon dioxide, acrylic, melamine, etc. on one side of a plastic film A method, or a method of forming a cured film on one side of a plastic film such as PET, and forming an antireflection layer thereon by vapor deposition of a magnesium fluoride layer, or forming a thin film refractive index layer on one side or both sides of a plastic film A general method is a method of reducing the reflectance by the interference of the light reflected from the surface reflected light of the thin film and the refractive reflected light at the interface.

  In the optical film of the present invention, it is particularly preferable to employ the following electromagnetic shielding material. This electromagnetic wave shielding material is provided on the surface of the transparent porous layer of a transparent resin substrate comprising a transparent porous layer containing at least one selected from the group consisting of oxide ceramics, non-oxide ceramics and metals as a main component. In addition, a conductive paste containing particulate silver oxide, tertiary fatty acid silver and a solvent is screen-printed on a geometric pattern, and the substrate after printing is heated (baked) to form a geometric pattern on the surface of the transparent porous layer. A conductive part is formed and a manufacturing method is performed.

Transparent resin base material The base resin of the transparent resin base material is not particularly limited as long as it has high heat resistance, is transparent, and can form the transparent porous layer on the base material.

  Specifically, polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polycarbonate resins; poly (meth) acrylate resins; silicone resins; cyclic polyolefin resins; polyarylate resins; Is exemplified. Of the above, polyester resins, particularly PET or PEN, are preferably employed from the viewpoint of transparency, cost, durability, heat resistance, and the like.

  Here, the transparency in the transparent resin base material is not particularly limited as long as it is transparent to the extent that it can be used for applications of display units such as PDP and CRT. Usually, the total light transmittance measured by JIS K7105 is about 85 to 90%, and the haze value measured by JIS K7105 is about 0.1 to 3%.

  As the form of the transparent resin base material, a form that can be used for a display unit such as PDP or CRT, that is, a film form, a sheet form, a flat form or the like is adopted. Such a form can be produced from the above base resin by a known method.

  The transparent resin base material has a transparent porous layer containing at least one selected from the group consisting of oxide ceramics, non-oxide ceramics and metals as a main component.

  Here, as oxide ceramics, simple oxides such as titania, alumina, magnesia, beryllia, zirconia, silica, etc., silicates such as silica, holsterite, steatite, wollastonite, zircon, mullite, cordierite, spodemen, etc. And double oxides such as aluminum titanate, spinel, apatite, barium titanate, PZT, PLZT, ferrite and lithium niobate.

  Non-oxide ceramics include nitrides such as silicon nitride, sialon, aluminum nitride, boron nitride and titanium nitride, carbides such as silicon carbide, boron carbide, titanium carbide and tungsten carbide, amorphous carbon, graphite, diamond, and crystal sapphire. For example, carbon such as Other examples include borides, sulfides and silicides.

  Examples of the metal include gold, silver, iron, copper, nickel and the like.

  At least one of these may be used as a raw material, and silica, titania, and alumina are more preferable, and other components and blends are not particularly limited.

  The method for forming the transparent porous layer on the transparent resin substrate may be either a wet process or a dry process, and is not particularly limited, but is preferably a wet process from the viewpoint of productivity and cost. In the wet process, the substrate may be coated (applied) by a known method. Examples of the coating method include gravure coating, offset coating, comma coating, die coating, slit coating, spray coating, plating method, sol-gel method, LB film method and the like, and sol-gel method is particularly preferable. Examples of starting materials for the sol-gel method include tetraethoxysilane, methyltriethoxysilane, and tetrachlorosilane for silica, and aluminum tri-sec-butoxide, aluminum (III) 2,4-pentanedionate for alumina, and the like. The above starting materials cause the sol-gel reaction to proceed in the presence of a catalyst and water, but these hydrolysates (reaction intermediates) in which the sol-gel reaction has already progressed may be used as the starting materials. Moreover, you may add suitably other components, such as resin and surfactant, as needed. Examples of the dry process include CVD, vapor deposition, sputtering, and ion plating.

  The thickness of the transparent porous layer on the transparent resin substrate is about 0.05 to 20 μm, particularly about 0.1 to 5 μm.

  The transparent porous layer is composed of an aggregate (aggregate) of fine particles mainly composed of at least one selected from the group consisting of oxide ceramics, non-oxide ceramics, and metals. have. The average particle size of the transparent porous layer is about 10 to 100 nm, and the pore size is about 10 to 100 nm. In this invention, since it has such a transparent porous layer, matching with the electrically conductive paste mentioned later is excellent, and a desired pattern formation is attained.

  The form of the transparent resin substrate having the transparent porous layer is a film shape, a sheet shape, a flat plate shape, or the like. In the case of a film or sheet, the thickness of the transparent resin substrate having a transparent porous layer is usually about 25 to 200 μm, preferably about 40 to 188 μm. In particular, when used as an electromagnetic shielding material for the entire surface of a display such as a PDP, about 50 to 125 μm is preferable. Moreover, in the case of plate shape, the thickness should just be about 0.5-5 mm normally, Preferably it is about 1-3 mm.

  The transparency of the transparent resin substrate having a transparent porous layer is generally about 85 to 90% of total light transmittance measured by JIS K7105 and about 0.1 to 3% of haze value measured by JIS K7105. It is.

  Moreover, you may provide a hard-coat layer in a transparent resin base material on the opposite surface to said transparent porous layer.

  As the hard coat layer, a general material may be used as long as the transparency is not impaired, and there is no particular limitation. Of these, ultraviolet curable acrylate resins are preferred. The main component is not particularly limited as long as it is an ultraviolet curable acrylate having two or more functional groups such as polyester acrylate, urethane acrylate, and epoxy acrylate. 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol acrylate, 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, neopentyl glycol PO modified diacrylate, EO modified bisphenol A di Bifunctional acrylate such as acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, trimethylolpropane EO modified triacrylate, PO modified glycerin triacrylate, trishydroxyethyl isocyanate Use of polyfunctional acrylates such as nurate triacrylate is preferred.

  In addition, a photopolymerization initiator is usually added to the ultraviolet curable acrylate resin. As a photopolymerization initiator, 1-hydroxycyclohexyl phenyl ketone (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.), 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and the like are added. Thus, a sufficient cured film can be obtained. Others, benzoin, benzoin derivatives, benzophenone, benzophenone derivatives, thioxanthone, thioxanthone, thioxanthone derivatives, benzyldimethyl ketal, α-aminoalkylphenone, monoacylphosphine oxide, bisacylphosphine oxide, alkenylphenylglyoxylate, diethoxyacetophenone, Photopolymerization initiators such as titanocene compounds can also be used.

