JP2015001649A - Optical filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical filter comprising an adhesive layer having durability even for use together with a tetraazaporphyrin dye while exhibiting excellent near-infrared absorptivity.SOLUTION: An optical filter comprises: a substrate; a tetraazaporphyrin dye disposed on the substrate; a near-infrared absorbing diimmonium dye comprising an amorphous diimmonium salt represented by the general formula (1) in the figure; an ultraviolet absorber; a photostabilizer comprising a copper complex or nickel complex; and an adhesive layer containing an acrylic adhesive.

Description

  The present invention relates to an optical filter having a color tone correction function used for a plasma display (hereinafter referred to as a 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

  In such an optical filter, materials used for shielding near infrared rays include inorganic dyes / organic dyes having near infrared absorption ability, and those having little absorption in the visible region are preferably used. In addition, when an optical filter is constituted using these near infrared absorbing dyes, the dye is mixed with an adhesive and present as an adhesive layer between a glass substrate and other functional films to provide near infrared shielding ability. In general, the optical filter is provided.

  As dyes having near infrared absorption ability, phthalocyanine dyes and diimonium dyes are widely used. Here, the phthalocyanine-based dye has strong durability even in the adhesive layer, but has a tendency to increase absorption in the visible region. Moreover, although the diimonium dye has a small absorption in the visible region, the durability in the adhesive layer tends to be weak. Therefore, Patent Document 1 attempts to improve the durability in the adhesive layer by using a diimonium dye that is dry-pulverized into an amorphous material.

  On the other hand, there is a demand for a tetraazaporphyrin-based dye as a dye that efficiently absorbs orange unnecessary light having a wavelength of about 590 nm emitted by PDP. The tetraazaporphyrin-based dye is generally mixed with an adhesive and applied to an optical filter as an adhesive layer, like the near-infrared absorbing dye.

  Here, the tetraazaporphyrin-based dye cannot be said to have sufficient durability, especially light resistance, and when an adhesive layer containing a diazanium-based dye together with a tetraazaporphyrin-based dye is applied to an optical filter, Patent Document 1 The dry pulverized diimonium dye described in 1) often suffers from problems such as discoloration due to deterioration of the tetraazaporphyrin dye.

International Publication No. 2011/0774619

  The present invention has been made to solve the above problems, and an object of the present invention is to provide an optical filter having an adhesive layer that is excellent in near-infrared absorption and has durability even when used with a tetraazaporphyrin-based dye. To do.

式（１）中、Ｒ^１〜Ｒ^８はそれぞれ同一でも異なっていてもよい１価有機基を示し、Ｘ⁻はアニオンを示す。 The optical filter of the present invention comprises a substrate, a tetraazaporphyrin-based dye disposed on the substrate, and a diimonium-based near-infrared absorption comprising an amorphous diimonium salt represented by the following general formula (1): A dye, an ultraviolet absorber, a light stabilizer made of a copper complex or a nickel complex, and an adhesive layer containing an acrylic adhesive.

In formula (1), R ^{1 to} R ⁸ each represent a monovalent organic group that may be the same or different, and X ⁻ represents an anion.

In the optical filter of the present invention, the complex contained in the adhesive layer 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 adhesive layer in the optical filter of the present invention preferably contains the light stabilizer in a proportion of 0.03 to 17 parts by mass with respect to 100 parts by mass of the acrylic adhesive.

The adhesive layer in the optical filter of the present invention preferably contains the diimonium-based near-infrared absorbing dye in a proportion of 0.6 to 6.7 parts by mass with respect to 100 parts by mass of the acrylic adhesive.
The pressure-sensitive adhesive layer in the optical filter of the present invention preferably contains the tetraazaporphyrin-based dye in a proportion of 0.06 to 0.6 parts by mass with respect to 100 parts by mass of the acrylic pressure-sensitive adhesive.

  ADVANTAGE OF THE INVENTION According to this invention, the optical filter provided with the adhesion layer which is excellent in near-infrared absorptivity and has durability even if used with a tetraazaporphyrin-type pigment | dye can be provided.

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

  The optical filter of the present invention is a diimonium-based near-infrared absorption comprising a substrate, a tetraazaporphyrin-based dye disposed on the substrate, and an amorphous material of the diimonium salt represented by the general formula (1). A dye, an ultraviolet absorber, a light stabilizer composed of a copper complex or a nickel complex, and an adhesive layer containing an acrylic adhesive (hereinafter also referred to as “near infrared absorbing adhesive layer” as necessary). .

  The optical filter of the present invention has the characteristics that the near-infrared absorbing adhesive layer contains the above-described components and has a near-infrared absorbing ability and a color tone correcting function for light having a wavelength of about 590 nm, and also has excellent durability.

  About the laminated structure of the optical filter of this invention, what is necessary is just a structure which has a near-infrared absorption adhesion layer arrange | positioned on a board | substrate and this board | substrate at least. In addition, that a near-infrared absorption adhesion layer is arrange | positioned on a board | substrate means installing in the at least one main surface of a board | substrate directly or through another layer.

  When the optical filter of the present invention is composed only of a substrate and a near-infrared absorbing adhesive layer, for example, an embodiment in which the near-infrared absorbing adhesive layer is directly attached to the display surface using an optical filter for display or the like can be mentioned. .

  Another laminated structure of the optical filter of the present invention is an optical filter in which one or more films are attached to a substrate, and the film in the case where there are two or more films between the film and the substrate. The structure provided with the near-infrared absorption adhesion layer is mentioned in any of the above. In this case, for example, the simplest laminated structure is a structure in which a single film is stuck on a substrate via a near-infrared absorbing adhesive layer. When two or more films are used, a plurality of adhesive layers are required to bond the films and substrates together. In that case, in the optical filter of the present invention, the plurality of adhesive layers may be the near-infrared absorbing adhesive layer having the above structure, but preferably the near-infrared absorbing adhesive layer is one layer, and the other adhesive layers have different functions. It is set as the adhesion layer comprised only with the adhesion layer or adhesive which has.

Furthermore, the optical filter of the present invention is provided with a near-infrared absorbing adhesive layer on the outermost layer obtained by laminating an adhesive layer other than the near-infrared absorbing adhesive layer and a film on the substrate, and this near-infrared absorbing adhesive layer is directly attached to the display surface. The aspect to do is also included.
Hereafter, each component which comprises the optical filter of this invention is demonstrated.

[substrate]
Examples of the substrate included in the optical filter of the present invention 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 when used for a display application. 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.

[Near-infrared absorbing adhesive layer]
The near-infrared absorbing adhesive layer of the optical filter of the present invention contains the following components (A) to (E).
(A) Tetraazaporphyrin-based dye (B) Diimonium-based near-infrared absorbing dye composed of an amorphous form of a diimonium salt represented by the above general formula (1) (hereinafter, a diimonium salt represented by the general formula (1) Is also referred to as a diimonium salt (1), and an amorphous form of the diimonium salt (1) is also referred to as a diimonium dye (b).)
(C) Ultraviolet absorber (D) Light stabilizer comprising copper complex or nickel complex (E) Acrylic pressure-sensitive adhesive In addition, for each of the above components, (A) component, (B) component, (C) It may be called a component, (D) component, and (E) component.
The near-infrared absorbing adhesive layer may contain optional components other than the above components (A) to (E) as necessary.

(A) Tetraazaporphyrin dye The tetraazaporphyrin 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 near infrared absorbing pressure-sensitive adhesive layer may contain one of the above compounds alone or in combination of two or more as a tetraazaporphyrin-based dye. The content of the tetraazaporphyrin pigment in the near-infrared absorbing adhesive layer is preferably 0.06 to 0.6 parts by mass and more preferably 0.09 to 0.45 parts by mass with respect to 100 parts by mass of the acrylic adhesive. . By setting the content of the tetraazaporphyrin-based pigment to 0.06 parts 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. The deterioration of durability can be suppressed by setting it to 6 parts by mass or less.

  The luminous transmittance of the optical filter of the present invention is preferably 20% or more, more preferably 25% or more, further preferably 30% or more, and particularly preferably 32% or more. Further, the luminous transmittance of the optical film is preferably 80% or less, and more preferably 70% or less. In the optical filter of the present invention, the average transmittance of near infrared rays in the wavelength region of 820 to 980 nm is preferably 35% or less, more preferably 30% or less, and particularly preferably 25% or less.

