JP2013129701A - Pressure-sensitive adhesive composition, pressure-sensitive adhesive film, and optical filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pressure-sensitive adhesive composition excellent in light resistance and containing a tetraazaporphyrin-based dye, and a pressure-sensitive adhesive film and an optical filter.SOLUTION: The pressure-sensitive adhesive composition for the optical filter contains a tetraazaporphyrin-based dye, an ultraviolet absorber, a light stabilizer composed of a copper complex or a nickel complex, an acrylic pressure-sensitive adhesive, and an organic solvent in which solubility of the tetraazaporphyrin-based dye is (1 g)/(100 g) or more at 25°C, wherein solubility of the light stabilizer in the organic solvent is (3 g)/(100 g) or more at 25°C. The pressure-sensitive adhesive film and the optical filter possess a pressure-sensitive adhesive layer formed by using the composition.

Description

  The present invention relates to an adhesive composition for an optical filter having a color tone correction function, an adhesive film, and an optical filter using the same, which are used for a plasma display (hereinafter referred to as PDP if necessary).

  Conventionally, a plasma display has the front surface of the PDP for the purpose of shielding electromagnetic waves radiated from the PDP, near-infrared rays, etc., preventing reflection of outside light, and converting the color of the PDP to a desired color tone. There has been a need for an optical filter disposed in

  Among these, in recent years, the function of converting the color development of the PDP to a desired color tone has been regarded as important. As a method of converting the color of PDP into a desired color tone, it is common to use various color tone correction dyes. Among the color correction dyes, there is an increasing demand for tetraazaporphyrin dyes as dyes that efficiently absorb unnecessary orange light having a wavelength of about 590 nm emitted by PDP. For example, tetraazaporphyrin-based dyes are contained in an adhesive film and used in an optical filter (see Patent Document 1). However, light resistance is not sufficient with respect to required characteristics that are becoming increasingly severe year by year.

  On the other hand, in an optical filter for PDP, a phthalocyanine-based dye having a near-infrared absorbing ability is used for shielding near-infrared rays, and Patent Document 2 contains a dithiol complex as a light stabilizer in combination in an adhesive film. The technique used for the optical filter is described.

  However, even if a dithiol complex is used as a light stabilizer in a tetraazaporphyrin-based dye, not all dithiol complexes can obtain a sufficient effect, and light that sufficiently increases the effect on a tetraazaporphyrin-based dye. There is a need for stabilizers.

JP 2010-287310 A International Publication No. 2006/090705

  The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a tetraazaporphyrin-based dye-containing pressure-sensitive adhesive composition, pressure-sensitive adhesive film, and optical filter that are excellent in light resistance.

The pressure-sensitive adhesive composition of the present invention has a tetraazaporphyrin-based dye, an ultraviolet absorber, a light stabilizer composed of a copper complex or a nickel complex, an acrylic pressure-sensitive adhesive, and a solubility of the tetraazaporphyrin-based dye at 25 ° C. And an organic solvent that is 1 g / 100 g or more, and the solubility of the light stabilizer in the organic solvent is 3 g / 100 g or more at 25 ° C.
However, the organic solvent does not include an organic solvent derived from an acrylic pressure-sensitive adhesive.
The pressure-sensitive adhesive composition of the present invention preferably further contains a near infrared absorbing dye.
The near-infrared absorbing dye contained in the pressure-sensitive adhesive composition of the present invention is preferably selected from phthalocyanine dyes represented by the following formula (1).

In Expression ^{(1), R} 1 ~R ¹⁶ each independently represent a hydrogen atom, a halogen atom, hydroxy group, amino group, hydroxy sulfonyl group, aminosulfonyl group or a hydrocarbon group (provided that the carbon number of 1 to 20, The hydrocarbon group may contain one or more atoms selected from the group consisting of a nitrogen atom, a sulfur atom, an oxygen atom and a halogen atom), and two adjacent substituents are connected via a linking group. It may be. Provided that at least four of R ² , R ³ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , R ¹⁴ , R ¹⁵ are unsubstituted or a phenyl group in which at least one of hydrogen atoms is substituted with an alkyl group or This is a group having a phenyl group at the terminal. M ² represents a divalent metal atom, a trivalent substituted metal atom, a tetravalent metal atom, or an oxy metal. ]

The complex contained in the pressure-sensitive adhesive composition of the present invention is preferably a complex in which a ligand selected from organic ligands having an oxygen atom or a sulfur atom as a coordination atom is coordinated to copper or nickel.
The pressure-sensitive adhesive composition of the present invention preferably contains the light stabilizer in a proportion of 0.001 to 10 parts by mass with respect to 100 parts by mass of the acrylic pressure-sensitive adhesive.

The pressure-sensitive adhesive film of the present invention has a pressure-sensitive adhesive layer formed on the film using the pressure-sensitive adhesive composition of the present invention.
The optical filter of the present invention is an optical filter in which one or more films are attached to a substrate, and between the film and the substrate, or between the films in the case where the number of the films is two or more, It has the adhesive layer formed using the adhesive composition of the said invention.

  ADVANTAGE OF THE INVENTION According to this invention, the adhesive composition and adhesive film which are excellent in the light resistance of the tetraazaporphyrin type pigment | dye to contain, an adhesive film, and an optical filter can be provided.

  Embodiments of the present invention will be described below. In addition, this invention is not limited to the following embodiment.

[Adhesive composition]
The pressure-sensitive adhesive composition of the present invention has a tetraazaporphyrin-based dye, an ultraviolet absorber, a light stabilizer composed of a copper complex or a nickel complex, an acrylic pressure-sensitive adhesive, and a solubility of the tetraazaporphyrin-based dye at 25 ° C. And an organic solvent that is 1 g / 100 g or more, and the solubility of the light stabilizer in the organic solvent is 3 g / 100 g or more at 25 ° C. Hereinafter, in the present specification, the solubility means the solubility at 25 ° C. unless otherwise specified.

(Tetraazaporphyrin dye)
The tetraazaporphyrin-based dye is not particularly limited as long as it is a compound having a tetraazaporphyrin skeleton. The compound having a tetraazaporphyrin skeleton can absorb orange unnecessary light near a wavelength of 590 nm emitted from a display, particularly a PDP.
Specific examples of the tetraazaporphyrin-based dye include compounds represented by the following formula (2).

In formula (2), R ^{23 to} R ³⁰ each independently represent a hydrogen atom, a halogen atom, a cyano group, a benzyl group, a phenyl group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms (provided that , A benzyl group, a phenyl group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, in which one or more hydrogen atoms may be substituted with halogen atoms. M ¹ is any ^one of Cu, Ni, Zn, Pd, Pt, VO, Co, and Mg.

R ^{23 to} R ³⁰ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or one or more hydrogen atoms substituted with a fluorine atom, bromine atom or chlorine atom.
6 alkoxy groups are preferable, and a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms is more preferable.

The alkyl group having 1 to 4 carbon atoms is preferably a methyl group, an ethyl group, a propyl group, a butyl group, or a tert-butyl group. The one or more alkoxy groups having 1 to 4 carbon hydrogen atoms are replaced by fluorine _{atom, -OCF 3, -OCH 2 CHF 2} , -OCH 2 CF 3, preferably -OCH 2 _CH 2 CF _3. R ^{23 to} R ³⁰ are preferably composed of two types of atoms or groups selected from these, and compounds in which they are alternately bonded to the tetraazaporphyrin skeleton. As a combination of two kinds of atoms or groups, the following combinations are preferable.
(2A) a combination of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms,
(2B) A combination of an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms.
M ¹ is preferably Cu or VO.

Examples of the tetraazaporphyrin-based dye represented by the formula (2) include, for example, a trade name “TAP-2” (a compound classified as (2B) above, R ^{23 to} R ³⁰ are manufactured by Yamada Chemical Co., Ltd. A tert-butyl group and —OCH ₂ CF ₃ ), “TAP-HTBX” (a compound classified as (2A) above, R ^{23 to} R ³⁰ are alternately a hydrogen atom and a tert-butyl group) Etc. These commercially available tetraazaporphyrin-based dyes can be preferably used because they can efficiently absorb the orange unnecessary light near the wavelength of 590 nm emitted from the display, particularly PDP.