  The blending ratio of these photopolymerization initiators is preferably 1 to 10 parts by weight with respect to 100 parts by weight of the ultraviolet curable acrylate resin. When the amount is less than 1 part by weight, the polymerization does not start sufficiently.

  The ultraviolet curable acrylate resin may contain a third component (UV absorber, filler, etc.) as long as the transparency is not impaired, and there is no limitation on the yield.

  The method for forming the hard coat layer on the transparent resin substrate may be a general coating method and is not particularly limited.

  By providing a hard coat layer on the transparent resin base material, whitening and yellowing due to oligomer precipitation from the base resin can be suppressed during firing, which will be described later, whereby the electromagnetic shielding material of the present invention is highly transparent. Sex is secured. In addition, it is possible to prevent scratches during the manufacturing process of the electromagnetic shielding material.

Conductive paste The conductive paste used in the present invention contains particulate silver oxide, tertiary fatty acid silver and a solvent.

  The average particle size of the particulate silver oxide is 2 μm or less, and when silver oxide having a particle size larger than this is used, the average particle size is set in the manufacturing process (kneading step, synthesis step, etc.) of the conductive paste. What is necessary is just to be 2 micrometers or less. The average particle size is more preferably 200 to 500 nm. When a particulate silver compound having an average particle size of 2 μm or less is used, the mesh of the screen plate is easily passed, and the fine lines printed on the transparent porous layer are prevented from being broken or blurred, and at a lower temperature, the silver oxide Reduction and thermal decomposition of tertiary fatty acid silver are preferable.

  The tertiary fatty acid silver salt is a silver salt of a tertiary fatty acid having a total carbon number of 5 to 30, preferably 10 to 30, and can be dissolved or homogeneously dispersed in a dispersion medium used during paste preparation. This tertiary fatty acid silver salt plays the role of a lubricant. When kneading silver oxide and tertiary fatty acid silver salt into a paste, the silver oxide is pulverized to promote micronization and silver oxide. It exists around the grains to suppress reaggregation of silver oxide grains and improve dispersibility. For this reason, it can be made into a paste without adding a binder. Further, this tertiary fatty acid silver salt has a function of precipitating silver during heating and fusing together silver particles produced by reduction from silver oxide.

  Specific examples of such tertiary fatty acid silver salts include silver pivalate, silver neoheptanoate, silver neononanoate, and silver neodecanoate. The production of the tertiary fatty acid silver salt is carried out, for example, by neutralizing the tertiary fatty acid with an alkali compound in water and reacting this with silver nitrate.

  The blending ratio of the particulate silver oxide and the tertiary fatty acid silver salt in the conductive paste is such that the weight ratio (A / B) is when the weight of the silver oxide is A and the weight of the tertiary fatty acid silver salt is B. It is preferable that it is 1 / 4-3 / 1.

  In the conductive paste, a solvent is contained in addition to silver oxide and tertiary fatty acid silver salt. The solvent is not particularly limited as long as it does not react with silver oxide and the tertiary fatty acid silver salt and can disperse them satisfactorily. For example, aromatic hydrocarbons such as toluene, ether esters of ethylene glycol such as triethylene glycol monobutyl ether, ether esters of propylene glycol such as tripropylene glycol normal butyl ether, and organic solvents such as terpineol are used. The usage-amount of a solvent should just be about 1-100 weight part with respect to 100 weight part of particulate silver oxide.

  Further, if necessary, a dispersing agent can be added to disperse the particulate silver oxide well, thereby preventing secondary aggregation of the particulate silver oxide. As the dispersant, a fiber-based polymer such as hydroxypropylcellulose, a water-soluble polymer such as polyvinylpyrrolidone, polyvinyl alcohol, or the like is used. The amount used may be 0 to 20 parts by weight with respect to 100 parts by weight of the particulate silver oxide.

  The conductive paste is produced, for example, by a method in which particulate silver oxide, tertiary fatty acid silver salt and a solvent are mixed and then kneaded with a roll mill to form a paste. Since this conductive paste has particulate silver oxide having an average particle diameter of 2 μm or less, it is easy to form metallic silver particles even under relatively low temperature heating conditions and fuse them together to continuously apply metallic silver. It becomes a film or a lump.

  In addition, the conductive paste is prepared to have a viscosity and thixotropy suitable for screen printing and used for screen printing. The viscosity and thixotropic properties can be appropriately selected according to the particle size of the particulate silver oxide, the type of tertiary fatty acid silver salt, the type of solvent, and the like. For example, the viscosity of the conductive paste may be about 10 to 10000 dPa · s, and the thixotropy index may be appropriately selected within the range of about 0.1 to 0.9.

  Examples of such a conductive paste include “Doutite XA-9080” and “Doutite XA-9083” manufactured by Fujikura Kasei Co., Ltd.

Production Method of Electromagnetic Shielding Material An electromagnetic shielding material is produced by screen-printing the above conductive paste on the transparent porous layer surface of a transparent resin base material, followed by heat treatment.

  By pattern-printing a specific conductive paste on a predetermined transparent porous layer, a pattern conductive portion with almost no disconnection or bleeding of fine lines is formed.

  The method of screen printing is not particularly limited, and can be performed using a known method. The screen plate used for printing has a continuous geometric pattern such as a lattice shape or a mesh shape, which can effectively shield electromagnetic waves and form a conductive portion to a degree that can ensure sufficient transparency. Things are used. For example, a screen plate in which a grid pattern having a line width of about 10 to 30 μm and a pattern pitch of about 200 to 400 μm is provided on a 360 to 700 mesh stainless steel basket woven with a stainless steel wire having a diameter of 11 to 23 μm.

  In screen printing, since a conductive paste containing fine particulate silver oxide is used, there is almost no unevenness in the pattern. In addition, since the matching between the conductive paste and the transparent porous layer is good, disconnection and bleeding hardly occur in the fine lines of the pattern formed on the transparent porous layer.