  In addition, in this specification, luminous transmittance refers to luminous transmittance with a C light source measured according to JIS Z8701 (1999). Further, in this specification, the luminous transmittance may be expressed as “Tv”.

  When the near-infrared absorbing adhesive layer contains a tetraazaporphyrin-based dye, the luminous transmittance is lowered. In the optical filter of the present invention, even when the near-infrared absorbing pressure-sensitive adhesive layer contains a tetraazaporphyrin-based dye at the above-mentioned preferable content, the near-infrared transmittance at a wavelength of 850 nm is 35% or less, and the visual sensitivity An embodiment in which the transmittance is 20% or more is preferable. In another aspect of the optical filter of the present invention, it is preferable that the near infrared transmittance at a wavelength of 850 nm is 25% or less and the luminous transmittance is 30% or more.

式（１）中、Ｒ^１〜Ｒ^８はそれぞれ同一でも異なっていてもよい１価有機基を示し、Ｘ⁻はアニオンを示す。 (B) Diimonium dye (b)
The diimonium dye (b) is composed of an amorphous material of a diimonium salt represented by the following formula (1).

In formula (1), R ^{1 to} R ⁸ each represent a monovalent organic group that may be the same or different, and X ⁻ represents an anion.

  Note that in this specification, an amorphous body is a state in which atoms or molecules are in a solid state without forming crystals having a regular periodic arrangement. The presence or absence of solid crystallinity is determined by measuring a diffraction pattern with a powder X-ray diffractometer. That is, the amorphous body is in a state where a clear diffraction peak showing crystallinity is not detected in a diffraction pattern obtained by a powder X-ray diffractometer. For example, when a diffraction peak is measured with a powder X-ray diffractometer and the peak of the maximum intensity detected is taken from the baseline, the half width of the peak is 2θ = 1 ° or more. . Such a solid is substantially free of crystals and is composed only of an amorphous material.

  By using an amorphous dimonium salt (1) as a near-infrared-absorbing dye, heat resistance is improved when it is contained in a near-infrared-absorbing pressure-sensitive adhesive layer as compared with a crystalline or aggregated state. It has characteristics such as high heat resistance and moist heat resistance and excellent transparency.

As preferred organic groups for R ^{1 to} R ^8, a linear or branched C _1-10 alkyl group, a C _3-12 cycloalkyl group, and a cycloalkyl ring which may be substituted with a halogen atom are substituted. And an _{optionally substituted} C _3-12 cycloalkyl-C _1-10 alkyl group.

As a linear or branched C _1-10 alkyl group, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, iso-propyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-amyl group, iso-amyl group, 1-methylbutyl group, 2-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 2-dimethylpropyl group, 1,1- A dimethylpropyl group etc. can be illustrated. Among these, n-propyl group, n-butyl group, n-pentyl group, and n-hexyl group are preferable because the crystallinity of the diimonium salt (1) is low and an amorphous body is easily formed. Moreover, by having such a low polarity alkyl group, the polarity with an acrylic adhesive becomes close and it is preferable also at the point which becomes easy to mix.

_Examples of the C _3-12 cycloalkyl group include a cyclopentyl group and a cyclohexyl group.

The C _3-12 cycloalkyl-C _1-10 alkyl group may be substituted or unsubstituted on the cycloalkyl ring. Examples of the substituent that can be substituted include an alkyl group, a hydroxyl group, a sulfonic acid group, Examples thereof include an alkylsulfonic acid group, a nitro group, an amino group, an alkoxy group, a halogenated alkyl group, and a halogen atom. Preferably, it is unsubstituted, and the cycloalkyl-alkyl group represented by the following general formula (3) is preferable because of its low solubility in acrylic pressure-sensitive adhesives.

  In the general formula (3), A represents a linear or branched alkyl group having 1 to 10 carbon atoms, and m represents an integer of 3 to 12. The carbon number of A is preferably 1 to 4, and m is preferably 5 to 8, and particularly preferably 5 or 6.

  Specific examples of the cycloalkyl-alkyl group of the general formula (3) include a cyclopentylmethyl group, 2-cyclopentylethyl group, 2-cyclopentylpropyl group, 3-cyclopentylpropyl group, 4-cyclopentylbutyl group, and 2-cyclohexyl. Examples thereof include a methyl group, a 2-cyclohexylethyl group, a 3-cyclohexylpropyl group, and a 4-cyclohexylbutyl group. Among these, a cyclopentylmethyl group, a cyclohexylmethyl group, a 2-cyclohexylethyl group, a 2-cyclohexylpropyl group, a 3- A cyclohexylpropyl group and a 4-cyclohexylbutyl group are preferable, and a cyclopentylmethyl group and a cyclohexylmethyl group are more preferable. In particular, a cyclohexylmethyl group is an acrylic type used for an adhesive, a hard coat resin, or the like. Low solubility in fat or the like, more preferable because as a low polarity.

Examples of the linear or branched C _1-10 alkyl group substituted with a halogen atom include a 2-halogenoethyl group, a 2,2-dihalogenoethyl group, a 2,2,2-trihalogenoethyl group, 3 -Halogenopropyl group, 3,3-dihalogenopropyl group, 3,3,3-trihalogenopropyl group, 4-halogenobutyl group, 4,4-dihalogenobutyl group, 4,4,4-trihalogenobutyl group And halogenated alkyl groups such as a 5-halogenopentyl group, a 5,5-dihalogenopentyl group, and a 5,5,5-trifluoropentyl group. Among these, a monohalogenated alkyl group represented by the following general formula (4) is preferable.

_{-C n H 2n -CH 2 Y (} 4)
In said general formula (4), n shows the integer of 1-9 and Y shows a halogen atom.
n is preferably 1 to 9, more preferably 1 to 4, and particularly preferably Y is a fluorine atom. Specific examples include monofluoroalkyl groups such as a 2-fluoroethyl group, a 3-fluoropropyl group, a 4-fluorobutyl group, and a 5-fluoropentyl group.

R ^{1 to} R ⁸ in the general formula (1) may all be the same monovalent organic group, but may be two or more different monovalent organic groups, preferably two different ones. Valent organic group. In particular, it is preferable that each combination of R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁷ and R ⁸ is a combination of two different monovalent organic groups. That is, the diimonium salt (1) in which two monovalent organic groups in each amino group are a combination of two different monovalent organic groups is preferable.

  The two monovalent organic groups are preferably a combination of monovalent organic groups selected from the group consisting of n-propyl group, n-butyl group, n-pentyl group, n-hexyl group and cyclohexylmethyl group, More preferably, one kind of monovalent organic group is a cyclohexylmethyl group, and another kind of monovalent organic group is selected from the group consisting of n-propyl group, n-butyl group, n-pentyl group and n-hexyl group. It is a monovalent organic group.

  When the monovalent organic group of one amino group is a combination of two different monovalent organic groups, the crystallinity of the diimonium salt (1) is lowered, and it tends to be amorphous. In particular, it is preferable that one of the two kinds of monovalent organic groups is a cyclohexylmethyl group, because crystallinity is lowered due to steric hindrance and the amorphous body is more easily formed.

X ⁻ in the general formula (1) is an anion necessary for neutralizing the charge of the diimonium cation, and an organic acid anion, an inorganic anion, or the like can be used. Specific examples of anions include halogen ions such as fluorine ion, chlorine ion, bromine ion and iodine ion, perchlorate ion, periodate ion, tetrafluoroborate ion, hexafluorophosphate ion and hexafluoroantimonate ion. Bis (trifluoromethanesulfonyl) imido ion, bis (fluorosulfonyl) imido ion, and the like.

  Of these, tetrafluoroborate ions, hexafluorophosphate ions, hexafluoroantimonate ions, bis (trifluoromethanesulfonyl) imidate ions, and bis (fluorosulfonyl) imidate ions are particularly preferably used. This is because the heat resistance and heat-and-moisture resistance of the obtained near-infrared absorbing adhesive layer can be improved. In particular, hexafluorophosphate ions, hexafluoroantimonate ions, and bis (fluorosulfonyl) imido ions are preferable because the resulting diimonium salt has low solubility in acrylic pressure-sensitive adhesives due to its large inorganicity.