  The content of the tetraazaporphyrin-based dye in the pressure-sensitive adhesive composition is 0.001 with respect to 100 parts by mass of an acrylic pressure-sensitive adhesive (however, when a cross-linking agent described later is included, the total amount of the acrylic pressure-sensitive adhesive and the cross-linking agent). -20 mass parts is preferable, and 0.01-10 mass parts is more preferable. Hereinafter, when referring to the mass ratio of other components to 100 parts by mass of the acrylic pressure-sensitive adhesive, unless otherwise specified, the total amount of the acrylic pressure-sensitive adhesive and the crosslinking agent in the case where the acrylic pressure-sensitive adhesive contains a crosslinking agent described later. The mass ratio with respect to 100 mass parts is said. By setting the content of the tetraazaporphyrin-based pigment to 0.001 part by mass or more with respect to 100 parts by mass of the acrylic pressure-sensitive adhesive, a color tone correction function that absorbs unnecessary light in the vicinity of a wavelength of 590 nm can be sufficiently exhibited. A decrease in durability can be suppressed by setting the amount to be equal to or less than part by mass.

(UV absorber)
The ultraviolet absorber is used for suppressing deterioration due to ultraviolet rays and improving durability without impairing the function of the tetraazaporphyrin-based dye. An ultraviolet absorber will not be restrict | limited especially if it has such an effect | action. Specifically, benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, salicylate ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, triazine ultraviolet absorbers, oxanilide ultraviolet absorbers, nickel complex ultraviolet absorbers, Inorganic ultraviolet absorbers are preferred.

A commercial item can be used as a ultraviolet absorber. As commercial products, all of BASF are trade names, and the following ultraviolet absorbers can be mentioned.
Benzotriazole ultraviolet absorbers: “TINUVIN PS”, “TINUVIN 99-2”, etc.
Benzophenone-based ultraviolet absorber: “CHIMASSORB 81” and the like.
Triazine ultraviolet absorbers: “TINUVIN 400”, “TINUVIN 405”, etc.

  The content of the ultraviolet absorber in the pressure-sensitive adhesive composition is such that the ultraviolet absorber can exert its function while ensuring the orange light absorption performance by the tetraazaporphyrin-based dye and other physical properties required for the pressure-sensitive adhesive composition. What is necessary is just a quantity (mixing ratio), and 0.1-30 mass parts is preferable with respect to 100 mass parts of acrylic adhesives, and 0.5-20 mass parts is more preferable.

(Organic solvent)
The pressure-sensitive adhesive composition contains an organic solvent in which the solubility of the tetraazaporphyrin-based dye is 1 g / 100 g or more. The solubility of the organic solvent varies depending on the type of tetraazaporphyrin-based dye that is a solute, for example, the types of R ^{23 to} R ³⁰ of the compound represented by the formula (2). Therefore, an organic solvent having a solubility of 1 g / 100 g or more is selected and used depending on the tetraazaporphyrin-based dye to be used.

  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, Candidates include alcohols such as i-propyl alcohol; hydrocarbons such as hexane; and tetrahydrofuran. In the present invention, among these, those satisfying the above-mentioned solubility conditions for the tetraazaporphyrin-based dye to be used may be appropriately selected and used, and methyl ethyl ketone and toluene are preferable, and methyl ethyl ketone is particularly preferable.

  These organic solvents may be used alone, or two or more kinds thereof may be appropriately mixed and used as necessary. When used alone, it is necessary to satisfy the above-mentioned solubility conditions alone, but when two or more kinds are mixed and used, even if either one does not satisfy the conditions, It can be used if the solubility condition is satisfied.

  Specifically, when the commercially available “TAP-2” and “TAP-HTBX” are used as the tetraazaporphyrin-based dye, methyl ethyl ketone, toluene, xylene, methyl are used as organic solvents that satisfy the above-mentioned solubility conditions. Examples include isobutyl ketone, acetone, methanol, ethanol, i-propyl alcohol, hexane, tetrahydrofuran, and dimethylformamide. Among these, methyl ethyl ketone and toluene are preferable, and methyl ethyl ketone is particularly preferable.

  The content of the organic solvent in the pressure-sensitive adhesive composition may be an amount that can uniformly dissolve the tetraazaporphyrin-based dye, the ultraviolet absorber, and the light stabilizer composed of a copper complex or a nickel complex. The content of the organic solvent in the pressure-sensitive adhesive composition is 100 parts by mass of the total pressure-sensitive adhesive composition in consideration of the content of the tetraazaporphyrin-based dye, the ultraviolet absorber, and the light stabilizer composed of a copper complex or a nickel complex. The amount is preferably 10 to 20 parts by mass, and more preferably 13 to 18 parts by mass.

  The viscosity of the pressure-sensitive adhesive composition is usually adjusted using an organic solvent in consideration of the efficiency when forming the pressure-sensitive adhesive layer in the pressure-sensitive adhesive film or optical filter. The organic solvent is usually an organic solvent that is brought into the pressure-sensitive adhesive composition together with the acrylic pressure-sensitive adhesive as a component that dissolves the acrylic pressure-sensitive adhesive (however, both of the acrylic pressure-sensitive adhesive and the cross-linking agent when a cross-linking agent described later is included). It consists of a solvent and the organic solvent for uniformly dissolving the tetraazaporphyrin-based dye, the ultraviolet absorber, and the light stabilizer composed of a copper complex or a nickel complex. As a component that dissolves the acrylic adhesive, the organic solvent brought into the adhesive composition together with the acrylic adhesive includes a tetraazaporphyrin dye, an ultraviolet absorber, and a light stabilizer comprising a copper complex or a nickel complex. An organic compound similar to the organic solvent for uniformly dissolving can be used.

  The content of the organic solvent in the pressure-sensitive adhesive composition takes into account the uniform dispersibility or solubility of the total solids contained in the pressure-sensitive adhesive composition, the efficiency when forming the pressure-sensitive adhesive layer in the pressure-sensitive adhesive film or optical filter, and the like. And 50-95 mass parts is preferable with respect to 100 mass parts of all the adhesive compositions, and 60-85 mass parts is more preferable.

(Light stabilizer)
The light stabilizer is a light stabilizer composed of a complex having copper or nickel as a central atom, and has a solubility of 3 g / 100 g or more in the organic solvent in which the solubility of the tetraazaporphyrin-based dye is 1 g / 100 g or more. Stabilizers are used. As the light stabilizer, one having a solubility of 3 g / 100 g or more is appropriately selected according to the organic solvent selected from the copper complex or the nickel complex according to the kind of the tetraazaporphyrin-based dye used.
In the pressure-sensitive adhesive composition of the present invention, by using such a light stabilizer, a pressure-sensitive adhesive layer excellent in light resistance of the tetraazaporphyrin-based dye can be formed.

  The complex having copper or nickel as the central atom is preferably a complex in which a ligand selected from organic ligands having an oxygen atom or a sulfur atom as a coordination atom coordinates to a copper atom or a nickel atom. The ligand may be a monodentate ligand or a polydentate ligand. In the present invention, from these complexes, those satisfying the above-mentioned solubility conditions with respect to the organic solvent to be used may be appropriately selected and used.

  As a complex in which a ligand selected from organic ligands having an oxygen atom or a sulfur atom as a coordination atom coordinates to a copper atom or a nickel atom, specifically, as a complex in which the coordination atom is a sulfur atom, dithiol A complex. As a dithiol complex, the dithiol complex shown by following formula (4) is mentioned, for example.

In Formula (4), R ^{39 to} R ⁵⁸ are each independently a hydrogen atom, a halogen atom, an amino group, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a carbon number. An aryl group having 1 to 20 carbon atoms, an aralkyl group having 1 to 20 carbon atoms, or an alkylamino group having 1 to 20 carbon atoms is represented, and M ³ represents copper or nickel.
Here, in the present specification, the “alkylamino group” means both one in which one hydrogen atom of an amino group (—NH ₂ ) is substituted with an alkyl group and one in which two hydrogen atoms are substituted with an alkyl group. It is used as a term including
A benzenedithiol complex represented by the following formula (5) can also be used.