  In general, the line width of a screen-printed pattern tends to be a little thicker in principle than the line width of a screen plate, but there is almost no deviation in line spacing or pattern distortion, and almost the same as the screen plate pattern. A faithful pattern will be reproduced on the transparent porous layer. In the case where the tendency to become thicker is disliked, the slit width of the screen plate may be set smaller than the desired line width formed in the transparent porous layer, and those skilled in the art can easily perform such setting.

  Subsequently, the screen-printed electromagnetic shielding material is heat-treated (baked) at a low temperature of about 150 to 200 ° C. (particularly about 160 to 180 ° C.) to form a conductive portion having a lattice pattern in the transparent porous layer. To do. As described above, since a specific conductive paste is used, the metallic silver particles are easily fused even under relatively low temperature heating conditions, and a continuous metallic silver coating film can be formed. In the heat treatment, for example, an external heating method (steam or electric heating hot air, infrared heater, heat roll, etc.), an internal heating method (induction heating, high-frequency heating, resistance heating, etc.), etc. are adopted. The heating time is usually about 5 minutes to 120 minutes, preferably about 10 minutes to 40 minutes.

  Note that the heat treatment (firing) may be performed in multiple stages. For example, after the heat treatment at 50 to 60 ° C. for about 10 to 20 minutes as the first step, the heat treatment at 160 to 180 ° C. for about 10 minutes to 40 minutes can be continued as the second step. By using multiple stages, bleeding can be further suppressed by volatilizing the solvent first.

  As described above, when the conductive paste is used, a silver coating film can be formed at a low temperature and in a short time, and therefore, adverse effects on the transparent resin substrate due to heat can be avoided. That is, it can suppress that a base material whitens by the oligomer precipitation from a transparent resin base material by heat, or that a base material turns yellow by heat.

  Moreover, when it has a hard-coat layer in the opposite surface to the transparent porous layer of a transparent resin base material, whitening and yellowing of base resin are further suppressed at the time of baking.

  As described above, the electromagnetic wave shielding material (layer) is manufactured. The electromagnetic wave shielding material of the present invention has a high aperture ratio, for example, 75% or more, particularly about 80 to 95%. Therefore, high transparency is achieved. In the present specification, the aperture ratio means (area B / area A) × 100 (%) in one grid pattern of the electromagnetic wave shielding material shown in FIG.

  Moreover, the line width (W) of the grid-like or mesh-like pattern of the conductive part is usually about 10 to 30 μm, preferably about 15 to 20 μm. A geometric pattern having a line width of less than about 10 μm tends to be difficult to produce, and if it exceeds 30 μm, the pattern tends to be noticeable, which is not preferable.

  It should be noted that the interval (pitch) (P) between the lines of the grid-like or mesh-like pattern to be printed can be appropriately selected within a range that satisfies the above aperture ratio and line width. Usually, it may be in the range of about 200 to 400 μm.

  The thickness of the fine line (maximum height of the fine line in the direction perpendicular to the transparent porous layer surface) may vary depending on the line width or the like, but is usually about 1 μm or more, and particularly about 1 to 30 μm.

  Moreover, the cross section of the thin line on the transparent porous layer formed by screen printing is substantially semicircular. Most of the fine lines of patterns that have been reported so far by lithography, plating, etc., have a rectangular cross section. For this reason, when a pressure-sensitive adhesive layer or the like is laminated thereon, bubbles are likely to remain, which adversely affects the transparency. On the other hand, since the cross section of the thin wire of the present invention is substantially semicircular, the adhesiveness is high when the pressure-sensitive adhesive layer or the like is bonded, and bubbles do not easily remain. Therefore, it has the merit that an electromagnetic wave shielding material excellent in transparency can be obtained.

  The electromagnetic shielding material has a high electromagnetic shielding effect and is excellent in transparency and transparency. In addition, there is a feature that resistance is low because there is almost no disconnection of the thin wire of the conductive portion. The surface resistance value of the electromagnetic wave shielding material of the present invention is 5Ω / □ or less, preferably 3Ω / □ or less, more preferably 2Ω / □ or less. When the surface resistance value is too large, it is not preferable in terms of shielding characteristics.

Here, the surface resistance value of the shield material having the conductive pattern can be designed by arbitrarily setting the line width and pitch of the pattern from the following equation.
R = Rs × (P / W)
Rs = ρv / t
R: Surface resistance value of shield material having conductive pattern (Ω / □)
Rs: Surface resistance value of conductive paste (Ω · cm)
ρv: Volume specific resistance of the conductive paste t: Film thickness of the conductive paste P: Spacing (pitch) of the lattice or mesh pattern
W: Line width of lattice-like or mesh-like pattern The total light transmittance (JIS K7105) of the electromagnetic wave shielding material of the present invention can achieve a high value of about 72 to 91%. The haze value (JIS K7105) is as low as about 0.5 to 6%.

  Furthermore, the conductive pattern formed on the transparent porous layer is substantially free of additives such as a binder, a curing agent, and a catalyst, and substantially consists of silver particles, and the silver particles Becomes a lump of high purity silver fused and bonded directly. For this reason, the electromagnetic wave shielding material has a lower and stable resistance value.

  Moreover, as for the electromagnetic wave shielding material, the protective film may be laminated | stacked on the electroconductive part formed on the transparent porous layer. As the protective film, commonly used known resins are used. These resins are laminated by a known method such as dry lamination or wet lamination.

  The electromagnetic shielding material may be further laminated with a functional film or the like. As functional films, anti-reflection film provided with anti-reflection layer to prevent light reflection on the surface of the film, colored film colored by coloring or additives, and preventing contaminants such as fingerprints from adhering to the surface Examples include antifouling films.

The electromagnetic shielding material has a high electromagnetic shielding effect and is excellent in transparency and transparency. Moreover, in the manufacturing method using the screen printing method of the present invention, a homogeneous conductive geometric pattern can be easily provided on a substrate with high accuracy.
[Neon (NE) absorbent adhesive layer]
When the above-mentioned near infrared absorbing pressure-sensitive adhesive layer does not contain a neon absorbing dye, the multilayer optical film of the present invention can be independently provided with a neon (NE) absorbing pressure-sensitive adhesive layer.

  As for a neon (NE) absorptive adhesive layer, what contains a neon cut pigment | dye (D) in the acrylic polymer (A) described above is mentioned. As the neon cut pigment (D), those described above can be used.

