JP6279406B2 - Filter comprising naphthalocyanine compound - Google Patents

Description

The present invention relates to a filter containing a naphthalocyanine compound having a substituent having a specific structure (for example, a heat ray shielding filter, an optical filter, a display filter).

In recent years, with the advancement of sophistication of society, various functional materials using organic compounds have been actively developed, including applications related to optoelectronics.
As such an organic material, for example, a phthalocyanine compound has attracted attention.
Phthalocyanine compounds include, for example, color toners, inkjet inks, anti-counterfeiting inks, goggles, lenses, optical recording media, photosensitive dyes for laser treatment, thermal transfer, thermal stencil, and other photothermal exchange agents, thermal rewritable recording. It is used for a wide range of applications such as photothermal exchange agents for lasers, photothermal exchange agents for laser transmission welding of plastic materials, heat ray shielding filter applications, optical filter applications, display filter applications, and near infrared absorbers.

Recently, from the viewpoint of energy saving, application to the field using the effect of blocking the heat ray has been actively studied.
For example, a near-infrared absorption filter using a phthalocyanine compound having an alkyl group has been proposed (Patent Document 1).
For example, it has been proposed to use an aryloxy-substituted phthalocyanine compound having vanadium oxide as a central metal as a heat ray shielding / absorbing material (Patent Document 2).
For example, a near-infrared absorption filter that includes copper as a central metal and includes a phthalocyanine compound having a substituted amino group and an aryloxy group has been proposed (Patent Document 3).
For example, it has been proposed to use a phthalocyanine compound having an alkyl substituent and an aryloxy substituent as a near-infrared absorbing material (Patent Document 4).
Filters using these phthalocyanine compounds as near-infrared absorbers have a certain heat ray shielding effect, but at present, further improvements are required.

Further, for example, a compound having an alkyl group or an alkoxy group at the α-position of a 1,2-naphthalocyanine skeleton is already known (Patent Document 5), but the compound is difficult to weather resistance (for example, light resistance). However, a filter containing the compound has a poor heat ray shielding ability, and further improvement is now required.

JP-A-2-138382 JP 2011-94127 A Special table 2012-514063 gazette JP2013-108060A JP-A-2-43269

An object of the present invention is to provide a filter having excellent optical characteristics containing a naphthalocyanine compound having a specific structure and excellent weather resistance (for example, light resistance and heat resistance).

As a result of intensive studies on the filter using various compounds, the present inventor has completed the present invention.
That is, the present invention
(I) A filter comprising at least one naphthalocyanine compound represented by the general formula (1).
(Wherein R _{1 to} R ₄ each independently represents a halogen atom or a substituted or unsubstituted aryl group, and X _{1 to} X ₂₀ each independently represent a hydrogen atom, a halogen atom, a straight chain, a branched chain or a cyclic group) An alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aryloxy group,
M represents two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or a metal oxide atom)
further,

(Ii) the filter according to (i), comprising a substrate and a transparent adhesive layer,
(Iii) The filter according to (i), comprising a substrate and a functional transparent layer.

According to the present invention, it is possible to provide a filter having excellent optical characteristics and excellent weather resistance, comprising at least one naphthalocyanine compound having a specific structure.

It is typical sectional drawing of the filter of this invention. It is typical sectional drawing of the filter of this invention. It is typical sectional drawing of the filter of this invention. It is typical sectional drawing of the filter of this invention. It is typical sectional drawing of the filter of this invention. It is typical sectional drawing of the filter of this invention. It is typical sectional drawing of the filter of this invention. It is typical sectional drawing of the filter of this invention. It is typical sectional drawing of the filter of this invention.

Hereinafter, the present invention will be described in detail.
The present invention is a filter comprising at least one naphthalocyanine compound represented by the general formula (1).

(Wherein R _{1 to} R ₄ each independently represents a halogen atom or a substituted or unsubstituted aryl group, and X _{1 to} X ₂₀ each independently represent a hydrogen atom, a halogen atom, a straight chain, a branched chain or a cyclic group) An alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aryloxy group,
M represents two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or a metal oxide atom)

The naphthalocyanine compound represented by the general formula (1) is a compound in which a halogen atom or a substituted or unsubstituted aryl group is substituted at the α-position of the naphthalocyanine skeleton, and has excellent optical characteristics (for example, light absorption characteristics). And excellent weather resistance (for example, light resistance and heat resistance).
Moreover, the filter of the present invention comprising a naphthalocyanine compound having such characteristics has excellent optical characteristics and excellent weather resistance.