In formula (5), R ⁶¹ and R ⁶² each independently represent a halogen atom, an amino group, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 1 carbon atom. -20 aryl group, C1-C20 aralkyl group, C1-C20 alkylamino group (however, C1-C20 alkyl group, C1-C20 alkoxy group, C1-C20 The aryl group, the aralkyl group having 1 to 20 carbon atoms, and the alkylamino group having 1 to 20 carbon atoms may be substituted with one or more hydrogen atoms by halogen atoms), or bonded via a sulfonyl group. Represents an organic group. M ⁴ represents copper or nickel.
R ⁶¹ and R ⁶² are preferably an organic group bonded via a sulfonyl group. The organic group includes a phenyl group, an alkylamino group in which a nitrogen atom is bonded to two alkyl groups, and a nitrogen atom as a constituent atom. An optionally substituted heterocyclo group having 4 to 6 carbon atoms bonded through the nitrogen atom is preferable. R ⁶¹ and R ⁶² are preferably the same group.

As the dithiol complex represented by the formula (5), specifically, as a commercial product, trade name “EST-3” (dithiol copper complex, bis (4-piperidylsulfonyl-1,2-benzene) manufactured by Sumitomo Seika Co., Ltd. Dithiolate-S, S ′) copper-tetra-nbutylammonium), trade name “EST-5” (dithiol copper complex, bis (4-morpholinosulfonyl-1,2-dithiophenolate) copper-tetra-n-) Butylammonium), trade name “EST-5Ni” (dithiol nickel complex, bis (4-morpholinosulfonyl-1,2-dithiophenolate) nickel-tetra-n-butylammonium) and the like.
Examples of the dithiol complex further include dithiocarbamate represented by the following formula (6).

In Formula (6), R ^{63 to} R ⁶⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms, or an aralkyl group having 1 to 20 carbon atoms. , M ⁵ represents copper or nickel.
R ^{63 to} R ⁶⁵ are preferably the same alkyl group having 1 to 4 carbon atoms, particularly preferably a methyl group, an ethyl group, an n-butyl group, a tert-butyl group, or the like. Specifically, bis (dibutyldithiocarbamate) nickel (II), bis (dibutyldithiocarbamate) copper (II), bis (diethyldithiocarbamate) copper (II), bis (diethyldithiocarbamate) nickel (II), etc. Can be mentioned.

Examples of the complex in which the coordination atom is an oxygen atom include a salicylate represented by the following formula (7), a benzenesulfonate represented by the following formula (8), and the like.

In Formula (7), X ¹ and X ² are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms, or an aralkyl group having 1 to 20 carbon atoms (however, In the alkyl group having 1 to 20 carbon atoms, the aryl group having 1 to 20 carbon atoms, and the aralkyl group having 1 to 20 carbon atoms, one or more hydrogen atoms may be substituted with halogen atoms. n and m each independently represent an integer of 0 to 4, and when n and m are 2 to 4, X ¹ and X ² may be the same or different. M ⁶ represents a copper or nickel.

In formula (8), X ³ and X ⁴ each independently represent a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms, an aralkyl group having 1 to 20 carbon atoms (provided that In the alkyl group having 1 to 20 carbon atoms, the aryl group having 1 to 20 carbon atoms, and the aralkyl group having 1 to 20 carbon atoms, one or more hydrogen atoms may be substituted with halogen atoms. s and t each independently represent an integer of 0 to 5, and when s and t are 2 to 5, X ³ and X ⁴ may be the same or different. M ⁷ represents copper or nickel.

  As a complex in which the coordination atom is an oxygen atom, a salt of phthalic acid or an analogous compound thereof can also be used.

  The chemical structure of the complex having copper or nickel as the central atom has been specifically described above, but the pressure-sensitive adhesive composition of the present invention includes the types of tetraazaporphyrin-based dyes used above among these light stabilizers. According to the organic solvent selected by the above, a light stabilizer having a solubility in the organic solvent of 3 g / 100 g or more at 25 ° C. is appropriately selected.

  For example, when a tetraazaporphyrin dye selected from the above-mentioned commercially available “TAP-2” and “TAP-HTBX” is used as the tetraazaporphyrin dye, and methyl ethyl ketone is used as the organic solvent, the solubility in methyl ethyl ketone is 3 g. Examples of the light stabilizer that is 100 g or more include bis (dibutyldithiocarbamate) nickel (II), bis (dibutyldithiocarbamate) copper (II), “EST-3”, and the like.

  The light stabilizer selected from these complexes having copper or nickel as the central atom may be used alone, or two or more kinds may be appropriately mixed and used as necessary. When used alone, it is necessary to satisfy the above-mentioned solubility condition alone, but when two or more kinds are mixed and used, even if either one does not satisfy the condition, the above-mentioned solubility is obtained. It can be used if the above conditions are satisfied.

  The light stabilizer is an amount (mixing ratio) in which the light stabilizer can exert its function while ensuring the orange light absorption performance by the tetraazaporphyrin-based dye and other physical properties required for the pressure-sensitive adhesive composition. The acrylic pressure-sensitive adhesive (however, when a cross-linking agent described below is included, the total amount of the acrylic pressure-sensitive adhesive and the crosslinking agent) is preferably 0.001 to 10 parts by weight, and 0.01 to 1 part by weight. Part is more preferred.

(Acrylic adhesive)
The acrylic pressure-sensitive adhesive functions as a binder having an adhesive property for forming a layer with the above components uniformly dispersed in the pressure-sensitive adhesive composition of the present invention to form a pressure-sensitive adhesive layer. The acrylic pressure-sensitive adhesive is made of a (co) polymer containing a polymerization unit based on an acrylic monomer as a main component. Examples of the acrylic monomer include (meth) acrylic acid, itaconic acid, (anhydrous) maleic acid, (anhydrous) fumaric acid, crotonic acid, and alkyl esters thereof. In order to increase the cohesive strength of the pressure-sensitive adhesive, it is preferable to use an acrylic monomer having a functional group that can serve as a crosslinking point (for example, a hydroxy group, an epoxy group, etc., hereinafter also referred to as “crosslinkable group”). . Here, “(meth) acrylic acid” is a generic term for acrylic acid and methacrylic acid. The same applies to (meth) acrylate.

  Among acrylic monomers, (meth) acrylic acid, alkyl esters thereof, and (meth) acrylic monomers selected from (meth) acrylic monomers having a crosslinkable group are the main components. It is preferable. Here, the main component means that the (meth) acrylic acid monomer is contained in an amount of 95% by mass or more, more preferably 98% by mass or more, and 99% by mass or more. Is more preferable.

Examples of alkyl esters of (meth) acrylic acid include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, and n-hexyl (meta ) Acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, and the like. .
Moreover, as a (meth) acrylic-acid type monomer which has a crosslinkable group, hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, etc. are mentioned preferably, for example.

  The acid value of the acrylic pressure-sensitive adhesive is preferably 10 mgKOH / g or less. The acid value may be 0 mgKOH / g. The acid value of the acrylic pressure-sensitive adhesive is more preferably 0 to 7 mgKOH / g, and particularly preferably 0 to 5 mgKOH / g. When the acid value of the acrylic pressure-sensitive adhesive is 10 mgKOH / g or less, discoloration after the moisture resistance test can be suppressed. The acid value here is a value obtained by titration of alcoholic potassium hydroxide (KOH) using phenolphthalein as an indicator.

  In order to set the acid value of the acrylic pressure-sensitive adhesive to 10 mgKOH / g or less, the amount of the monomer having a carboxyl group used for copolymerization so that the acid value falls within this range when the acrylic monomer is polymerized. Adjust. Similarly, in order to make the degree of crosslinking within a desired range, the amount of the monomer having a crosslinkable group used for copolymerization may be adjusted. Hereinafter, in the present specification, an acrylic pressure-sensitive adhesive made of a copolymer containing a monomer having a crosslinkable group is referred to as a crosslinkable acrylic pressure-sensitive adhesive.