  Specific examples of the diimonium salt (1) include hexafluorophosphoric acid-N, N, N ′, N′-tetrakis {p-di (cyclohexylmethyl) aminophenyl} -p-phenylenediimonium, hexafluoroantimonic acid-N. , N, N ′, N′-tetrakis {p-di (cyclohexylmethyl) aminophenyl} -p-phenylenediimonium, bis (trifluoromethanesulfonyl) imidic acid-N, N, N ′, N′-tetrakis {p- Di (cyclohexylmethyl) aminophenyl} -p-phenylenediimonium, bis (fluorosulfonyl) imidic acid-N, N, N ′, N′-tetrakis {p-di (cyclohexylmethyl) aminophenyl} -p-phenylenediimonium, Hexafluorophosphate-N, N, N ′, N′-tetrakis {p-di (n Propyl) aminophenyl} -p-phenylenediimonium, hexafluoroantimonic acid-N, N, N ′, N′-tetrakis {p-di (n-propyl) aminophenyl} -p-phenylenediimonium, bis (trifluoromethanesulfonyl) ) Imido acid-N, N, N ′, N′-tetrakis {p-di (n-propyl) aminophenyl} -p-phenylenediimonium, bis (fluorosulfonyl) imidic acid-N, N, N ′, N ′ -Tetrakis {p-di (n-propyl) aminophenyl} -p-phenylenediimonium, hexafluorophosphate-N, N, N ', N'-tetrakis {p-di (n-butyl) aminophenyl} -p -Phenylenediimonium, hexafluoroantimonic acid-N, N, N ', N'-tetrakis {p-di (n-butyl Aminophenyl} -p-phenylenediimonium, bis (trifluoromethanesulfonyl) imidic acid-N, N, N ′, N′-tetrakis {p-di (n-butyl) aminophenyl} -p-phenylenediimonium, bis (fluoro Sulfonyl) imidic acid-N, N, N ′, N′-tetrakis {p-di (n-butyl) aminophenyl} -p-phenylenediimonium, hexafluoroantimonic acid-N, N, N ′, N′-tetrakis {P-di (n-pentyl) aminophenyl} -p-phenylenediimonium, bis (fluorosulfonyl) imidic acid-N, N, N ′, N′-tetrakis {p-di (n-pentyl) aminophenyl} — p-phenylenediimonium, hexafluorophosphate-N, N, N ′, N′-tetrakis {p- (cyclohexylmethy Ru-n-propyl) aminophenyl} -p-phenylenediimonium, bis (fluorosulfonyl) imidic acid-N, N, N ′, N′-tetrakis {p- (cyclohexylmethyl-n-propyl) aminophenyl} -p -Phenylenediimonium, hexafluorophosphoric acid-N, N, N ', N'-tetrakis {p- (cyclohexylmethyl-n-butyl) aminophenyl} -p-phenylenediimonium, bis (fluorosulfonyl) imidic acid-N, N, N ′, N′-tetrakis {p- (cyclohexylmethyl-n-butyl) aminophenyl} -p-phenylenediimonium, hexafluorophosphoric acid-N, N, N ′, N′-tetrakis {p- (cyclohexyl) Methyl-n-pentyl) aminophenyl} -p-phenylenediimonium, bis (full (Rosulfonyl) imidic acid-N, N, N ′, N′-tetrakis {p- (cyclohexylmethyl-n-pentyl) aminophenyl} -p-phenylenediimonium and the like are superior in heat resistance, moist heat resistance and transparency. preferable.

  Among these, hexafluorophosphoric acid-N, N, N ′, N′-tetrakis {p-di (cyclohexylmethyl) aminophenyl} -p-phenylenediimonium, bis (trifluoromethanesulfonyl) imidic acid-N, N, N ′, N′-tetrakis {p-di (cyclohexylmethyl) aminophenyl} -p-phenylenediimonium, bis (fluorosulfonyl) imidic acid-N, N, N ′, N′-tetrakis {p-di ( (Cyclohexylmethyl) aminophenyl} -p-phenylenediimonium, hexafluorophosphoric acid-N, N, N ′, N′-tetrakis {p-di (n-propyl) aminophenyl} -p-phenylenediimonium, hexafluoroantimonic acid -N, N, N ', N'-tetrakis {p-di (n-butyl) aminophenyl -P-phenylenediimonium, bis (fluorosulfonyl) imidic acid-N, N, N ', N'-tetrakis {p-di (n-butyl) aminophenyl} -p-phenylenediimonium, hexafluoroantimonic acid-N, N, N ′, N′-tetrakis {p-di (n-pentyl) aminophenyl} -p-phenylenediimonium, hexafluorophosphate-N, N, N ′, N′-tetrakis {p- (cyclohexylmethyl- n-propyl) aminophenyl} -p-phenylenediimonium, hexafluorophosphoric acid-N, N, N ′, N′-tetrakis {p- (cyclohexylmethyl-n-butyl) aminophenyl} -p-phenylenediimonium, etc. This is preferable in that it has low crystallinity and tends to be an amorphous body.

  The diimonium dye (b) used in the present invention can be obtained by dry grinding the crystalline solid of the diimonium salt (1) to make it amorphous. The crystalline solid of the dimonium salt (1) can be produced by a conventionally known method, for example, a method described in International Publication No. 2011/0774619. Moreover, the amorphous state of the crystalline solid of the diimonium salt (1) by dry pulverization may be performed by the method described in International Publication No. 2011/0774619.

  As the diimonium dye (b), a commercially available product such as a product name “CIR-FS265” manufactured by Nippon Carlit Co., Ltd. may be used.

  The near-infrared absorbing pressure-sensitive adhesive layer may contain one of the above-described amorphous forms of the diimonium salt (1) as the diimonium-based dye (b), or may contain two or more kinds in combination. The content of the diimonium dye (b) in the near-infrared absorbing adhesive layer is preferably 0.6 to 6.7 parts by mass and more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the acrylic adhesive. By making the content of the diimonium dye (b) 0.6 parts by mass or more with respect to 100 parts by mass of the acrylic pressure-sensitive adhesive, the near infrared absorptivity, particularly the near infrared absorptivity in the wavelength range of 820 to 980 nm. It can be sufficiently exhibited, and by setting it to 6.7 parts by mass or less, it is possible to sufficiently suppress absorption in the visible region in the wavelength range of approximately 380 to 780 nm.

  In addition, the preferable optical characteristic of the optical filter of the present invention is as described in the component (A). When used in combination with the component (A), the near-infrared absorption is performed so that the preferable optical characteristic can be achieved. It is preferable to appropriately adjust the content of the diimonium dye (b) in the adhesive layer.

  More preferably, even when the near-infrared absorbing pressure-sensitive adhesive layer contains the component (A) at the above-mentioned preferable content, the optical filter of the present invention having the near-infrared absorbing pressure-sensitive adhesive layer transmits near-infrared light having a wavelength of 850 nm. An optical characteristic having a transmittance of 35% or less and a luminous transmittance of 20% or more, or an optical having a near infrared transmittance of a wavelength of 850 nm of 25% or less and a luminous transmittance of 30% or more. In order to achieve the characteristics, the content of the diimonium dye (b) in the near-infrared absorbing adhesive layer is appropriately adjusted.

(C) Ultraviolet absorber An ultraviolet absorber is used in order to suppress the deterioration by an ultraviolet-ray and to improve durability, without impairing the function of the said tetraaza porphyrin type pigment | dye or a diimonium type pigment | dye (b). 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 near-infrared absorbing pressure-sensitive adhesive layer may contain one of the above-mentioned various ultraviolet absorbers alone as an ultraviolet absorber, or may contain two or more in combination. The content of the ultraviolet absorber in the near-infrared absorbing adhesive layer ensures the light absorption performance of each specific wavelength by the tetraazaporphyrin-based dye and the diimonium-based dye (b) and other physical properties required for the near-infrared absorbing adhesive layer. The amount of the ultraviolet absorber that can exhibit its function (mixing ratio) may be sufficient, and is preferably 0.1 to 30 parts by mass and more preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the acrylic pressure-sensitive adhesive. preferable.

(D) Light stabilizer As the light stabilizer, a light stabilizer composed of a complex having copper or nickel as a central atom is used. When the near-infrared absorbing adhesive layer contains such a light stabilizer, the light resistance of the tetraazaporphyrin-based dye and the diimonium-based dye (b) is improved, and the near-infrared absorbing adhesive layer has excellent durability. An optical filter is obtained.