  Specific examples include ADEKA Corporation, Adeka Arcles TY-100, Adeka Arcles TY-102, Adeka Arcles TY-171, and Adeka Arcles TY-171 is particularly preferable. Eosin Y (600 nm), Phloxine B (540 nm) [Red 104], Rose Bengal (550 nm) [Red 105] may be used.

The neon-cut dye content is adjusted so that the obtained wavelength selective absorption filter has sharp absorption in the wavelength region of 550 nm to 620 nm and the transmittance at the maximum absorption wavelength is 30% or less. It is preferable to do this. It is 0.001 mass part or more with respect to 100 mass parts of said acrylic polymers (A), Preferably it is 0.005-1 mass part, More preferably, it is 0.01-0.5 mass part.
[Multilayer optical film]
The multilayer optical film of the present invention has a functional layer such as a near-infrared absorbing pressure-sensitive adhesive layer, an antireflection layer, an electromagnetic wave shielding layer, and a transparent resin substrate. In addition to the above-described typical functional layers, for example, an ultraviolet absorbing layer for preventing deterioration of a dye due to ultraviolet rays and improving light resistance, a hard coat layer for imparting an abrasion resistance function or a layer having self-repairing property, or Examples thereof include an antifouling layer for preventing surface contamination and an adhesive or adhesive layer for laminating each layer.

  The functional layer may be provided on the peelable substrate in advance before forming the near-infrared absorbing pressure-sensitive adhesive layer on the peelable substrate, for example. After forming the absorbent pressure-sensitive adhesive layer, it may be provided on the near-infrared-absorbing pressure-sensitive adhesive layer, and the peelable substrate on which the near-infrared-absorbing pressure-sensitive adhesive layer is formed is peeled off to expose the near-infrared absorption May be provided on the adhesive layer. Moreover, you may provide previously on this support film before forming a near-infrared absorptive adhesive layer on a support film. Moreover, you may give the function as a functional layer to support film itself.

  The multilayer optical film of the present invention can be used by sticking, for example, a near-infrared absorbing pressure-sensitive adhesive layer, which is exposed by peeling off a release film, to a transparent substrate having high rigidity. As a material for the transparent substrate, it can be appropriately selected from glass (transparent glass substrate) and a transparent and highly rigid polymer material (transparent resin substrate). Preferred examples include glass, tempered or semi-tempered glass, polycarbonate, PET, and polyacrylate.

  Each functional layer (film) is pressure-bonded to a functional substrate and combined with each other to form a multilayer optical film. However, even if it is directly bonded to the PDP module, it can be applied to a transparent glass plate or plastic plate. You may adhere and attach to the front surface of PDP.

  Although an example of a structure of the multilayer optical film of this invention is described below, it is not necessarily restricted to these.

When the neon absorbing dye layer is not included in the near infrared absorbing pressure-sensitive adhesive layer, the basic layer structure is, for example, an antireflection layer / transparent resin substrate / electromagnetic wave shielding layer / near infrared absorbing pressure sensitive adhesive layer in this order. Examples include laminated multilayer optical films. Furthermore, a neon-absorbing pressure-sensitive adhesive layer can be provided, and as the layer configuration, for example, as shown in FIG.
Antireflection layer / transparent resin substrate / electromagnetic wave shielding layer / near infrared absorbing pressure-sensitive adhesive layer / neon absorbing layer,
Antireflection layer / transparent resin substrate / near infrared absorbing pressure-sensitive adhesive layer / electromagnetic wave shield layer / transparent resin substrate / neon absorption layer,
Antireflection layer / Transparent resin substrate / Near infrared absorbing pressure-sensitive adhesive layer / Transparent resin substrate / Electromagnetic wave shielding layer / Neon absorption layer or Antireflection layer / Transparent resin substrate / Neon absorption layer / Transparent resin Base material / electromagnetic wave shielding layer / near-infrared absorbing adhesive layer,
The multilayer optical film laminated | stacked in order of these is mentioned. Especially, the multilayer optical film laminated | stacked in order of the antireflection layer / transparent resin base material / electromagnetic wave shield layer / near-infrared absorptive adhesive layer / neon absorption layer is preferable.

When the near-infrared-absorbing pressure-sensitive adhesive layer contains a neon-absorbing dye, if the layer is described as a near-infrared and neon-absorbing pressure-sensitive adhesive layer, the layer structure is, for example, as shown in FIG.
Antireflection layer / transparent resin substrate / electromagnetic wave shielding layer / near infrared and neon absorbing pressure-sensitive adhesive layer,
Antireflection layer / transparent resin substrate / infrared and neon absorbing adhesive layer / electromagnetic wave shield layer / transparent resin substrate,
Antireflection layer / transparent resin substrate / infrared and neon absorbing adhesive layer / transparent resin substrate / electromagnetic shielding layer,
The multilayer optical film laminated | stacked in order of these is mentioned. Especially, the multilayer optical film laminated | stacked in order of the reflection preventing layer / transparent resin base material / electromagnetic wave shield layer / near infrared rays and a neon absorptive adhesive layer is preferable.

  In addition to the above basic layer configuration, other functional layers (films) can be laminated according to the mode of the optical film.

  When a multilayer optical film attached to a transparent substrate is used as an optical filter, it can also function as a protective plate for a display device such as a PDP.

  The multilayer optical film of the present invention, or a film obtained by sticking the multilayer optical film on a transparent substrate, is a flat display device such as a PDP, a plasma addressed liquid crystal (PALC) display panel, a field emission display (FED) panel, and a cathode. It can be used as an optical filter for a display device such as a tube display device (CRT).

EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example with a comparative example, this invention is not limited to these Examples.
1. Production of near-infrared absorbing adhesive sheet [Production Example 1] (acrylic polymer A1)
93.8 parts by mass of n-butyl acrylate (BA), 6 parts by mass of acrylic acid (AA), 0.2 parts by mass of 2-hydroxyethyl acrylate (2HEA), 150 parts by mass of ethyl acetate, azobisisobutyronitrile (AIBN) ) 0.2 parts by mass was put into a reaction vessel, and the air in the reaction vessel was replaced with nitrogen gas, and then the reaction vessel was heated to 60 ° C. in a nitrogen atmosphere with stirring and reacted for 4 hours. Thereafter, 50 parts by mass of ethyl acetate was added, and the mixture was further reacted at 60 ° C. for 6 hours. After the reaction, 200 parts by mass of methyl ethyl ketone was added and diluted to obtain an acrylic polymer A1 solution (weight average molecular weight 1,200,000, glass transition temperature -48 ° C.). The results are shown in Table 1.
[Production Example 2] (Acrylic polymer A2)
An acrylic polymer A2 solution (weight average molecular weight 1,200,000, glass transition temperature -44 ° C.) was obtained in the same manner as in Production Example 1 except that the ratio of the acrylic polymer composition and the amount of the solvent used were changed. The results are shown in Table 1.