In the compound represented by the general formula (1), R _{1 to} R ₄ each independently represents a halogen atom or a substituted or unsubstituted aryl group, preferably a halogen atom or a substitution having 4 to 20 carbon atoms. Or an unsubstituted aryl group is represented, More preferably, a fluorine atom, a chlorine atom, a bromine atom, or a C4-C16 substituted or unsubstituted aryl group is represented.
In addition, as a substituent of a substituted aryl group, Preferably, halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, C4-C20 Can be mentioned.
The aryl group may be monosubstituted or polysubstituted with these substituents.
In the present specification, the aryl group represents, for example, a carbocyclic aromatic group such as a phenyl group or a naphthyl group, for example, a heterocyclic aromatic group such as a furyl group, a thienyl group or a pyridyl group, Represents a carbocyclic aromatic group.

In the general formula (1), specific examples of the halogen atom represented by R _{1 to} R ₄ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In the general formula (1), specific examples of the substituted or unsubstituted aryl group represented by R _{1 to} R ₄ include, for example, a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, and 4-methylphenyl. Group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 4-n-propylphenyl group, 4-isopropylphenyl group, 4-n-butylphenyl group, 4-isobutylphenyl group, 4- tert-butylphenyl group, 4-n-pentylphenyl group, 4-isopentylphenyl group, 4-tert-pentylphenyl group, 4-n-hexylphenyl group, 4-cyclohexylphenyl group, 4-n-heptylphenyl group 4-n-octylphenyl group, 4-n-nonylphenyl group, 4-n-decylphenyl group, 4-n-undecylphenyl group 4-n-dodecylphenyl group, 4-n-tetradecylphenyl group, 4-n-hexadecylphenyl group, 4-n-octadecylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,5,6- Tetramethylphenyl group,
2,6-diethylphenyl group, 3,5-di-tert-butylphenyl group,
5-indanyl group, 1,2,3,4-tetrahydro-5-naphthyl group, 1,2,3,4-tetrahydro-6-naphthyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxy Phenyl group, 3-ethoxyphenyl group, 4-ethoxyphenyl group, 4-n-propoxyphenyl group, 4-isopropoxyphenyl group, 4-n-butoxyphenyl group, 4-isobutoxyphenyl group, 4-n-pentyl Oxyphenyl group, 4-n-hexyloxyphenyl group, 4-cyclohexyloxyphenyl group, 4-n-heptyloxyphenyl group, 4-n-octyloxyphenyl group, 4-n-nonyloxyphenyl group, 4-n -Decyloxyphenyl group, 4-n-undecyloxyphenyl group, 4-n-dodecyloxyphenyl group, 4-n-tetra Siloxyphenyl group, 4-n-hexadecyloxyphenyl group, 4-n-octadecyloxyphenyl group, 2,3-dimethoxyphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 3, 4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,5-diethoxyphenyl group,
3,4-methylenedioxyphenyl group, 3-trifluoromethoxyphenyl group, 4-trifluoromethoxyphenyl group,

2-methoxy-4-methylphenyl group, 2-methoxy-5-methylphenyl group, 3-methoxy-4-methylphenyl group, 2-methyl-4-methoxyphenyl group, 3-methyl-4-methoxyphenyl group, 3-methyl-5-methoxyphenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 4-bromophenyl group, 2 , 4-Difluorophenyl group, 3,5-difluorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2-methyl-4-chlorophenyl Group, 2-chloro-4-methylphenyl group, 3-chloro-4-methylphenyl group, 2-chloro-4- Toxiphenyl group, 3-methoxy-4-fluorophenyl group, 3-methoxy-4-chlorophenyl group, 3-fluoro-4-methoxyphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 3 , 5-bis (trifluoromethyl) phenyl group, 4-phenylphenyl group, 3-phenylphenyl group, 2-phenylphenyl group, 4- (4′-methylphenyl) phenyl group, 4- (4′-methoxyphenyl) ) Phenyl group, 3,5-diphenylphenyl group, 1-naphthyl group, 2-naphthyl group, 4-methyl-1-naphthyl group, 4-ethoxy-1-naphthyl group, 6-n-butyl-2-naphthyl group 6-methoxy-2-naphthyl group, 7-ethoxy-2-naphthyl group, 2-furyl group, 2-thienyl group, 5-ethyl-2-thienyl group 5-n-pentyl-2-thienyl group, 5-n-decyl-2-thienyl group, 5-phenyl-2-thienyl group, 5- (2′-thienyl) -2-thienyl group, 3-thienyl group And substituted or unsubstituted aryl groups such as 2-pyridyl group, 3-pyridyl group, 4-pyridyl group and the like.