  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.

  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 (5) is mentioned, for example.

In Formula (5), 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 (6) can also be used.

In formula (6), 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 (6), 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 (7).

In formula (7), 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 salicylates represented by the following formula (8), benzenesulfonates represented by the following formula (9), and the like.

In formula (8), 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, 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. p and q each independently represent an integer of 0 to 4, and when p and q are 2 to 4, X ¹ and X ² may be the same or different. M ⁶ represents a copper or nickel.

In formula (9), 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.

  Here, the near-infrared absorbing adhesive layer is usually a composition for forming a near-infrared absorbing adhesive layer by dissolving the components (A) to (E) in an organic solvent, and then applying this to the coated surface and drying. It is formed by removing the organic solvent.

  The light stabilizer contained in the near-infrared absorbing adhesive layer is preferably a light stabilizer having a solubility of 3 g / 100 g or more in an organic solvent (described later) in which the solubility of the tetraazaporphyrin-based dye is 1 g / 100 g or more. That is, in the present invention, among the complexes having copper or nickel as the central atom described above, the solubility is preferably 1 g / 100 g or more depending on the type of tetraazaporphyrin-based dye used in the near-infrared absorbing adhesive layer. Depending on the organic solvent appropriately selected, a light stabilizer having a solubility in the organic solvent of 3 g / 100 g or more is appropriately selected. Here, the solubility in this specification refers to the solubility at 25 ° C. unless otherwise specified.

  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. As the light stabilizer used in the present invention, bis (dibutyldithiocarbamate) nickel (II) is particularly preferable from the viewpoint of improving light resistance of a tetraazaporphyrin-based dye and a diimonium-based dye (b).

  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. As for the above solubility conditions, when used alone, it is necessary to satisfy the above solubility conditions alone, but when using a mixture of two or more, the mixture may be used even if either one does not satisfy the conditions. In this case, it can be used if the solubility condition is satisfied.

  The content of the light stabilizer in the near-infrared absorbing adhesive layer ensures the light absorption performance of each specific wavelength by the tetraazaporphyrin-based dye and the diimonium-based dye (b) and other physical properties required for the near-infrared absorbing adhesive layer. The range of the amount (blending ratio) that the light stabilizer can exhibit its function is preferably 0.03 to 17 parts by mass, more preferably 0.15 to 10 parts by mass with respect to 100 parts by mass of the acrylic pressure-sensitive adhesive. .

(E) Acrylic pressure-sensitive adhesive The acrylic pressure-sensitive adhesive contained in the near-infrared-absorbing pressure-sensitive adhesive layer forms a layer with the components (A) to (D) uniformly dispersed to form a near-infrared-absorbing pressure-sensitive adhesive layer. It functions as a binder having adhesiveness.

  As the acrylic pressure-sensitive adhesive, a pressure-sensitive adhesive (E1) made of an acrylic (co) polymer containing a polymerization unit based on an acrylic monomer as a main component, and a crosslinking point in order to increase the cohesive strength of the pressure-sensitive adhesive A pressure-sensitive adhesive (E2) obtained by crosslinking an acrylic (co) polymer having a functional group (for example, a hydroxy group, an epoxy group, etc., hereinafter also referred to as “crosslinkable group”) and a crosslinking agent. . The acrylic (co) polymer constituting the pressure-sensitive adhesive (E1) may have a crosslinkable group.

  Examples of acrylic monomers used to obtain acrylic (co) polymers include (meth) acrylic acid, itaconic acid, (anhydrous) maleic acid, (anhydrous) fumaric acid, crotonic acid, and alkyl esters thereof. It is done. Here, “(meth) acrylic acid” is a generic term for acrylic acid and methacrylic acid. The same applies to (meth) acrylate. In addition, in order to raise the cohesion force of the adhesive in a near-infrared absorption adhesive layer, use of the acrylic monomer which has a crosslinkable group is 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.

  As the composition of the monomer used to obtain the acrylic (co) polymer, among the acrylic monomers, (meth) acrylic acid, its alkyl ester, and (meth) acrylic acid having a crosslinkable group A composition having as a main component a (meth) acrylic acid monomer selected from the monomer based monomers is preferred. Here, the main component means that the (meth) acrylic acid monomer is contained in an amount of 95% by mass or more based on the total amount of the acrylic (co) polymer, more preferably 98% by mass or more. The mass% or more is more preferable. The monomer other than the (meth) acrylic acid monomer in the acrylic (co) polymer may be a monomer other than the acrylic monomer, but is preferably a (meth) acrylic acid monomer. An acrylic monomer other than a monomer.

  The acid value of the acrylic (co) polymer is preferably 10 mgKOH / g or less. The acid value may be 0 mgKOH / g. The acid value of the acrylic (co) polymer is more preferably 0 to 7 mgKOH / g, and particularly preferably 0 to 5 mgKOH / g. When the acid value of the acrylic (co) polymer is 10 mg KOH / 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 (co) polymer to 10 mgKOH / g or less, the monomer having a carboxyl group used for copolymerization so that the acid value is within this range when the acrylic monomer is polymerized. Adjust body volume. 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 (co) polymer.

  Crosslinkable acrylic (co) polymers 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 acryl-type (co) polymer, -30-10 degreeC is more preferable.

  When the acrylic pressure-sensitive adhesive is used in the pressure-sensitive adhesive (E1) mode, only the acrylic (co) polymer is contained in the composition for forming a near-infrared-absorbing pressure-sensitive adhesive layer described above to absorb near-infrared light. An adhesive layer is obtained. An acrylic (co) polymer may be used individually by 1 type, and may be used in combination of 2 or more type. However, among the acrylic (co) polymers, when the crosslinkable acrylic (co) polymer is used, it is preferable that the pressure sensitive adhesive (E2) is used. That is, the composition for forming a near-infrared absorbing adhesive layer contains a crosslinking agent together with a crosslinkable acrylic (co) polymer, and the crosslinked acrylic resin obtained by crosslinking when forming the near-infrared absorbing adhesive layer is acrylic. The aspect made into a system adhesive (adhesive (E2)) is preferable. Each of the crosslinkable acrylic (co) polymer and the crosslinking agent may be used alone or in combination of two or more. A cohesive force can be secured by reacting a crosslinkable group of the crosslinkable acrylic (co) polymer with a crosslinker to crosslink the acrylic (co) polymer.

  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 the crosslinkable acrylic (co) polymer, when the crosslinkable group is a hydroxy group, polyisocyanate is preferable. For example, a commercial name such as “CORONATE HL” manufactured by Nippon Polyurethane Co., Ltd. Can be used.

  The ratio of the crosslinking agent to the crosslinkable acrylic (co) polymer in the pressure-sensitive adhesive (E2) is the ratio of the reactive group possessed by the crosslinking agent to the molar amount of the crosslinkable group in the crosslinkable acrylic (co) polymer. The amount that the molar amount is 0.01 to 10 times is preferable, and the amount that is 0.1 to 5 times is more preferable.

  The composition for forming a near-infrared-absorbing pressure-sensitive adhesive layer when the pressure-sensitive adhesive (E1) made of an acrylic (co) polymer is used as the acrylic pressure-sensitive adhesive in the near-infrared-absorbing pressure-sensitive adhesive layer. It can be calculated as a ratio of the mass of the acrylic (co) polymer to the mass of the total solid content contained. In the case of the pressure-sensitive adhesive (E2) obtained by cross-linking the cross-linkable acrylic (co) polymer and the cross-linking agent, the cross-linkable acrylic with respect to the total solid content contained in the composition for forming a near-infrared absorbing pressure-sensitive adhesive layer. It can be calculated as a ratio of the total mass of the system (co) polymer and the crosslinking agent.

  80-99.2 mass% is preferable with respect to the total solid, and, as for content of the acrylic adhesive in a near-infrared absorption adhesive layer, 85-98.2 mass% is more preferable.