  Crosslinkable acrylic pressure-sensitive adhesives having an acid value of 10 mgKOH / g or less are commercially available, and may be appropriately selected from them. For example, product name: “NCK101” manufactured by Toyo Ink Co., Ltd. (acid value = 0 mgKOH / g, organic solvent content 70 parts by mass), product name: “EXK04-488” manufactured by Toyo Ink Co., Ltd. (acid value: 6.2 mgKOH / g ) And the like.

  Moreover, -40-40 degreeC is preferable and, as for the glass transition temperature (Tg) of an acrylic adhesive, -30-10 degreeC is more preferable.

When using the said crosslinkable acrylic adhesive as an acrylic adhesive, it is preferable to add a crosslinking agent to an adhesive composition. The cohesive force can be secured by reacting the crosslinking agent with a crosslinkable group to crosslink the acrylic copolymer. Examples of the crosslinking agent include melamine resin, urea resin, epoxy resin, metal oxide, metal salt, metal hydroxide, metal chelate, polyisocyanate, carboxy group-containing polymer, acid anhydride, polyamine, etc. It is suitably selected according to the type of
As the crosslinking agent used in combination with these acrylic pressure-sensitive adhesives, when the crosslinkable group is a hydroxy group, a polyisocyanate is preferable. it can.

  The content of the acrylic pressure-sensitive adhesive solid content and the crosslinking agent in the pressure-sensitive adhesive composition is preferably 5 to 50% by mass and more preferably 15 to 40% by mass with respect to the total amount of the composition for the acrylic pressure-sensitive adhesive. The amount of the crosslinking agent is preferably such that the molar amount of the reactive group of the crosslinking agent is 0.01 to 10 times the molar amount of the crosslinkable group in the acrylic pressure-sensitive adhesive. Is more preferred.

(Near-infrared absorbing dye)
The pressure-sensitive adhesive composition of the present invention may contain a near-infrared absorbing dye as an optional component. The near infrared absorbing dye is not particularly limited as long as it is a dye having absorption in the near infrared wavelength region (750 to 1100 nm).
As the near infrared absorbing dye, for example, polymethine dye, phthalocyanine dye, naphthalocyanine dye, metal complex dye, aminium dye, imonium dye, diimonium dye, anthraquinone dye, dithiol metal complex dye, Examples thereof include naphthoquinone dyes, indolephenol dyes, azo dyes, triallylmethane dyes, and tungsten oxide dyes. Among these, dithiol metal complex dyes, aminium dyes, phthalocyanine dyes, naphthalocyanine dyes, diimonium dyes, and tungsten oxide dyes are preferable.

  The near-infrared absorbing dye may be one kind or a mixture of two or more kinds. From the viewpoint of durability of the near-infrared absorbing dye, it is preferable to use only one kind or a combination of two or more phthalocyanine dyes. Further, in addition to durability, it is more preferable to use a combination of two or more phthalocyanine dyes because they can absorb near infrared rays sufficiently and efficiently. Furthermore, in order to suppress unnecessary absorption of light in the visible light region and to absorb light in the near infrared wavelength region sufficiently specifically, it has a maximum wavelength in the wavelength region of 800 to 1000 nm, but has different maximum wavelengths. It is particularly preferable to contain four or more phthalocyanine dyes having

<Phthalocyanine dye>
As the phthalocyanine-based dye, as long as it is a compound having a phthalocyanine skeleton, 16 atoms or substituents bonded to the skeleton are not particularly limited. From the viewpoint of durability, a phthalocyanine dye having 4 or more phenyl groups in which at least one hydrogen atom is unsubstituted or substituted with an alkyl group or a group having the phenyl group at the terminal is preferable as the atom or substituent. Specific examples of such phthalocyanine dyes include phthalocyanine dyes represented by the above formula (1).

In formula (1), R ^{1 to} R ¹⁶ are each independently a hydrogen atom, a halogen atom, a hydroxy group, an amino group, a hydroxysulfonyl group, an aminosulfonyl group, or a hydrocarbon group having 1 to 20 carbon atoms (however, the carbon A hydrogen group may contain one or more atoms selected from the group consisting of a nitrogen atom, a sulfur atom, an oxygen atom and a halogen atom), and two adjacent substituents are connected via a linking group. May be. Provided that at least four of R ² , R ³ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , R ¹⁴ , R ¹⁵ are unsubstituted or a phenyl group in which at least one of hydrogen atoms is substituted with an alkyl group or This is a group having a phenyl group at the terminal (hereinafter referred to as “Ph-containing group”).
Hereinafter, R ² , R ³ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , R ¹⁴ , R ¹⁵ are group A, and other R ¹ , R ⁴ , R ⁵ , R ⁸ , R ⁹ , R ¹² , Let R ¹³ and R ¹⁶ be group B. It is preferable that all eight groups or atoms of the group A are Ph-containing groups, for example, a group represented by the following formula (9).

［式（９）中、Ｒ^７１〜Ｒ^７５は、それぞれ独立に水素原子またはアルキル基であり、Ｘは、単結合、Ｏ、Ｓ、ＮＨ、または炭素数１〜６の直鎖アルキレン基を示す。］
式（９）中、Ｒ^７１〜Ｒ^７５が、アルキル基である場合、炭素数１〜３のアルキル基が好ましく、メチル基が特に好ましい。
式（９）で示される基として、好ましくは、フェニルチオール基（−Ｓ−Ｐｈ）、２−メチルフェニルオキシ基、２，４，６−トリメチルフェニルチオール基等が挙げられる。

Wherein ^{(9), R} 71 ~R ⁷⁵ are each independently a hydrogen atom or an alkyl group, X represents a single bond, O, S, NH, or a straight-chain alkylene group having 1 to 6 carbon atoms . ]
Wherein ^{(9), R} 71 ~R ⁷⁵ is when it is alkyl group, preferably an alkyl group having 1 to 3 carbon atoms, a methyl group is particularly preferred.
Preferred examples of the group represented by the formula (9) include a phenylthiol group (—S—Ph), a 2-methylphenyloxy group, and a 2,4,6-trimethylphenylthiol group.

M ² represents a divalent metal atom, a trivalent substituted metal atom, a tetravalent metal atom, or an oxy metal. Specific examples of M ² include Cu, Ni, Zn, Pd, Pt, VO, Co, and Mg. Among these, M ² is preferably Cu or VO from the viewpoints of economy, safety, solubility, and optical characteristics.

  When the group A or atom is not a Ph-containing group, they are a hydrogen atom, a halogen atom, a hydroxy group, an amino group, a hydroxysulfonyl group, an aminosulfonyl group, or a hydrocarbon group having 1 to 20 carbon atoms (provided that The hydrogen group is a group other than a Ph-containing group which may contain one or more atoms selected from the group consisting of a nitrogen atom, a sulfur atom, an oxygen atom and a halogen atom.

  Group B group or atom is hydrogen atom, halogen atom, hydroxy group, amino group, hydroxysulfonyl group, aminosulfonyl group, or hydrocarbon group having 1 to 20 carbon atoms (however, hydrocarbon group is nitrogen atom, sulfur atom) , One or more atoms selected from the group consisting of an oxygen atom and a halogen atom may be contained, or a Ph-containing group.

Here, the hydrocarbon group having 1 to 20 carbon atoms (however, the hydrocarbon group may contain one or more atoms selected from the group consisting of a nitrogen atom, a sulfur atom, an oxygen atom and a halogen atom) is alkyl. An amino group is included.
Two groups or atoms of group B exist for every four benzene rings of the phthalocyanine skeleton, one of which may be an alkylamino group. Examples of the alkylamino group include —NHR ⁸⁰ (R ⁸⁰ is a benzyl group, a phenyl group, or a linear or branched alkyl group having 1 to 20 carbon atoms), and —NR ⁸¹ R ⁸² (R ⁸¹ , R ⁸² is each independently a linear or branched alkyl group having 1 to 10 carbon atoms. In the case of —NHR ⁸⁰ , examples of R ⁸⁰ include a benzyl group, a 2-ethylhexyl group, an n-propyl group, and an n-butyl group. In the case of —NR ⁸¹ R ⁸² , examples of R ⁸¹ and R ⁸² include a combination in which both are a methyl group, an ethyl group, or an isobutyl group.