<Measurement of molecular weight>
The weight average molecular weight (Mw) of the acrylic polymer was determined by gel permeation chromatography (GPC) in terms of standard polystyrene.

Measurement condition:
Apparatus: HLC-8120 (manufactured by Tosoh Corporation)
Column: G7000HXL (manufactured by Tosoh Corporation)
GMHXL (manufactured by Tosoh Corporation)
G2500HXL (manufactured by Tosoh Corporation)
Sample concentration: 1.5 mg / ml (diluted with tetrahydrofuran)
Mobile phase solvent: Tetrahydrofuran Flow rate: 1.0 ml / min
Column temperature: 40 ° C
[Production Example 3] (Near-infrared absorbing adhesive sheet B1)
To 100 parts by mass of the solid content of the acrylic polymer A1 solution, 2.5 parts by mass of an aromatic diimonium compound (Nippon Kayaku IRG022, solubility in 1 g of ethyl acetate at 25 ° C. is 1.1 mg), an isocyanate curing agent ( A pressure-sensitive adhesive composition was prepared by adding 0.2 parts by mass of L-45) manufactured by Soken Chemical Co., Ltd. and 0.05 parts by mass of a metal chelate curing agent (M-12AT manufactured by Soken Chemical Co., Ltd.). Methyl ethyl ketone (MEK) was added thereto, and the mixture was put into a homogenizer and stirred at 10000 rpm for 10 minutes to obtain an adhesive composition having a solid content concentration of 10%.

The prepared pressure-sensitive adhesive composition was applied onto a peelable substrate S-71 (manufactured by Teijin Ltd.) using a bar coater so that the thickness after drying was 20 μm, and dried with a dryer at 65 ° C. for 3 minutes. did. After drying, a peelable substrate A-31 (manufactured by Teijin Limited) was bonded to the pressure-sensitive adhesive layer side and aged at 23 ° C. for 7 days to obtain a near-infrared absorbing pressure-sensitive adhesive sheet B1 (transfer sheet).
[Production Example 4] (Near-infrared absorbing adhesive sheet B2)
2.5 parts by mass of aromatic diimonium compound (Nippon Kayaku IRG022, solubility in 1 g of ethyl acetate at 25 ° C) is 100 parts by mass with respect to the solid content of acrylic polymer A2 solution, neon cut dye (ADEKA 0.05 parts by mass of TY171), 0.2 parts by mass of isocyanate curing agent (manufactured by Soken Chemical Co., Ltd., L-45) and 0.05 parts by mass of metal chelate curing agent (M-12AT by Soken Chemical Co., Ltd.) A composition was prepared. Methyl ethyl ketone (MEK) was added thereto, and the mixture was put into a homogenizer and stirred at 10000 rpm for 10 minutes to obtain an adhesive composition having a solid content concentration of 10%.

The prepared pressure-sensitive adhesive composition was applied onto a peelable substrate S-71 (manufactured by Teijin Ltd.) using a bar coater so that the thickness after drying was 20 μm, and dried with a dryer at 65 ° C. for 3 minutes. did. After drying, a peelable substrate A-31 (manufactured by Teijin Limited) was bonded to the pressure-sensitive adhesive layer side and aged at 23 ° C. for 7 days to obtain a near-infrared absorbing pressure-sensitive adhesive sheet B2 (transfer sheet).
[Production Example 5] (Near-infrared absorbing adhesive sheet B3)
2.5 parts by mass of aromatic diimonium compound (IRG022 manufactured by Nippon Kayaku), 0.05 parts by mass of neon cut dye (TY171 manufactured by ADEKA), and isocyanate-based curing agent L-45 with respect to 100 parts by mass of the solid content of the acrylic polymer A1 solution 0.2 parts by mass (manufactured by Soken Chemical) and 0.05 parts by mass of metal chelate curing agent M-12AT (manufactured by Soken Chemical) were added to prepare an adhesive composition. Methyl ethyl ketone (MEK) was added thereto, and the mixture was put into a homogenizer and stirred at 10000 rpm for 10 minutes to obtain an adhesive composition having a solid content concentration of 10%.

  The prepared pressure-sensitive adhesive composition was applied onto a peelable substrate S-71 (manufactured by Teijin Ltd.) using a bar coater so that the thickness after drying was 20 μm, and dried with a dryer at 65 ° C. for 3 minutes. did. After drying, a peelable substrate A-31 (manufactured by Teijin Limited) was bonded to the pressure-sensitive adhesive layer side and aged at 23 ° C. for 7 days to obtain a near-infrared absorbing pressure-sensitive adhesive sheet B3 (transfer sheet).

2. Production of electromagnetic shielding material [Production Example 6] (Electromagnetic shielding layer C1)
A transparent porous layer (layer thickness: 20 μm) of an alumina film is formed on the opposite surface of the polyethylene terephthalate transparent base material to which an antireflection film (Nyalfa Realc L7800) is attached, and a screen printing machine ( Using a conductive paste (manufactured by Fujikura Kasei Co., Ltd., trade name “Dotite XA-9080”) by New Long Seimitsu Kogyo Co., Ltd., screen printing of a lattice pattern was performed. For the screen plate, use a screen plate (manufactured by Nakanuma Art Screen Co., Ltd.) with a grid mesh pattern with a line width of 20μ, a pattern pitch of 250μm, and an aperture ratio of 84.6% on a 500 mesh stainless steel basket woven with a 18μm diameter stainless steel wire. It was.