(Optional component)
The near-infrared absorbing pressure-sensitive adhesive layer of the present invention further includes a near-infrared absorbing dye (hereinafter also referred to as a near-infrared absorbing dye (f)) other than the diimonium dye (b) as component (F), if necessary. ) As a component, a color correction dye other than the tetraazaporphyrin-based dye (hereinafter also referred to as a near color correction dye (g)) may be optionally contained within a range not impairing the effects of the present invention. In addition, as other optional components, optional components such as a leveling agent, an antistatic agent, a heat stabilizer, an antioxidant, a dispersant, a flame retardant, a lubricant, and a plasticizer are contained within a range not impairing the effects of the present invention. Also good.

(F) Near-infrared absorbing dye (f)
The near-infrared-absorbing dye (f) is a near-infrared-absorbing dye other than the diimonium dye (b) and does not impair the effects of the present invention as long as it is a dye having absorption in the near-infrared wavelength region (750 to 1100 nm). It can be used without particular limitation in the range.

  Examples of the near infrared absorbing dye (f) include polymethine dyes, phthalocyanine dyes, naphthalocyanine dyes, metal complex dyes, aminium dyes, imonium dyes, and diimonium dyes other than diimonium dyes (b), Examples include anthraquinone dyes, dithiol metal complex dyes, naphthoquinone dyes, indolephenol dyes, azo dyes, triallylmethane dyes, and tungsten oxide dyes.

  Depending on the near-infrared wavelength absorption region required for the optical filter, among these, as the near-infrared absorbing dye (f) that efficiently absorbs near-infrared light when used together with the diimonium dye (b), a dithiol metal complex dye, Examples include aminium dyes, phthalocyanine dyes, naphthalocyanine dyes, and tungsten oxide dyes.

  The near-infrared absorbing dye (f) may be one kind or a mixture of two or more kinds. The near-infrared absorbing dye (f) is preferably used alone or in combination of two or more phthalocyanine dyes from the viewpoint of durability. 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. It is particularly preferable to contain three or more phthalocyanine dyes having different maximum wavelengths, which are different from the maximum wavelength of b).

  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 following formula (10).

In formula (10), R ^{71 to} R ⁸⁶ each independently represent 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 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. However, at least four of R ⁷² , R ⁷³ , R ⁷⁶ , R ⁷⁷ , R ⁸⁰ , R ⁸¹ , R ⁸⁴ , R ⁸⁵ 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 ⁷² , R ⁷³ , R ⁷⁶ , R ⁷⁷ , R ⁸⁰ , R ⁸¹ , R ⁸⁴ , R ⁸⁵ are group A, and other R ⁷¹ , R ⁷⁴ , R ⁷⁵ , R ⁷⁸ , R ⁷⁹ , R ⁸² , R ⁸³ and R ⁸⁶ are group B. It is preferable that all eight groups or atoms of group A are Ph-containing groups, for example, groups represented by the following formula (11).

In Formula (11), R ^{91 to} R ⁹⁵ each independently represent a hydrogen atom or an alkyl group, and X represents a single bond, O, S, NH, or a linear alkylene group having 1 to 6 carbon atoms.
Wherein ^{(11), R} 91 ~R ⁹⁵ 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 (11) 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 ¹⁰⁰ (R ¹⁰⁰ is a benzyl group, a phenyl group, or a linear or branched alkyl group having 1 to 20 carbon atoms), and —NR ¹⁰¹ R ¹⁰² (R ¹⁰¹ , R ¹⁰² may be independently a linear or branched alkyl group having 1 to 10 carbon atoms. In the case of -NHR ¹⁰⁰ , examples of R ¹⁰⁰ include a benzyl group, a 2-ethylhexyl group, an n-propyl group, and an n-butyl group. In the case of —NR ¹⁰¹ R ¹⁰² , examples of R ¹⁰¹ and R ¹⁰² 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, the following commercial products are mentioned as trade names manufactured by Nippon Shokubai Co., Ltd.
“EX color IR-14” (in the above formula (10), all 8 groups A are 2,5-dichlorophenyloxy groups, 4 groups B are benzylamino groups, 4 groups are 2,6 groups) - dimethylphenyl group, ^{M 2} is copper).
“E-ex color IR-10A”, “e-ex color IR-28”, “e-ex color IR-12”, “TX-EX-820” (in the above formula (10), all eight groups of groups A phenyl thiol groups, four groups of the group B is a 2-ethylhexyl group, 4 is 2,6-dimethylphenyl group, ^{M 2} is copper.),
“TX-EX-906”, “EEX Color IR-915”, “EEX Color IR-910”, “EEX Color IR-906” and the like.

Moreover, all are the brand names made from Yamada Chemical Co., Ltd., and the following commercial products are mentioned.
“KSK-5” (in the above formula (10), all eight groups in group A are 4-trifluoromethylphenyloxy groups, all eight groups in group B are 2,4,6-triisopropylphenylthiol groups, M ² is VO).
“KSK-10” (in the above formula (10), all eight groups of group A are phenylthiol groups, four of group B groups are diisobutylamino groups, four are 2,6-dimethylphenyloxy groups, M ² is VO).
“KSK-15” (in the above formula (10), all 8 groups A are phenylthiol groups, 4 groups B are dimethylamino groups, 4 groups are 2,6-dimethylphenyloxy groups, M ² is VO).

“KSK-16” (in the above formula (10), all 8 groups A are 2-methylphenyloxy groups, 4 groups B are dimethylamino groups, 4 groups are 2,6-dimethylphenyloxy groups) Group M ² is VO).
“KSK-17” (in the above formula (10), all 8 groups A are 2-methylphenyloxy groups, 4 groups B are dimethylamino groups, 4 groups are 2,4,6-trimethyl) isopropylphenyl thiol group, ^{M 2} is VO.),
“KSK-20” (in the above formula (10), 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 (10), eight groups A and four groups B are 2,4,6-trimethylphenylthiol groups, and four groups B are n- Butylamino group, M ² is VO).
"KSK-100" (the same structure as the above-mentioned "EX color IR-14"), "KSK-101" (the same structure as the above-mentioned "TX-EX-820"), and the like.

  The content of the near-infrared absorbing dye (f) in the near-infrared-absorbing adhesive layer is used together with the component (B), the diimonium dye (b), to suppress unnecessary absorption of light in the visible light region, and to reduce the near-infrared wavelength. As a range in which an optical filter that absorbs light in a region sufficiently specifically is obtained, for example, 0.03 to 3.3 parts by mass is preferable with respect to 100 parts by mass of the acrylic pressure-sensitive adhesive, and 0.05 to 1. 7 parts by mass is more preferable. Regarding the ratio of the content of the near-infrared absorbing dye (f) to the diimonium-based dye (b) in the near-infrared-absorbing adhesive layer, the near-infrared absorbing dye (f) is 0 with respect to 100 parts by mass of the diimonium-based dye (b). The ratio of .75 to 250 parts by mass is preferable, and 5 to 200 parts by mass is more preferable.

  By adjusting the content of the near-infrared absorbing dye (f) within the above range, the near-infrared absorption in which the near-infrared absorbing function of the diimonium-based dye (b) is reinforced while maintaining a state in which a decrease in durability is suppressed. An adhesive layer is obtained.

  In addition, the preferable optical characteristic of the optical filter of this invention is as having described with the said (A) component, When using in combination with said (A)-(D) component, especially (A) component and (B) component In addition, it is preferable to appropriately adjust the content of the near-infrared absorbing dye (f) in the near-infrared-absorbing pressure-sensitive adhesive layer so that the above preferable optical characteristics can be achieved. More preferably, the content of the near-infrared absorbing dye (f) in the near-infrared-absorbing adhesive layer is appropriately adjusted so that the optical characteristics of a more preferable aspect of the optical filter of the present invention described above can be achieved.

(G) Color tone correction dye (g)
Similar to the tetraazaporphyrin-based dye, the color tone correction dye (g) absorbs a part of a specific wavelength range 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 the color correction dyes (g), one or two or more kinds selected from, for example, anthraquinone dyes and quinophthalone dyes, which have good weather resistance and good compatibility or dispersibility with acrylic pressure-sensitive adhesives Are preferably used in appropriate combination. 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.
Examples of the quinophthalone-based dye include commercially available products such as those manufactured by BASF Corporation and trade name “Paliotol Yellow K0961HD”.