  The other group or atom of the group B group or atom bonded to each of the four benzene rings includes a 2,6-dimethylphenyloxy group, an alkylamino group, a trimethylphenylthiol group, and the like.

As the phthalocyanine-based dye, those having desired characteristics may be appropriately selected from commercially available products. For example, all of them are trade names manufactured by Nippon Shokubai Co., Ltd., “EEX Color IR-14” (in the above formula (1), all eight groups of group A are 2,5-dichlorophenyloxy groups, group B groups 4 are benzylamino groups, 4 are 2,6-dimethylphenyloxy groups, and M ² is copper.), “Ex color IR-10A”, “Ex color IR-28”, “Ex color. IR-12 "," TX-EX-820 "(in the above formula (1), all 8 groups A are phenylthiol groups, 4 groups B are 2-ethylhexylamino groups, 4 are 2 groups) , 6-dimethylphenyl group, ^{M 2} is copper.), "TX-EX-906", "EXCOLOR IR-915", "EXCOLOR IR-910", "EXCOLOR IR 906 ", and the like.

In addition, the trade name “KSK-5” manufactured by Yamada Chemical Co., Ltd. (in the above formula (1), all eight groups in group A are all 4-trifluoromethylphenyloxy groups, all eight groups in group B are 2, 4,6-triisopropylphenyl thiol group, ^{M 2} is VO.), "KSK-10" 4 in (the above formula (1), group 8 with phenyl thiol group of the group a, the group of group B Are diisobutylamino groups, 4 are 2,6-dimethylphenyloxy groups, M ² is VO), “KSK-15” (in the above formula (1), all 8 groups A are phenylthiol Group, four of group B groups are dimethylamino groups, four are 2,6-dimethylphenyloxy groups, M ² is VO), “KSK-16” (in the above formula (1), group A All 8 groups -.-Methylphenyl group, a group B of four dimethylamino group group, 4 is 2,6-dimethylphenyl group, ^{M 2} is VO), "KSK-17" (the above formula (1) in the group of group a with eight 2-methylphenyl group, 4 groups of the group B is dimethylamino group, 4 is 2,4,6-triisopropyl-phenyl thiol group, ^{M 2} is a VO ), “KSK-20” (in the above formula (1), all eight groups in group A are 2-methylphenyloxy groups, all eight groups in group B are dimethylamino groups, and M ² is VO.) ), “KSK-22” (in the above formula (1), 8 groups A and 4 groups B are 2,4,6-trimethylphenylthiol groups, 4 groups B groups are n- butylamino group, M There is a VO.), The same structure as the "KSK-100" (the "EXCOLOR IR-14"), such as "KSK-101" (the same structure as the above-mentioned "TX-EX-820") is given It is done.

  Among these, from the viewpoint that group A in the above formula (1) contains 4 or more Ph-containing groups, “KSK-10”, “KSK-15”, “KSK-16”, “KSK-17”, “KSK-20”, “KSK-22”, “KSK-101”, and “TX-EX-820” are preferable.

  The content of the near-infrared absorbing dye in the pressure-sensitive adhesive composition is 0.1 to 100 parts by mass with respect to 100 parts by mass of the acrylic pressure-sensitive adhesive (however, when a cross-linking agent described later is included). 20 mass parts is preferable and 0.2-10 mass parts is more preferable. By setting the content of the near-infrared absorbing pigment to 0.1 parts by mass or more, the function of absorbing near infrared rays in the wavelength region of 820 to 980 nm can be sufficiently exhibited, and by setting the content to 20 parts by mass or less, the durability is lowered. Can be suppressed.

  The pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition of the pressure-sensitive adhesive film or optical filter of the present invention preferably has a near infrared transmittance of 20% or less in the wavelength region of 820 to 980 nm, and 15% or less. More preferred. The content of each pigment in the pressure-sensitive adhesive layer is preferably adjusted appropriately so that the near-infrared transmittance is in the above range.

(Other optional ingredients)
The pressure-sensitive adhesive composition of the present invention further includes, as an optional component, a color tone correction dye other than the tetraazaporphyrin-based dye, a leveling agent, an antistatic agent, a heat stabilizer, and an antioxidant as necessary in addition to the near infrared absorbing dye. In addition, components such as a dispersant, a flame retardant, a lubricant, and a plasticizer may be contained within a range that does not impair the effects of the present invention.

<Color tone correction dye>
Similar to the tetraazaporphyrin-based dye, the color tone correction dye absorbs a part of a specific wavelength region of visible light and improves the color tone of transmitted visible light. Examples of color correction dyes include azo, condensed azo, diimonium, phthalocyanine, anthraquinone, indigo, perinone, perylene, dioxazine, quinacridone, methine, isoindolinone, and quinophthalone. Preferable organic pigments and organic dyes such as pyrrole, thioindigo, metal complex, and porphyrin other than tetraazaporphyrin, and inorganic pigments are preferable.

  Among color correction dyes, they have good weather resistance and good compatibility or dispersibility with acrylic pressure-sensitive adhesives, for example, one kind selected from anthraquinone dyes and quinophthalone dyes, or a combination of two or more kinds as appropriate Are preferably used. It is more preferable to use one or two or more selected from anthraquinone dyes in appropriate combination.

  Examples of anthraquinone dyes include commercial products such as trade names “Kayaset Violet AR”, “Kayaset Blue N”, “Kayaset Blue FR”, and “Kayaset Green AB” manufactured by Nippon Kayaku Co., Ltd. It is done.

As the color tone correcting dye, a dye having no hydroxy group (—OH) and amino group (—NH ₂ ) is preferable. Dye in the pressure-sensitive adhesive composition of the present invention preferably contains only the dye having substantially no hydroxy group (-OH) and amino group (-NH _2). The phrase “substantially containing only a dye having no hydroxy group and amino group” means that 95% by mass or more of the dye having no hydroxy group and amino group is contained with respect to the total amount of the dye in the pressure-sensitive adhesive composition. Meaning 98% by mass or more is more preferable, and 99% by mass or more is more preferable. By using a dye having no hydroxy group and amino group, the pressure-sensitive adhesive composition containing the dye does not change color due to moisture, and deterioration such as fading can be suppressed.

  The intensity and wavelength distribution of visible light emission vary depending on the type and model of the display. Therefore, the color tone correction dye used arbitrarily in the pressure-sensitive adhesive composition of the present invention is appropriately selected from the type and combination of color tone correction dyes used depending on the type and model of the display. From the viewpoint of durability, anthraquinone dyes are preferable.

  The content of the color tone correction pigment in the pressure-sensitive adhesive composition is adjusted according to the luminous transmittance of the C light source required for the optical filter and the color tone of the transmitted light. The content of the color tone correction dye is appropriately selected depending on the kind of the dye to be used, and is 100 parts by weight of the acrylic pressure-sensitive adhesive (however, when the cross-linking agent is included as described above, the total amount of the acrylic pressure-sensitive adhesive and the cross-linking agent). 0.001 to 20 parts by mass is preferable, and 0.01 to 10 parts by mass is more preferable.

  In preparing the pressure-sensitive adhesive composition, the types and blending amounts of various dyes are appropriately selected according to the optical characteristics required for the optical filter having a pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive composition.

  In the above-mentioned pressure-sensitive adhesive composition of the present invention, the pressure-sensitive adhesive layer formed by using the above composition is a layer excellent in light resistance of the contained tetraazaporphyrin-based dye.

[Adhesive film]
In the pressure-sensitive adhesive film of the present invention, a pressure-sensitive adhesive layer made of the above-described pressure-sensitive adhesive composition is formed on a film as a substrate.

(the film)
The film in the present invention may be in the form of a film or a plate, and the material, thickness, etc. are not particularly limited.
Examples of such a film include a peelable film having a peelability, a support film, and a film having a function other than those (hereinafter, functional film). Further, the film may be a single layer or two or more layers.

The material of the film is not limited, but a resin film is preferable from the viewpoint of ease of handling when the film is handled when manufacturing an adhesive film.
Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT); polyolefins such as polyethylene and polypropylene; polyacrylates such as polymethyl methacrylate (PMMA); polycarbonates (PC); A film made of any one of triacetate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, ethylene-vinyl acetate copolymer, polyvinyl butyral, polyurethane, cellophane, and the like. The thickness of the film is preferably 30 to 130 μm.