After printing, the silver compound base together with the film is baked at 55 ° C. for 15 minutes using electric heating hot air, and then baked at 150 ° C. for 30 minutes to form a conductive part in which a square pattern is drawn in a lattice shape, and the electromagnetic shielding material C1 is formed. Manufactured.
[Production Example 7] (Electromagnetic wave shielding layer C2)
As a transparent resin base material having no antireflection film, a polyethylene terephthalate with a thickness of 125 μm (trade name: A4300, manufactured by Toyobo Co., Ltd.) is used. A transparent porous layer of an alumina film is formed on the easy-adhesion surface. Manufactured.
3. Preparation of Neon Absorbing Adhesive Sheet [Production Example 8] (Neon Absorbing Adhesive Sheet D1)
0.05 part by weight of neon cut dye (ADEKA TY171), 0.2 part by weight of isocyanate curing agent L-45 (manufactured by Soken Chemical), 100 parts by weight of solid content of acrylic polymer A1 solution, metal chelate curing agent An adhesive composition was prepared by adding 0.05 parts by mass of M-12AT (manufactured by Soken Chemical). Methyl ethyl ketone (MEK) was added thereto, and the mixture was put into a homogenizer and stirred at 10000 rpm for 10 minutes to obtain an adhesive composition having a solid content concentration of 10%.

The prepared pressure-sensitive adhesive composition was applied onto a peelable substrate S-71 (manufactured by Teijin Ltd.) using a bar coater so that the thickness after drying was 20 μm, and dried with a dryer at 65 ° C. for 3 minutes. did. After drying, a peelable substrate A-31 (manufactured by Teijin Ltd.) was bonded to the pressure-sensitive adhesive layer side and aged at 23 ° C. for 7 days to obtain a neon absorbent pressure-sensitive adhesive sheet D1 (transfer sheet).
[Production Example 9] (neon absorbent pressure-sensitive adhesive sheet D2)
A neon-absorbing pressure-sensitive adhesive sheet D2 was obtained in the same manner as in Production Example 8, except that the pressure-sensitive adhesive composition prepared in Production Example 8 was coated on 125 μm thick polyethylene terephthalate (trade name A4300, manufactured by Toyobo Co., Ltd.).
4). Preparation of multilayer optical film [Example 1]
The electromagnetic shielding material C1 and the near-infrared absorbing adhesive sheet B1 were bonded together by a laminating machine. Specifically, the peelable substrate A-31 (manufactured by Teijin Ltd.) of the near-infrared absorbing pressure-sensitive adhesive sheet B1 was peeled off and bonded to the surface on which the electromagnetic wave shielding mesh of the electromagnetic wave shielding material C1 was formed.

Next, the peelable substrate S-71 (manufactured by Teijin Limited) on the near infrared absorbing pressure-sensitive adhesive sheet surface is peeled off and laminated with the polyethylene terephthalate substrate side of the neon cut pressure-sensitive adhesive sheet D2 to form a multilayer optical film. Produced. See (1) in FIG.
[Example 2]
The electromagnetic wave shielding material C2 and the near-infrared absorbing adhesive sheet B1 were bonded together by a laminating machine. Specifically, the peelable substrate A-31 (manufactured by Teijin Limited) of the near-infrared absorbing pressure-sensitive adhesive sheet B1 was peeled off and bonded to the surface on which the electromagnetic wave shielding mesh of the electromagnetic wave shielding material C2 was formed.

  Next, the peelable substrate S-71 (manufactured by Teijin Ltd.) on the surface of the near-infrared absorbing pressure-sensitive adhesive sheet is peeled off and laminated on the polyester film side of an antireflective film L7800 (polyester film substrate) made of NOF Bonding was performed using a machine.

Finally, the peelable substrate A-31 (manufactured by Teijin Ltd.) of the neon cut absorbent pressure-sensitive adhesive sheet D1 (transfer sheet) is peeled off and bonded to the polyester substrate opposite to the antireflection surface, and a multilayer optical film Got. See (2) in FIG.
[Example 3]
The electromagnetic wave shielding material C2 and the near-infrared absorbing adhesive sheet B1 were bonded together by a laminating machine. Specifically, the peelable substrate A-31 (manufactured by Teijin Limited) of the near-infrared absorbing pressure-sensitive adhesive sheet B1 was peeled off and bonded to the opposite surface on which the electromagnetic wave shielding mesh of the electromagnetic wave shielding material C2 was formed. .

  Next, the release substrate S-71 (manufactured by Teijin Limited) of the near-infrared absorbing pressure-sensitive adhesive sheet B1 is peeled off and laminated on the polyester film side of an antireflective film L7800 (polyester film substrate) made of Japanese fats and oils. Were bonded together.

Finally, the peelable substrate A-31 (manufactured by Teijin Limited) of the neon cut absorbent pressure-sensitive adhesive sheet D1 (transfer sheet) was peeled off and bonded to the electromagnetic shielding mesh surface to obtain a multilayer optical film. See (3) in FIG.
[Example 4]
The peelable base material A-31 (manufactured by Teijin Ltd.) of the neon absorbent pressure-sensitive adhesive sheet D1 is peeled off from the polyester base surface of the anti-reflective film L7800 (polyester film base material) made of Japanese fats and oils and pasted by a laminating machine. Combined (Intermediate H).

  Next, the electromagnetic shielding material C2 and the peelable substrate A-31 (manufactured by Teijin Ltd.) of the near-infrared absorbing adhesive sheet B1 were peeled off and bonded to the electromagnetic shielding mesh surface with a laminating machine ( Intermediate I).

The peelable substrate S-71 (manufactured by Teijin Limited) of the intermediate H was peeled off, and the neon cut absorbing surface and the polyester substrate side of the intermediate I were bonded together by a laminating machine to obtain a multilayer optical film. . See (4) in FIG.
[Example 5]
The electromagnetic wave shielding material C1 and the near-infrared absorbing adhesive sheet B3 were bonded together by a laminating machine to obtain a multilayer optical film. Specifically, the peelable substrate A-31 (manufactured by Teijin Limited) of the near-infrared absorbing pressure-sensitive adhesive sheet B3 was peeled off and bonded to the surface on which the electromagnetic wave shielding mesh of the electromagnetic wave shielding material C1 was formed. See (1) in FIG.
[Example 6]
The electromagnetic wave shielding material C2 and the near-infrared absorbing adhesive sheet B3 were bonded together by a laminating machine. Specifically, the peelable substrate A-31 (manufactured by Teijin Limited) of the near-infrared absorbing pressure-sensitive adhesive sheet B3 was peeled off and bonded to the surface of the electromagnetic wave shielding material C2 on which the electromagnetic wave shielding mesh was formed.