As the color tone correction dye (g), a dye having no hydroxy group (—OH) and amino group (—NH ₂ ) is preferable. Here, the dye containing the near infrared absorbing adhesive layer, to be composed of only substantially dyes having no hydroxy group (-OH) and amino groups (-NH ₂₎ is preferred. The phrase “substantially composed only of a dye having no hydroxy group and amino group” includes 95% by mass or more of the dye having no hydroxy group and amino group with respect to the total amount of the dye in the near-infrared absorbing adhesive layer. This means that 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 near-infrared absorbing adhesive layer containing the dye does not change color due to moisture, and deterioration such as fading can be suppressed. The coloring matter in this case means all of the component (A), the component (B), the component (F), and the component (G), and the total amount of the coloring matter is the total amount of these components.

  The intensity and wavelength distribution of visible light emission vary depending on the type and model of the display. Therefore, for example, when the optical filter of the present invention is used in a display, the color correction dye (g) optionally contained in the near infrared absorbing adhesive layer is appropriately selected from the type and combination of color correction dyes used depending on the type and model of the display. Is done. From the viewpoint of durability, anthraquinone dyes are preferable.

  The content of the color tone correcting dye (g) in the near-infrared absorbing adhesive layer is used together with the tetraazaporphyrin-based dye as the component (A) to absorb unnecessary light in the visible light region while maintaining the luminous transmittance. As a range in which the color tone of the transmitted light of the optical filter can be corrected to a required color tone, a combination with the (A) component, (B) component, (F) component, etc. contained in the near-infrared absorbing adhesive layer or a color tone correction dye used ( Although depending on the type of g), for example, 0.003-0.3 parts by mass is preferable and 0.016-0.27 parts by mass is more preferable with respect to 100 parts by mass of the acrylic pressure-sensitive adhesive.

  As for the color tone required for the transmitted light of the optical filter, for example, when the optical filter is used for a display application, the optical filter is generally arranged on the viewing side of a display such as a PDP, and therefore generally achromatic. 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). Therefore, the optical filter of the present invention has (x, y) = (0.310 ± 0.100, 0.316 ± 0.100) as chromaticity coordinates measured on the same basis as the above for display applications. The aspect which becomes is preferable.

  Here, the optical filter of the present invention is colored by the near-infrared absorbing pigment of at least the component (B) contained in the near-infrared-absorbing pressure-sensitive adhesive layer, and further optionally used by the component (F). Examples of the method for bringing the chromaticity coordinates of the optical filter into the above range include, for example, the type and content of the near-infrared absorbing dye comprising the component (B) and the optionally used component (F) to be contained in the near-infrared absorbing adhesive layer. , (A) and a method of performing by appropriately selecting the type and content of the color tone correcting dye comprising the (G) component optionally used.

  However, since it is difficult to adapt the color tone to the above range while achieving the desired near-infrared absorption characteristics only with the near-infrared-absorbing adhesive layer, the types of substrates and films constituting the optical filter together with the near-infrared-absorbing adhesive layer are different. A method may be adopted in which the color tone of the transmitted light of the obtained optical filter is adapted to the above range by appropriately selecting.

  The thickness of the near-infrared absorbing adhesive layer in the optical filter of the present invention 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 exerted, and by setting the thickness to 50 μm or less, the residual organic solvent during molding is reduced. be able to.

When the near-infrared absorbing adhesive layer in the optical filter of the present invention has the above-described configuration, the tetraazaporphyrin-based dye and the diimonium-based near-infrared absorbing dye having excellent near-infrared absorbing ability are excellent in durability such as light resistance. . Therefore, the optical filter is corrected to a desired color tone, and unnecessary absorption of light in the visible light region is suppressed, and the near-infrared absorption ability of absorbing light in the near-infrared wavelength region sufficiently specifically is excellent, Its performance is durable and sustainable.
Such a near-infrared absorbing adhesive layer can be produced, for example, by the following method.

(Preparation of near-infrared absorbing adhesive layer)
The near-infrared absorbing adhesive layer is usually produced by a method including the following steps (i) to (iii).
(I) The (A) to (E) components contained in the near infrared absorbing adhesive layer described above as essential components, the (F) component, (G) component optionally contained, and the other optional components described above as they are Or a pressure-sensitive adhesive composition preparatory step for preparing a composition for forming a near-infrared absorbing pressure-sensitive adhesive layer (hereinafter referred to as “pressure-sensitive adhesive composition”) by being contained in the organic solvent (S) as a raw material component of the component.
(Ii) A coating step of coating the obtained pressure-sensitive adhesive composition on a substrate or film as a base material.
(Iii) A drying step of drying the coating layer of the pressure-sensitive adhesive composition to remove the organic solvent.
Hereinafter, each step will be described.

(I) Pressure-sensitive adhesive composition preparation step The various components contained in the pressure-sensitive adhesive composition as a solid content are as described above, and the content is also as described above. Among these components, each component other than the acrylic adhesive of component (E) is directly blended into the adhesive composition. The component (E) is directly blended into the pressure-sensitive adhesive composition for the pressure-sensitive adhesive (E1), and the pressure-sensitive adhesive composition in the form of a crosslinkable acrylic (co) polymer as a raw material and a cross-linking agent for the pressure-sensitive adhesive (E2). Is blended into the product. Hereinafter, the pressure-sensitive adhesive composition “containing an acrylic pressure-sensitive adhesive” is used as an expression including both the case where the pressure-sensitive adhesive composition itself is contained and the case where it is contained in the form of a raw material.

  In the next step (ii), the viscosity of the pressure-sensitive adhesive composition is usually adjusted using an organic solvent (S) in consideration of the efficiency when the composition is applied. The pressure-sensitive adhesive composition is preferably prepared by first dissolving the above-mentioned various solid components other than the acrylic pressure-sensitive adhesive of component (E) in the organic solvent (S1) and the organic solvent (S2). (E) It mixes with the 2nd liquid composition which melt | dissolved the acrylic adhesive of a component. In addition, other solid components among solid content which a 1st liquid composition contains may be mix | blended with (E) component with a 2nd liquid composition as needed. Moreover, when (E) component is an adhesive (E2), a crosslinking agent is prepared separately from a 2nd liquid composition, and is added when mixing a 1st liquid composition and a 2nd liquid composition. And may be mixed with these.

  Since the pressure-sensitive adhesive composition is prepared as described above, the organic solvent (S) contained in the pressure-sensitive adhesive composition is usually an organic solvent for uniformly dissolving the various solid components other than the component (E). It consists of (S1) and an organic solvent (S2) brought into the pressure-sensitive adhesive composition together with the acrylic pressure-sensitive adhesive as a component for dissolving the acrylic pressure-sensitive adhesive of the component (E).

As the organic solvent (S1), an organic solvent (S1) in which the solubility of the tetraazaporphyrin-based dye as the component (A) is 1 g / 100 g or more is preferable. Since the solubility of the organic solvent (S1) 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), the solubility depends on the tetraazaporphyrin-based dye used. It is preferable to appropriately select and use an organic solvent (S1) having a weight of 1 g / 100 g or more.

  Examples of the organic solvent (S1) include aromatic systems such as toluene and xylene; amide systems such as N-methyl-2-pyrrolidone, dimethylformamide, and dimethylacetamide; ketone systems such as methyl ethyl ketone, methyl isobutyl ketone, and acetone; methanol Alcohols such as ethanol and i-propyl alcohol; hydrocarbons such as hexane; and tetrahydrofuran. In the present invention, among these, it is preferable to appropriately select those satisfying the above solubility conditions with respect to the tetraazaporphyrin-based dye to be used. Specifically, methyl ethyl ketone and toluene are preferable, and methyl ethyl ketone is particularly preferable.

  These compounds are used alone or in combination of two or more as necessary to form an organic solvent (S1). When defining the above-mentioned solubility conditions, when used alone, it is necessary to satisfy the above-mentioned solubility conditions alone, but when using a mixture of two or more, even if either one does not satisfy the conditions When the mixed solvent is used, the above solubility condition may be satisfied.

  Specifically, when the commercially available “TAP-2” or “TAP-HTBX” is used as the tetraazaporphyrin-based dye as the component (A), the organic solvent (S1) that satisfies the above-described solubility condition is used. , Methyl ethyl ketone, toluene, xylene, methyl isobutyl ketone, acetone, methanol, ethanol, i-propyl alcohol, hexane, tetrahydrofuran, dimethylformamide and the like. Among these, methyl ethyl ketone and toluene are preferable, and methyl ethyl ketone is particularly preferable.