About the support film, the said resin film itself can be used as a support film. The thickness of the support film is preferably 80 to 130 μm, particularly preferably 100 to 125 μm.
About a peelable film, what has sufficient peelability among the said resin films may be used as it is as a peelable film as it is, The thing by which the release agent was coated to the said resin film can be used preferably. 30-90 micrometers is preferable and, as for the thickness of a peeling film, 38-75 micrometers is especially preferable.

  Examples of the functional film include an ultraviolet absorbing film for improving light resistance by preventing deterioration of a pigment due to ultraviolet rays, and a color tone correcting film for absorbing light in a specific wavelength region other than ultraviolet rays. The specific wavelength absorbed by the color tone correction film may include not only visible light but also near infrared light, and may absorb a plurality of specific wavelength regions. Furthermore, examples of the functional film include an antireflection film for improving image visibility, an electromagnetic wave shielding film for cutting electromagnetic waves emitted from a display such as a PDP, a contrast improving film, and an antiglare film. .

  In addition, a hard coat layer or a self-healing layer that provides a scratch-resistant function on the resin film, or an antifouling layer for preventing dirt on the outermost surface, an adhesive or adhesive layer for laminating each layer, etc. May be used as a functional film.

Examples of the electromagnetic wave shielding film include those in which an electromagnetic wave shielding film is formed on the above resin film by a sputtering method and those in which copper is formed in a mesh shape. Examples of the electromagnetic wave shielding film include a layer of metal oxide (oxide of In and Sn, oxide of Ti and Zn, oxide of Al and Zn, niobium oxide, etc.) and metal (Ag, Ag alloy, etc.) ), And the number of metal layers is n, and the number of metal oxide layers is n + 1 (where n is an integer of 1 or more). Moreover, as an electromagnetic wave shielding film, for example, copper formed in a mesh shape on the resin film may be used.
A commercially available product can be used as the electromagnetic wave shielding film. As a commercial item, Dai Nippon Printing Co., Ltd. product name "AR50GA0T-75" etc. are mentioned as an electromagnetic wave shielding etching mesh film, for example.

  Examples of the antireflection film include those in which an antireflection film made of a low refractive index material containing a fluoropolymer is formed on one surface of the resin film, for example, a polyethylene terephthalate film. Specifically, commercial products such as trade name: ARCTOP (URP2199) manufactured by Asahi Glass Co., Ltd. and trade names: Realak (RL7800, RL9000, RL9200, RL9900) manufactured by Nippon Oil & Fats Co., Ltd. may be mentioned. Specifically, the low refractive index is preferably 1.1 to 1.6, more preferably 1.2 to 1.5, and still more preferably 1.3 to 1.48.

  Examples of the contrast enhancement film include a film in which a plurality of linear dark color portions arranged in parallel on the resin film and a translucent region disposed between the dark color portions are formed. The translucent region is, for example, a trapezoidal shape whose width gradually increases toward the resin film in the cross section in the side-by-side direction, and is formed so as to be connected to another adjacent translucent region at the end on the resin film side. ing. Moreover, a dark color part is comprised by filling a dark color particle and transparent resin in the recessed part between adjacent translucent area | regions, for example.

  An anti-glare film is a functional film in which an anti-glare film (anti-glare film) for reducing reflection due to reflection of visible light is provided on the resin film, and has an uneven surface. There is an effect of blurring the outline by diffusing a reflection image reflected on the surface of the antiglare film due to the unevenness. As an antiglare film, a solution in which inorganic fine particles such as silica or organic fine particles such as acrylic resin and styrene resin are dispersed in a binder resin is coated on the resin film, and the solvent is volatilized, sandblasted, or etched. What formed the unevenness | corrugation in resin film itself by the above etc. is mentioned. Further, an antireflection treatment may be applied to the outermost layer. As the anti-glare film, for example, commercially available products such as trade names “DS-LR” and “DS-21” manufactured by Dai Nippon Printing Co., Ltd. and product names manufactured by NOF Corporation: Rialc (RL5500, RL7300) are preferably used. .

(Adhesive layer)
The pressure-sensitive adhesive layer can be formed, for example, by coating a pressure-sensitive adhesive composition on a film, volatilizing an organic solvent and drying it. Examples of the coating method for the pressure-sensitive adhesive composition include dip coating, spray coating, spinner coating, bead coating, wire bar coating, blade coating, roller coating, curtain coating, and slitting. A coating method such as a die coater method, a gravure coater method, a slit reverse coater method, a micro gravure method, or a comma coater method can be employed.

  The thickness of the pressure-sensitive adhesive layer is preferably 0.3 to 50.0 μm, and more preferably 0.5 to 30.0 μm. By setting the thickness to 0.3 μm or more, the color tone correction function of absorbing unnecessary light in the vicinity of a wavelength of 590 nm possessed by the tetraazaporphyrin-based dye can be sufficiently exhibited. be able to.

  After providing the pressure-sensitive adhesive layer on the film, it is preferable from the viewpoint of workability that a release film is stuck on the pressure-sensitive adhesive layer because the pressure-sensitive adhesive layer can be protected until use. As the release film, the same film as the above-described peelable film can be used.

[Optical filter]
The optical filter of the present invention is an optical filter in which one or more films are attached to a substrate, and between the film and the substrate, or between the films in the case where the number of the films is two or more, It has the adhesive layer formed using the adhesive composition of the said invention.

  As a film, films other than the peelable film which has peelability among the films used for said adhesive film, for example, a support film, a functional film, etc. are mentioned similarly. The preferred embodiments of these films are the same as above. In the optical filter of the present invention, one or more of the above functional films are usually used as the film.

Examples of the substrate include a transparent substrate made of glass, a transparent and highly rigid polymer material, and the like. Specific examples of transparent and highly rigid polymer materials include polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate, polyacrylates such as polymethyl methacrylate (PMMA), polycarbonate (PC), polystyrene, triacetate, and polyvinyl alcohol. , Polyvinyl chloride, polyvinylidene chloride, polyethylene, ethylene-vinyl acetate copolymer, polyvinyl butyral, metal ion crosslinked ethylene methacrylic acid copolymer, polyurethane, cellophane and the like.
Preferably, a transparent substrate made of glass, tempered or semi-tempered glass, polycarbonate, polyacrylate or the like is used. An optical filter having an adhesive film attached to a transparent substrate exhibits a function as a protective plate for a display such as a PDP.

The thickness of the substrate is preferably 1 to 10 mm, and more preferably 1.5 to 5 mm. By being 1 mm or more, a display such as a PDP can be sufficiently protected from an impact. The weight of the optical filter can be reduced by being 10 mm or less. Further, the Young's modulus of the substrate is preferably 1 × 10 ⁹ Pa or more, more preferably 5 × 10 ⁹ Pa or more, and further preferably 1 × 10 ¹⁰ Pa or more. The upper limit of Young's modulus is not particularly limited, but the upper limit is preferably 5 × 10 ¹¹ Pa. It is preferable that the Young's modulus of the substrate is within the above range because the optical filter can be made sufficiently hard to protect a display such as a PDP.

The method for producing the optical filter is not particularly limited. An optical filter having an adhesive layer made of the above-mentioned adhesive composition between a substrate and a film, for example, prepares an adhesive film in which an adhesive layer is formed on a peelable film, and adheres the adhesive film to the substrate. Adhere the agent layer. Thereafter, the peelable film is peeled off from the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film, a functional film is stuck on the exposed pressure-sensitive adhesive layer, and another functional film can be bonded as necessary.
Moreover, as another manufacturing method, the adhesive film in which the adhesive layer is formed on the functional film is prepared, and the adhesive layer of an adhesive film is stuck on a board | substrate. And an optical filter can be obtained by bonding another functional film as needed.