Next, the release substrate S-71 (manufactured by Teijin Ltd.) of the near-infrared absorbing pressure-sensitive adhesive sheet B3 is peeled off and laminated on the polyester film side of an antireflective film L7800 (polyester film substrate) made of NOF. Were laminated together to obtain a multilayer optical film. See (2) in FIG.
[Example 7]
The electromagnetic wave shielding material C2 and the near-infrared absorbing adhesive sheet B3 were bonded together by a laminating machine. Specifically, the peelable substrate A-31 (manufactured by Teijin Ltd.) of the near-infrared absorbing pressure-sensitive adhesive sheet B3 was peeled off and bonded to the opposite surface on which the electromagnetic wave shielding mesh of the electromagnetic wave shielding material C2 was formed. .

Next, the release substrate S-71 (manufactured by Teijin Limited) of the near-infrared absorbing pressure-sensitive adhesive sheet B3 is peeled off and applied to the polyester film substrate side of the antireflective film L7800 (polyester film substrate) made of NOF. Lamination was performed to obtain a multilayer optical film. See (3) in FIG.
[Example 8]
2.5 parts by mass of aromatic diimonium compound (IRG022 manufactured by Nippon Kayaku), 0.05 parts by mass of neon cut dye (TY171 manufactured by ADEKA), and isocyanate-based curing agent L-45 with respect to 100 parts by mass of the solid content of the acrylic polymer A1 solution 0.2 parts by mass (manufactured by Soken Chemical) and 0.05 parts by mass of metal chelate curing agent M-12AT (manufactured by Soken Chemical) were added to prepare an adhesive composition. Methyl ethyl ketone (MEK) was added thereto, and the mixture was put into a homogenizer and stirred at 10000 rpm for 10 minutes to obtain an adhesive composition having a solid content concentration of 10%.

The prepared pressure-sensitive adhesive composition was applied onto the electromagnetic wave shielding mesh of the electromagnetic wave shielding material C1 using a bar coater so that the thickness after drying was 20 μm, and dried with a dryer at 65 ° C. for 3 minutes. After drying, a peelable substrate A-31 (manufactured by Teijin Limited) was bonded to the pressure-sensitive adhesive layer side and aged at 23 ° C. for 7 days to obtain a multilayer optical film. See (1) in FIG.
[Comparative Example 1]
The electromagnetic wave shielding material C1 and the near-infrared absorbing pressure-sensitive adhesive sheet B2 were bonded together by a laminating machine to produce a multilayer optical film. Specifically, the peelable substrate A-31 (manufactured by Teijin Ltd.) of the near-infrared absorbing pressure-sensitive adhesive sheet B2 was peeled off and bonded to the opposite surface on which the electromagnetic wave shielding mesh of the electromagnetic wave shielding material C1 was formed. . See (1) in FIG.
[Test Example 1]
The peelable substrate A-31 (manufactured by Teijin Ltd.) of the multilayer optical film obtained in Examples 1 to 8 and Comparative Example 1 was peeled off and stuck on a slide glass to prepare test pieces, respectively. About the multilayer optical film of the structure without a peeling base material, it stuck together on the slide glass using the adhesion transfer sheet (SK8763 by Soken Chemical) separately. The following test was done about this test piece. The results are shown in Tables 2 and 3.

According to this, the multilayer optical film of the Example obtained a good result in any durability test. On the other hand, in the multilayer optical film of Comparative Example 1, since the acrylic polymer A2 (the content of acrylic acid (AA) is 10 parts by weight) is used as the base material of the pressure-sensitive adhesive layer, the durability test (particularly, total light transmission) Rate, haze, and transmittance at each wavelength) were confirmed to be poor.
<Durability test>
About each test piece of a near-infrared absorption adhesive film, the total light transmittance in an initial stage after being left for 1000 hours in an environment of 80 ° C./90% (Evaluation A) and after being left for 1000 hours in an environment of 85 ° C. (Evaluation B) (%), Haze (%), transmittance (850 nm, 950 nm, 590 nm), and resistance value of the electromagnetic shielding material were measured. In addition, appearance evaluation was performed after leaving for 1000 hours in an environment of 80 ° C./90% (Evaluation A) and after leaving for 1000 hours in an environment of 85 ° C. (Evaluation B).
<Total light transmittance and haze value>
Using Nippon Denshoku NDH-2000, total light transmittance and haze value were measured according to the method of JIS-K-6882.
<Transmission at 850 nm, 950 nm, and 590 nm>
Using a spectrophotometer (Hitachi U-3410), the transmittance of 300 nm to 1500 nm was measured, and the transmittances of 850 nm, 950 nm, and 590 nm were measured.
<Appearance evaluation>
Visual changes in the appearance of the test piece, such as color change and interlayer float, were confirmed. The evaluation method is as follows.

  ◯: No change in color, lifting of the pressure-sensitive adhesive layer, or peeling was not confirmed.

X: Change in color and precipitation of pigment were observed.
<Resistance value of electromagnetic shielding material>
A multi-layer optical film of 7 cm × 5 cm was prepared so that the mesh surface was exposed at both ends of 1 cm, and silver paste was applied to both ends, 1 cm × 5 cm wide and dried to produce electrodes at both ends (FIG. 4). See). The both ends were squeezed with clips, and the electrical resistance value was measured. Measurement was performed using a measuring instrument Yokogawa DEGITAL MULTIMETER.

It is the figure which showed typically the measuring method of an aperture ratio. The basic layer structure of a multilayer optical film when a neon absorbing dye is not included in the near-infrared absorbing pressure-sensitive adhesive layer is shown. AR indicates an antireflection layer, PET indicates a transparent resin layer, EMI indicates an electromagnetic wave shielding layer, and NIR cut adhesive indicates a near-infrared absorbing adhesive layer. The basic layer structure of a multilayer optical film in the case of including a neon absorbing dye in the near-infrared absorbing pressure-sensitive adhesive layer is shown. AR indicates an antireflection layer, PET indicates a transparent resin layer, EMI indicates an electromagnetic wave shielding layer, and NIR + Ne cut adhesive indicates a near infrared and neon absorbing adhesive layer. It is a figure which shows the measuring method of the resistance value of the electromagnetic wave shielding material in a multilayer optical film.