  The content of the organic solvent (S1) in the pressure-sensitive adhesive composition may be an amount that can uniformly dissolve each component other than the component (E). The content of the organic solvent (S1) in the pressure-sensitive adhesive composition is preferably 10 to 40% by mass with respect to 100% by mass of the pressure-sensitive adhesive composition in consideration of the content of each component other than the component (E). 15-35 mass% is more preferable.

  As the component that dissolves the acrylic pressure-sensitive adhesive of component (E), as the organic solvent (S2) brought into the pressure-sensitive adhesive composition together with the acrylic pressure-sensitive adhesive, the same organic compounds as the organic solvent (S1) can be used. is there.

  The content of the organic solvent (S) in the pressure-sensitive adhesive composition is the total amount of the organic solvents (S1) and (S2), and the uniform dispersibility or solubility of all solids contained in the pressure-sensitive adhesive composition. And in the next step (ii), in consideration of efficiency at the time of applying the composition, 50 to 95% by mass is preferable with respect to 100% by mass of the pressure-sensitive adhesive composition, and 60 to 85% by mass is more preferable. .

  In addition, 5-50 mass% is preferable with respect to 100 mass% of adhesive compositions, and, as for content of the acrylic adhesive of (E) component in an adhesive composition, 15-40 mass% is more preferable.

(Ii) Application process The pressure-sensitive adhesive composition is then applied onto a substrate or film as a base material. In this case, the base material includes the above-mentioned substrate constituting the optical filter and various functional films (described later). In addition, as a base material, a film is preferable.

  Moreover, as a film to be a base material, a peelable film having peelability that does not eventually become an element constituting an optical filter, or a support film for supporting a near-infrared absorbing adhesive layer having no optical function in particular. There may be.

  As for the support film, the material of the film is not limited, but a resin film is preferable from the viewpoint of easy handling. 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 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 method for applying the adhesive composition to the substrate include dip coating, spray coating, spinner coating, bead coating, wire bar coating, blade coating, roller coating, curtain coating, A coating method such as a slit die coater method, a gravure coater method, a slit reverse coater method, a micro gravure method, or a comma coater method can be employed.

  Moreover, it is preferable that the film thickness of the coating layer formed in this way is set to such a film thickness that the film thickness of the finally obtained near-infrared absorbing pressure-sensitive adhesive layer falls within the above preferable range.

(Iii) Drying process Next, the near-infrared absorbing adhesive layer is obtained by drying the coating layer of the adhesive composition to remove the organic solvent. Examples of the drying process include heating and decompression. Specific drying treatment includes heat treatment at 50 to 120 ° C. for 0.5 to 5 minutes.

  It is preferable in terms of workability to provide a release film on the near-infrared absorbing adhesive layer after providing the near-infrared absorbing adhesive layer on the substrate because the adhesive layer can be protected until use. As the release film, the same film as the above-described peelable film can be used.

[the film]
As one aspect of the optical filter of the present invention, as described above, an optical filter in which one or more films are attached to a substrate, between the film and the substrate, or when the number of the films is two or more. The structure provided with the near-infrared absorption adhesion layer in any between films is mentioned.

  As a film used for an optical filter, the support film and various functional films of the said near-infrared absorption adhesion layer are mentioned, for example. In addition, it is preferable that the optical filter of this invention has 1 or 2 or more of a functional film as a film. As the functional film, basically, a resin film similar to the resin film constituting the support film is used as a base, and a functional film is preferably used. Specifically, a functional film containing various functional materials in the resin film, a functional film formed on the surface of the resin film by a method such as coating or sputtering, and the surface of the resin film are modified. For example, those that are functional and functional. The thickness of each functional film depends on the type of functional film, but is preferably 30 to 300 μm, and more preferably 50 to 250 μm.

  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, commercially available products such as trade name: ARCTOP (URP2199) manufactured by Asahi Glass Co., Ltd. and trade names: Realak (RL7800, RL9000, RL9200, RL9900, RL1700) manufactured by NOF Corporation 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. .

  The optical filter of this invention has a board | substrate and a near-infrared absorption adhesion layer as above-mentioned, and also has the said film as needed, Preferably it has a 1 or 2 or more functional film. In the case of having two or more films, usually, at least two adhesive layers are required between the film and the substrate. In this invention, at least 1 layer of this adhesion layer consists of a near-infrared absorption adhesion layer. The pressure-sensitive adhesive layer other than the near-infrared absorbing pressure-sensitive adhesive layer may be a pressure-sensitive adhesive layer composed of a functional material and a pressure-sensitive adhesive other than the combination of the components (A) to (D) as necessary, and does not contain a functional material. It may be an adhesive layer made of only an adhesive. As such an adhesive used for an adhesive layer other than the near-infrared absorbing adhesive layer, the same acrylic adhesive as the component (E) can be used.

  The configuration of the optical filter of the present invention can be appropriately adjusted within a range that does not impair the effects of the present invention except that it has a substrate and a near-infrared absorbing adhesive layer. What is necessary is just to select a required function suitably from the adhesive layers other than the said various function film and a near-infrared absorption adhesive layer according to the function for which an optical filter is calculated | required.

  However, when the optical filter of the present invention is used for a display as described above, it is preferable that the transmitted light from the C light source is achromatic, so that the chromaticity coordinates of the transmitted light can be within the above range. desired. Therefore, after forming the near infrared absorption adhesive layer as an optical filter so that the above preferable optical characteristics and durability can be compatible, the type of the functional film or substrate is changed according to the chromaticity of the transmitted light of the optical filter. It is preferable to select appropriately such that the chromaticity coordinates are in the above range.

The preferable luminous transmittance and near infrared transmittance of the optical filter are as described above. For example, when the near infrared absorbing pressure-sensitive adhesive layer is used as an optical filter in order to make the luminous transmittance within the preferable range, the optical filter described above. It is preferable to appropriately select the luminous transmittance of the above-described substrate and functional film after forming so as to satisfy both preferable optical characteristics and durability. Furthermore, it is particularly preferable that the chromaticity coordinates (x, y) and the luminous transmittance are simultaneously satisfied.
Hereafter, the manufacturing method of the optical filter of this invention is demonstrated.

[Manufacture of optical filters]
The method for producing the optical filter is not particularly limited, and a conventionally known method can be applied.
An optical filter comprising a substrate and a near-infrared absorbing adhesive layer is prepared, for example, by preparing an adhesive film in which a near-infrared absorbing adhesive layer is formed on a peelable film, and sticking the near-infrared absorbing adhesive layer of the adhesive film to the substrate To do. Thereafter, the peelable film is peeled from the near-infrared absorbing adhesive layer of the adhesive film, and the exposed near-infrared absorbing adhesive layer is directly attached to, for example, the display surface to obtain an optical filter.

  Moreover, the optical filter with which the board | substrate and the functional film were affixed through the near-infrared absorption adhesive layer is manufactured by sticking a functional film on the exposed near-infrared absorption adhesive layer in the above. Moreover, as another manufacturing method, the method of preparing the adhesive film in which the near-infrared absorption adhesive layer is formed on the functional film, and sticking the near-infrared absorption adhesive layer of an adhesive film to a board | substrate is mentioned. On the functional film of the laminate laminated in the order of the substrate / near infrared absorbing adhesive layer / functional film, if necessary, another functional film may be used using an adhesive layer other than the near infrared absorbing adhesive layer. It is good also as an optical filter of the structure of a board | substrate / near-infrared absorption adhesion layer / functional film / adhesion layer / other functional films (however, "adhesion layer" is adhesion layers other than a near-infrared absorption adhesion layer).

  As for the optical filter having an adhesive layer between a plurality of functional films, as described above, an adhesive film having a near infrared absorption adhesive layer formed on a substrate, a peelable film or a functional film, a peelable film or a functional film. Using an adhesive film on which an adhesive layer other than the near-infrared absorbing adhesive layer is formed and, if necessary, one or two or more functional films, in the same manner as described above, however, the layers are laminated and bonded together as appropriate. It can be manufactured.

  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 is suitably used as an optical filter for flat displays such as PDP, plasma addressed liquid crystal (PALC) display panel, field emission display (FED) panel, and displays such as cathode ray tube display (CRT). be able to.
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.