The optical filter having the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition between a plurality of films, for example, firstly, a functional film is bonded to a substrate, and then the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is formed on a peelable film. The formed adhesive film is prepared and the adhesive layer of the adhesive film is stuck on the functional film. Subsequently, it can obtain by peeling a peelable film from the adhesive layer of the said adhesive film, and sticking another functional film on the exposed adhesive layer.
As another manufacturing method, first, a functional film is bonded to a substrate, and then an adhesive film in which an adhesive layer made of the above-mentioned adhesive composition is formed on the other functional film is prepared. An optical filter can be obtained by sticking the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film on the film.

  In the above bonding, the surface of the pressure-sensitive adhesive film opposite to the substrate is subjected to pressure treatment by moving a pressure roller covered with an elastic material such as rubber from one end side to the other end side. Also good. The treatment with the pressure roller may be performed for each bonding, may be performed once after all the bonding is performed, or all the bonding is performed, and the processing with the pressure roller is performed. After the pressure treatment is performed, it is preferable to perform a heat treatment for about 20 to 120 minutes in an atmosphere at a temperature of 30 to 80 ° C. and a pressure of 0.6 to 1.2 MPa. By this treatment, the bubbles between the functional films are eliminated, and the appearance can be improved.

The optical filter of the present invention can be used as an optical filter for a flat display such as a PDP, a plasma addressed liquid crystal (PALC) display panel, a field emission display (FED) panel, and a display such as a cathode ray tube display (CRT). it can.
In this case, the optical filter may be installed on the viewing side of the display, may be installed away from the display, or may be directly attached to the display surface.

  In the optical filter, the pressure-sensitive adhesive layer is colored with a pigment, but since the optical filter is generally disposed on the viewing side of a display such as a PDP, an achromatic color is preferred. In the C light source standard calculated according to JIS Z 8701 (1999), the chromaticity coordinates corresponding to the achromatic color are (x, y) = (0.310, 0.316). The filter preferably has chromaticity coordinates (x, y) = (0.310 ± 0.100, 0.316 ± 0.100). Examples of a method for setting the chromaticity coordinates of the optical filter to such values include, for example, the type and content of the dye to be contained in the pressure-sensitive adhesive, and a color tone correction dye as appropriate. For example, a method of selecting the type of substrate.

Further, the luminous transmittance of the optical filter is preferably 20% or more, and more preferably 25% or more. Examples of the method for setting the luminous transmittance of the optical filter to 20% or more include, for example, a method for selecting a highly transparent film, the type and content of the dye contained in the pressure-sensitive adhesive, and a color correction dye. The method of doing is mentioned. The luminous transmittance of the optical film is preferably 80% or less, and more preferably 70% or less. Most preferably, it is 60% or less.
Furthermore, it is preferable that the above chromaticity coordinate (x, y) and luminous transmittance are simultaneously satisfied.

  Since the optical filter described above has a pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive composition of the present invention, a color tone correction function that absorbs unnecessary light in the vicinity of a wavelength of 590 nm possessed by a tetraazaporphyrin-based dye. In addition, it has excellent light resistance to provide its functions stably over a long period of time.

  Hereinafter, the pressure-sensitive adhesive composition, pressure-sensitive adhesive film, and optical filter for display of the present invention will be described more specifically with reference to examples. Examples 1 to 6 are examples, and examples 7 to 11 are comparative examples.

The compounds used below will be described. Here, λ _max represents the maximum absorption wavelength, and ε represents the molar extinction coefficient.
(Tetraazaporphyrin dye)
Hereinafter, manufactured by Yamada Chemical Co., Ltd., trade name “TAP-HTBX”: solubility in methyl ethyl ketone (MEK); 1.2 g / 100 g, λ _max ; 595 nm, ε; 112000
“TAP-2”: solubility in MEK; 10 g / 100 g, λ _max ; 593 nm, ε; 81000

(Light stabilizer)
“Nicarbamate”: Wako Pure Chemical Industries, bis (dibutyldithiocarbamate) nickel (II), solubility in MEK; 5 g / 100 g.
“EST-3”: manufactured by Sumitomo Seika Co., Ltd., trade name, solubility in MEK; 16.7 g / 100 g.
“AQ-1”: manufactured by Yamada Chemical Co., Ltd., trade name, compound represented by the following formula (cf-1), solubility in MEK; 1 g / 100 g.

“AQ-2”: Yamada Chemical Co., Ltd., trade name, compound represented by the following formula (cf-2), solubility in MEK; 2 g / 100 g.

“AQ-5”: manufactured by Yamada Chemical Co., Ltd., trade name, compound represented by the following formula (cf-3), solubility in MEK; 0.5 g / 100 g.

“AQ-6”: manufactured by Yamada Chemical Co., Ltd., trade name, compound represented by the following formula (cf-4), solubility in MEK; 1.8 g / 100 g.

(Phthalocyanine dye)
Hereinafter, the product name “IR-...” Manufactured by Nippon Shokubai Co., Ltd. is an abbreviation for “e-EX color IR-.
“IR-14”: λ _max : 836 nm, ε; 45900
“IR-28”: λ _max : 885 nm, ε; 42100
“TX-EX-906”: λ _max : 938 nm, ε; 49000
“IR-915”: λ _max : 963 nm, ε; 53600
Hereinafter, trade name “KSK-10” manufactured by Yamada Chemical Co., Ltd .: λ _max : 965 nm, ε; 158000
“KSK-15”: λ _max : 934 nm, ε; 120,000
“KSK-16”: λ _max : 875 nm, ε; 118000
“KSK-20”: λ _max : 978 nm, ε; 92400

[Example 1]
MEK 6 parts by mass tetraazaporphyrin-based dye “TAP-HTBX” 0.0153 parts by mass, as light stabilizer Nicarbamate (made by Wako Pure Chemical Industries) 0.0428 parts by mass, UV absorber (BASF company name, trade name) “CHIMASSORB 81”) 1.125 parts by mass was added and dissolved by stirring for 10 minutes with a mixer. To this solution, 30 parts by mass of an acrylic pressure-sensitive adhesive (trade name “NCK101” manufactured by Toyo Ink Co., Ltd., acid value: 0 mg KOH / g, Tg: −20 ° C., organic solvent content 70 parts by mass) and a crosslinking agent (Nippon Polyurethane Co., Ltd.) (Trade name “Coronate HL”) was added in an amount of 0.35 parts by mass, and the mixture was further stirred and dissolved for 10 minutes to prepare a dye-containing pressure-sensitive adhesive composition. The composition of the dye-containing pressure-sensitive adhesive composition is shown in Table 1.

  The above-mentioned dye-containing pressure-sensitive adhesive composition is applied with an applicator on a separator having a silicone resin layer formed on the surface of a PET film, and dried in an oven at 100 ° C. for 5 minutes to form a dye-containing pressure-sensitive adhesive layer having a thickness of 25 μm. Thus, an adhesive film was obtained.

Moreover, the contrast improvement film was manufactured as shown below.
A 100 μm thick strip-like PET film (trade name “A4300”, manufactured by Toyobo Co., Ltd.) treated with easy adhesion on both sides as a transparent support was prepared, and an ultraviolet curable prepolymer comprising urethane acrylate prepolymer and light A composition for forming a translucent region containing a polymerization initiator was applied to a thickness of 89 μm.

  A metal shaping roll is pressed against the surface of the coating layer, and the composition for forming a translucent region is cured by irradiating ultraviolet rays from the back while engraving grooves for forming dark portions. Sex regions were formed. The grooves were formed in a substantially trapezoidal cross section, with a width of 10 μm on the opening side, a width of 7 μm on the bottom side, a depth of 69 μm, and a pitch of 51 μm. The shaping roll has a convex portion corresponding to the groove portion in the circumferential direction, and is rotated in the longitudinal direction on a strip-shaped PET film coated with the above-described translucent region forming composition. A groove was formed.

  On the other hand, in 100 parts by mass of a transparent acrylic UV-curable prepolymer, 50 parts by mass of black spherical bead-like particles having a minimum particle size of 2 μm and a maximum particle size of 3 μm, and 1-hydroxy-cyclohexyl as a photopolymerization initiator -2 parts by mass of phenyl-ketone (trade name “Irgacure 184” manufactured by Ciba Specialty Chemicals Co., Ltd.) was mixed to prepare a liquid dark part forming composition.