Claims (17)

(A-1) acrylic acid alkyl ester and / or methacrylic acid alkyl ester 82-96 parts by mass,
(A-2) 4-8 parts by mass of a carboxyl group-containing monomer, and (a-3) 0-10 parts by mass of other monomers copolymerizable with the above (a-1) and / or (a-2) (provided that The total amount of (a-1) to (a-3) is 100 parts by mass)
A near-infrared absorbing pressure-sensitive adhesive layer comprising an acrylic polymer (A) having a weight average molecular weight of 1,200,000 to 1,500,000 and a diimonium dye (B1), wherein the diimonium dye (B1) Near-infrared absorbing pressure-sensitive adhesive having a solubility in 1 g of ethyl acetate at 25 ° C. of 0.6 mg or more and containing 1 to 10 parts by mass of the diimonium dye (B1) with respect to 100 parts by mass of the acrylic polymer (A) A multilayer optical film comprising: an antireflection layer; an electromagnetic wave shielding layer; and a transparent resin substrate. In the near-infrared absorbing pressure-sensitive adhesive layer, with respect to 100 parts by mass of the acrylic polymer (A), at least one selected from the group consisting of an isocyanate curing agent, an epoxy curing agent, and a metal chelate curing agent. The multilayer optical film of Claim 1 containing 0.001-10 mass parts of hardening | curing agents (C). The said near-infrared absorptive pressure-sensitive adhesive layer contains 1 to 10 parts by mass of the diimonium dye (B1) and the phthalocyanine dye (B2) in total with respect to 100 parts by mass of the acrylic polymer (A). 2. The multilayer optical film according to 2. Either of the said transparent resin base materials has a transparent porous layer, and the conductive part (electromagnetic wave shield layer) of a geometric pattern is provided on this transparent porous layer surface. A multilayer optical film as described in 1.   The electromagnetic wave shielding layer is formed by screen-printing a conductive paste containing particulate silver oxide, tertiary fatty acid silver and a solvent in a geometric pattern on the transparent porous layer surface of the transparent resin substrate, and then printing the transparent The multilayer optical film according to claim 4, wherein the multilayer optical film is a layer obtained by heat-treating a conductive resin substrate.   The multilayer optical film according to claim 4 or 5, further comprising an antireflection layer on a surface opposite to the electromagnetic wave shielding layer of the transparent resin substrate. The multilayer optical film according to any one of claims 1 to 6, wherein the multilayer optical film is laminated in the order of antireflection layer / transparent resin substrate / electromagnetic wave shield layer / near infrared absorbing pressure-sensitive adhesive layer. . Furthermore, the multilayer optical film in any one of Claims 1-7 containing a neon absorption layer. The layer structure of the multilayer optical film is
Antireflection layer / transparent resin substrate / electromagnetic wave shielding layer / near infrared absorbing pressure-sensitive adhesive layer / neon absorbing layer,
Antireflection layer / transparent resin substrate / near infrared absorbing pressure-sensitive adhesive layer / electromagnetic wave shield layer / transparent resin substrate / neon absorption layer,
Antireflection layer / Transparent substrate / Near infrared absorbing pressure-sensitive adhesive layer / Transparent resin substrate / Electromagnetic wave shield layer / Neon absorption layer or Antireflection layer / Transparent resin substrate / Neon absorption layer / Transparent resin substrate / Electromagnetic wave shielding layer / near infrared absorbing adhesive layer,
The multilayer optical film according to claim 8, which is laminated in the order of. (A-1) acrylic acid alkyl ester and / or methacrylic acid alkyl ester 82-96 parts by mass,
(A-2) 4-8 parts by mass of a carboxyl group-containing monomer, and (a-3) 0-10 parts by mass of other monomers copolymerizable with the above (a-1) and / or (a-2) (provided that The total amount of (a-1) to (a-3) is 100 parts by mass)
A near-infrared and neon-absorbing pressure-sensitive adhesive layer containing an acrylic polymer (A) having a weight average molecular weight of 1,200,000 to 1,500,000, a diimonium dye (B1), and a neon cut dye (D). The solubility of the diimonium dye (B1) in 1 g of ethyl acetate at 25 ° C. is 0.6 mg or more, and the diimonium dye (B1) is added in an amount of 1 to 10 with respect to 100 parts by mass of the acrylic polymer (A). A multilayer optical film comprising a near-infrared and neon-absorbing pressure-sensitive adhesive layer containing 0.001 part by mass or more of neon-cut dye (D); an antireflection layer; an electromagnetic wave shielding layer; and a transparent resin substrate. At least 1 selected from the group consisting of an isocyanate curing agent, an epoxy curing agent and a metal chelate curing agent with respect to 100 parts by mass of the acrylic polymer (A) in the near infrared and neon absorbing pressure-sensitive adhesive layer. The multilayer optical film of Claim 10 containing 0.001-10 mass parts of seed | species hardening | curing agents (C). The near-infrared and neon-absorbing pressure-sensitive adhesive layer contains 1 to 10 parts by mass of the diimonium dye (B1) and the phthalocyanine dye (B2) with respect to 100 parts by mass of the acrylic polymer (A). The multilayer optical film as described in 10 or 11. The transparent resin base material has a transparent porous layer on one surface, and a conductive portion (electromagnetic wave shielding layer) having a geometric pattern is provided on the surface of the transparent porous layer. A multilayer optical film as described in 1.   The electromagnetic wave shielding layer is formed by screen-printing a conductive paste containing particulate silver oxide, tertiary fatty acid silver and a solvent in a geometric pattern on the transparent porous layer surface of the transparent resin substrate, and then printing the transparent The multilayer optical film according to claim 13, wherein the multilayer optical film is a layer obtained by heat-treating a conductive resin substrate.   The multilayer optical film in any one of Claims 10-14 which has an antireflection layer in the surface on the opposite side to the electromagnetic wave shielding layer of the said transparent resin base material. The multilayer structure according to any one of claims 10 to 15, wherein the multilayer optical film is laminated in the order of antireflection layer / transparent resin substrate / electromagnetic wave shield layer / near infrared and neon absorbing pressure-sensitive adhesive layer. Optical film. The layer structure of the multilayer optical film is an antireflection layer / transparent resin substrate / electromagnetic wave shielding layer / near infrared and neon absorbing pressure-sensitive adhesive layer,
Antireflection layer / transparent resin substrate / infrared and neon absorbing adhesive layer / electromagnetic wave shielding layer / transparent resin substrate, or antireflection layer / transparent resin substrate / infrared and neon absorbing adhesive layer / transparent Resin base material / electromagnetic wave shielding layer,
The multilayer optical film according to claim 10, which is laminated in the order of.

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