Hereinafter, although the optical filter of this invention is demonstrated more concretely with reference to an Example, this invention is not limited to a following example. Examples 1 to 5 are examples, and examples 6 and 7 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.

Component (A): Tetraazaporphyrin-based dye “TAP-HTBX”: manufactured by Yamada Chemical Co., Ltd., trade name, solubility in methyl ethyl ketone (MEK); 1.2 g / 100 g, λ _max ; 595 nm, ε; 112000
Component (B): Diimonium dye (b)
“CIR-FS265”: manufactured by Nippon Carlit Co., Ltd., trade name (C) component: UV absorber “CHIMASORB 81”: manufactured by BASF, trade name (D) component: light stabilizer “Nicarbamate Ni”: Wako Pure Chemical Industries, Ltd. Product, solubility in bis (dibutyldithiocarbamate) nickel (II), MEK; 5 g / 100 g.
“EST-3”: manufactured by Sumitomo Seika Co., Ltd., trade name, solubility in MEK; 16.7 g / 100 g.
(E) Component: Acrylic pressure-sensitive adhesive Pressure-sensitive adhesive (E2): Crosslinkable acrylic (co) polymer ("NCK101": Toyo Ink, trade name, solid content 30%) and a cross-linking agent ("Coronate HL") : Nippon Polyurethane, product name)

(F) component: near-infrared absorbing dye (f)
(F1) Phthalocyanine type dyes “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
“IR-915”: λ _max : 963 nm, ε; 53600
(F2) Diimonium dye (not classified as diimonium dye (b))
“CIR-RL”: manufactured by Nippon Carlit Co., Ltd., trade name, diimonium-bis (trifluoromethanesulfonyl) imidoate (G) component: color tone correction dye (g)
“Kayaset Violet A-R”: Nippon Kayaku, trade name “Kayaset Green AB”: Nippon Kayaku, trade name “ORASOL YELLOW 190”: BASF, trade name

(Example 1)
By the following method, an optical filter in which an antireflection film was stuck on a glass substrate via a near-infrared absorbing adhesive layer was produced.

  Tetraazaporphyrin dye "TAP-HTBX" 0.0144 parts by mass, diimonium dye (b) "CIR-FS265" 0.1167 parts by mass, light stabilizer "Ni carbamate" 0.0330 parts by mass, UV absorber 1.125 parts by mass of “CHIMASSORB 81” was dissolved in 6 parts by mass of methyl ethyl ketone. In this, 30 parts by mass of “NCK101” (containing 30 wt% of crosslinkable acrylic (co) polymer as a solid content) and 0.24 parts by mass of “Coronate HL” (crosslinking agent) are added as an acrylic adhesive. The pressure-sensitive adhesive composition 1 for forming a near-infrared absorbing pressure-sensitive adhesive layer was prepared by stirring.

  On the release film having a silicone resin layer formed on the surface of the PET film, the above-mentioned pressure-sensitive adhesive composition 1 is applied by an applicator and dried by performing a heat treatment for 5 minutes in an oven at 100 ° C. to a thickness of about 25 μm. An adhesive film 1 was obtained by forming an infrared absorbing adhesive layer.

  The obtained adhesive film 1 was bonded to the PET surface of an antireflection film (manufactured by NOF Corporation, trade name “Realak (RL1700)”), and then the release film was peeled off. The optical filter 1 was obtained by pasting this on a glass substrate.

(Example 2)
An adhesive film 2 was obtained in the same manner as in Example 1 except that 0.0330 parts by mass of a light stabilizer ("EST-3") was added instead of 0.0330 parts by mass of the light stabilizer "Ni carbamate". It was. An optical filter 2 was obtained in the same manner as in Example 1 using the adhesive film 2 instead of the adhesive film 1.

(Example 3)
A pressure-sensitive adhesive film 3 was obtained in the same manner as in Example 1 except that 0.0130 parts by mass of a phthalocyanine dye “IR-14” was further added. An optical filter 3 was obtained in the same manner as in Example 1 using the adhesive film 3 instead of the adhesive film 1.

(Example 4)
The addition amount of the diimonium dye (b) “CIR-FS265” is 0.2440 parts by mass, and the phthalocyanine dye “IR-14” is 0.0507 parts by mass, and the phthalocyanine dye “IR-28” is 0.0289 parts by mass. In the same manner as in Example 1, except that 0.0217 parts by mass of a phthalocyanine dye “IR-915” was added and 0.0058 parts by mass of a color tone correction dye (g) “Kayaset Violet A-R”) was added. The adhesive film 4 was obtained. An optical filter 4 was obtained in the same manner as in Example 1 using the adhesive film 4 instead of the adhesive film 1.

(Example 5)
The added amount of the tetraazaporphyrin-based dye “TAP-HTBX” is 0.0332 parts by mass, and further, the color tone correction dye (g) “Kayaset Green AB” 0.0058 parts by mass, “ORASOL YELLOW 190” 0.0087 parts by mass A pressure-sensitive adhesive film 5 was obtained in the same manner as in Example 3 except that the part was added. An optical filter 5 was obtained in the same manner as in Example 1 using the adhesive film 5 instead of the adhesive film 1.

(Example 6)
An adhesive film 6 was obtained in the same manner as in Example 1 except that 0.0330 parts by mass of the light stabilizer “Ni carbamate” was not added. An optical filter 6 was obtained in the same manner as in Example 1 using the adhesive film 6 instead of the adhesive film 1.

(Example 7)
Example 1 except that 0.1463 parts by mass of a diimonium dye “CIR-RL” not classified as a diimonium dye (b) was added instead of 0.1167 parts by mass of the diimonium dye (b) “CIR-FS265”. In the same manner, an adhesive film 7 was obtained. An optical filter 7 was obtained in the same manner as in Example 1 using the adhesive film 7 instead of the adhesive film 1.

[Evaluation]
Using the optical filters 1 to 7 obtained in Examples 1 to 7 as samples, the optical properties of each sample (luminous transmittance, chromaticity, near infrared transmittance as transmittance at 850 nm, and transmittance at neon cut wavelength (593 nm) ) And light resistance were evaluated by the following methods. The results are shown in Table 1 together with the types of components contained in the near-infrared absorbing adhesive layer.

(Initial optical properties)
Using a spectrophotometer (manufactured by Shimadzu Corporation, trade name “SolidSpec-3700”), the spectrum of a 20 × 20 mm square specimen 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 850 nm and the transmittance | permeability in a neon cut wavelength (593 nm) were calculated | required as near-infrared transmittance.

(Light resistance)
Using a light resistance tester (Suga Test Instruments Co., Ltd., xenon weather meter X25), after irradiating light of 320 nm or more with 300 MJ / m ² , the luminous transmittance Tv and near infrared transmittance of each sample at 850 nm The transmittance and the transmittance at the neon cut wavelength (593 nm) were measured, and the measured values before and after the test were compared.

  “◯” if the difference in transmittance before and after the test is less than 3%, “△” if any one is 3% or more and less than 8%, “×” if any one is 8% or more. "

Claims (5)

A substrate,
A tetraazaporphyrin-based dye disposed on the substrate, a diimonium-based near-infrared absorbing dye composed of an amorphous form of a diimonium salt represented by the following general formula (1), an ultraviolet absorber, and a copper complex An optical filter comprising a light stabilizer made of a nickel complex and an adhesive layer containing an acrylic adhesive.

In formula (1), R ^{1 to} R ⁸ each represent a monovalent organic group that may be the same or different, and X ⁻ represents an anion.   The optical filter according to claim 1, wherein a ligand of the complex is selected from organic ligands having an oxygen atom or a sulfur atom as a coordination atom.   The optical filter of Claim 1 or 2 which contains the said light stabilizer in the ratio of 0.03-17 mass parts with respect to 100 mass parts of said acrylic adhesives.   The optical filter of any one of Claims 1-3 which contains the said diimonium type | system | group near-infrared absorption pigment | dye in the ratio of 0.6-6.7 mass parts with respect to 100 mass parts of said acrylic adhesives.   The optical filter according to any one of claims 1 to 4, wherein the tetraazaporphyrin-based pigment is contained at a ratio of 0.06 to 0.6 parts by mass with respect to 100 parts by mass of the acrylic pressure-sensitive adhesive.