  This composition for forming a dark color part was applied mainly to the groove part of the above-described translucent region, and was wiped with a doctor blade. At the time of wiping, the composition for forming a dark color part was cured by irradiating ultraviolet rays from the back side at the same time. The wiping was repeated twice with the gap between the flat part of the translucent region and the doctor blade being 1.5 μm. As a result, a dark color portion is formed in the groove portion, and only the resin component is left on the flat portion of the translucent region with a thickness of 1.5 μm, and cured by irradiation with the above-described ultraviolet rays, thereby transparent protection with a thickness of 1 μm. A layer was formed to produce a contrast enhancement film. [Refractive index of resin portion (dark color portion, in transparent protective layer)] − [Refractive index of spherical beads] = − 0.003. Further, a concave portion that was depressed toward the groove portion was formed on the surface of the dark color portion, and the depth thereof was 3 μm from the surface of the transparent protective layer.

  The obtained pressure-sensitive adhesive film having a dye-containing pressure-sensitive adhesive layer was laminated on an antireflection film (trade name “RL9900”, manufactured by NOF Corporation, thickness 100 μm) to obtain an antireflection film having a dye-containing pressure-sensitive adhesive layer. A soda-lime glass substrate is bonded to the PET surface of an electromagnetic wave absorbing film (manufactured by Dai Nippon Printing Co., Ltd.) in which copper is formed in a mesh shape on the surface of the PET film through a transparent adhesive layer, and transparent on the surface. The contrast improvement film manufactured above was bonded through the adhesive layer. On the contrast improving film, the separator of the antireflection film with a dye-containing pressure-sensitive adhesive layer is peeled off, the dye-containing pressure-sensitive adhesive layer is bonded, and autoclaved (60 ° C., 0.5 MPa, 30 minutes) to obtain an optical filter. It was. The laminated structure of the obtained optical filter, that is, the laminated structure of “RL9900” / dye-containing pressure-sensitive adhesive layer / contrast improving film / electromagnetic wave absorbing film / glass substrate is referred to as “Configuration A”.

[Examples 2, 3, 5, 6 and Examples 8 to 11]
With the composition shown in Table 1, a dye-containing pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 above. Using the obtained dye-containing pressure-sensitive adhesive composition, an optical filter having “Configuration A” was produced in the same manner as in Example 1.

[Example 4]
With the composition shown in Table 1, a dye-containing pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 above. Using the resulting dye-containing pressure-sensitive adhesive composition, a pressure-sensitive adhesive film was obtained in the same manner as in Example 1.
The obtained pressure-sensitive adhesive film having a dye-containing pressure-sensitive adhesive layer was laminated on an antireflection film (trade name “A4100”, manufactured by Toyobo Co., Ltd., thickness: 100 μm) to obtain an antireflection film having a dye-containing pressure-sensitive adhesive layer. On the soda lime glass substrate, the separator of the antireflection film with the dye-containing pressure-sensitive adhesive layer is peeled off, the dye-containing pressure-sensitive adhesive layer is bonded, and autoclaved (60 ° C., 0.5 MPa, 30 minutes) to obtain an optical filter. Obtained. The laminated structure of the obtained optical filter, that is, the laminated structure of “A4100” / dye-containing pressure-sensitive adhesive layer / glass substrate is defined as “Configuration C”.

[Example 7]
With the composition shown in Table 1, a dye-containing pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 above. Using the resulting dye-containing pressure-sensitive adhesive composition, a pressure-sensitive adhesive film was obtained in the same manner as in Example 1.
The obtained pressure-sensitive adhesive film having a dye-containing pressure-sensitive adhesive layer was laminated on an antireflection film (trade name “RL7800”, manufactured by NOF Corporation, thickness 100 μm) to obtain an antireflection film having a dye-containing pressure-sensitive adhesive layer. A soda-lime glass substrate is bonded to the PET surface of an electromagnetic wave absorbing film (Dai Nippon Printing Co., Ltd.) via a transparent adhesive layer, and a conductive thin film (Asahi Glass Co., Ltd.) is formed on the transparent adhesive layer. The PET surface of the company) was bonded. On the conductive thin film, the separator of the antireflection film with the dye-containing pressure-sensitive adhesive layer is peeled off, the dye-containing pressure-sensitive adhesive layer is bonded, and autoclaved (60 ° C., 0.5 MPa, 30 minutes) to obtain an optical filter. Obtained. The laminated structure of the obtained optical filter, that is, the laminated structure of “RL7800” / dye-containing pressure-sensitive adhesive layer / conductive thin film / electromagnetic wave absorbing film / glass substrate is referred to as “Configuration B”.

[Evaluation]
Using the optical filters obtained in Examples 1 to 11 as samples, optical characteristics of each sample (luminous transmittance, chromaticity, transmittance at the maximum absorption wavelength (λ _max ), transmittance at neon cut wavelengths (595 nm and 593 nm)) The light resistance was evaluated by the following method. The results are shown in Table 2.

(Initial optical properties)
Using a spectrophotometer (SolidSpec-3700, manufactured by Shimadzu Corporation), the spectrum of a 20 × 20 mm square test piece cut out from each sample was measured in a wavelength range of 380 to 1000 nm using a C light source. According to JIS Z8701 (1999), luminous transmittance Tv (%) and color coordinates (x, y) in the XYZ color system were calculated. Moreover, the transmittance | permeability in a maximum absorption wavelength ((lambda) _max ) and the transmittance | permeability in a neon cut wavelength (595 nm and 593 nm) were calculated | required.

(Light resistance)
Using a light resistance tester (Suga Test Instruments Co., Ltd., xenon weather meter X25), after irradiating light of 380 nm or more with 100 MJ / cm ² , luminous transmittance Tv and color coordinates (x, y) The transmittance at x, y and the maximum absorption wavelength (λ _max ) and the transmittance at neon cut wavelengths (595 nm and 593 nm) were measured, and the measured values before and after the test were compared.
“◯” if all the changes before and after the test are less than 5%, “△” if any one is 5% or more and less than 10%, and “×” if any one is 10% or more. did.

Claims (7)

  Tetraazaporphyrin-based dye, ultraviolet absorber, light stabilizer made of copper complex or nickel complex, acrylic pressure-sensitive adhesive, and organic solvent in which the solubility of the tetraazaporphyrin-based dye is 1 g / 100 g or more at 25 ° C. And a solubility of the light stabilizer in the organic solvent is 3 g / 100 g or more at 25 ° C.   Furthermore, the adhesive composition of Claim 1 containing a near-infrared absorption pigment | dye. The pressure-sensitive adhesive composition according to claim 1 or 2, wherein the near-infrared absorbing dye is selected from phthalocyanine dyes represented by the following formula (1).

In Expression ^{(1), R} 1 ~R ¹⁶ each independently represent a hydrogen atom, a halogen atom, hydroxy group, amino group, hydroxy sulfonyl group, aminosulfonyl group or a hydrocarbon group (provided that the carbon number of 1 to 20, The hydrocarbon group may contain one or more atoms selected from the group consisting of a nitrogen atom, a sulfur atom, an oxygen atom and a halogen atom), and two adjacent substituents are connected via a linking group. It may be. Provided that at least four of R ² , R ³ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , R ¹⁴ , R ¹⁵ are unsubstituted or a phenyl group in which at least one of hydrogen atoms is substituted with an alkyl group or This is a group having a phenyl group at the terminal. M ² represents a divalent metal atom, a trivalent substituted metal atom, a tetravalent metal atom, or an oxy metal. ]   The pressure-sensitive adhesive composition according to any one of claims 1 to 3, wherein the ligand of the complex is selected from organic ligands having an oxygen atom or a sulfur atom as a coordination atom.   The pressure-sensitive adhesive composition according to any one of claims 1 to 4, comprising the light stabilizer in a proportion of 0.001 to 10 parts by mass with respect to 100 parts by mass of the acrylic pressure-sensitive adhesive.   The adhesive film which has an adhesive layer formed using the adhesive composition of any one of Claims 1-5 on a film.   An optical filter in which one or more films are attached to a substrate, wherein the filter is either between the film and the substrate or between the films in the case where the number of the films is two or more. An optical filter having a pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive composition according to claim 1.