In the compound represented by the general formula (1), X _{1 to} X ₂₀ each independently represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a linear, linear, branched or cyclic alkoxy group, Represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted aryloxy group,
Preferably, a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a linear, branched or cyclic alkoxy group having 2 to 20 carbon atoms, or a carbon number Represents 4 to 20 substituted or unsubstituted aryl groups,
More preferably, a hydrogen atom, a fluorine atom, a chlorine atom, a linear, branched or cyclic alkyl group having 1 to 14 carbon atoms, a linear, branched or cyclic alkoxy group having 2 to 14 carbon atoms, or 4 to 4 carbon atoms. Represents 16 substituted or unsubstituted aryl groups.
In addition, as a substituent of a substituted aryl group, Preferably, halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, C4-C20 Can be mentioned.
The aryl group may be monosubstituted or polysubstituted with these substituents.

In the general formula (1), specific examples of the halogen atom represented by X _{1 to} X ₂₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In the general formula (1), specific examples of the linear, branched or cyclic alkyl group represented by X _{1 to} X ₂₀ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl. Group, isobutyl group, sec-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 2-pentyl group, 3-pentyl group, 1,2-dimethylpropyl group, 1-methylbutyl group, 2 -Methylbutyl group, 3-methyl-2-butyl group, 2-ethylpropyl group,
n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methylpentyl group, 4-methyl-2-pentyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3, 3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group,
n-heptyl group, 1-methylhexyl group, 3-methylhexyl group, 5-methylhexyl group, 2,4-dimethylpentyl group, 2,4-dimethyl-3-pentyl group,

Cyclohexylmethyl group, 2-cyclohexylethyl group, n-octyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, 2,5-dimethylhexyl group, 2,5,5 -Trimethylhexyl group, n-nonyl group, 2,2-dimethylheptyl group, 2,6-dimethyl-4-heptyl group, 3,5,5-trimethylhexyl group, n-decyl group, 4-ethyloctyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, 1,3,5,7-tetramethyloctyl group, n-tridecyl group, 1-hexylheptyl group, n-tetradecyl group, n-pentadecyl group, n -Hexadecyl group, n-heptadecyl group, n-octadecyl group, n-eicosyl group, cyclopentyl group, cyclohexyl group, 4-methyl Kurohekishiru group, 4-tert-butylcyclohexyl group, cycloheptyl group, and a straight-chain, branched or cyclic alkyl groups such as cyclooctyl group.

In the general formula (1), specific examples of the linear, branched or cyclic alkoxy group represented by X _{1 to} X ₂₀ include, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n- Butoxy group, isobutoxy group, sec-butoxy group, n-pentyloxy group, isopentyloxy group, neopentyloxy group, tert-pentyloxy group, 2-pentyloxy group, 3-pentyloxy group, 1,2-dimethyl Propyloxy group, 1-methylbutyloxy group, 2-methylbutyloxy group, 3-methyl-2-butyloxy group, 2-ethylpropyloxy group,
n-hexyloxy group, 1-methylpentyloxy group, 2-methylpentyloxy group, 4-methylpentyloxy group, 4-methyl-2-pentyloxy group, 1,2-dimethylbutyloxy group, 2,3- Dimethylbutyloxy group, 3,3-dimethylbutyloxy group, 1-ethylbutyloxy group, 2-ethylbutyloxy group,
n-heptyloxy group, 1-methylhexyloxy group, 3-methylhexyloxy group, 5-methylhexyloxy group, 2,4-dimethylpentyloxy group, 2,4-dimethyl-3-pentyloxy group,

Cyclohexylmethyloxy group, n-octyloxy group, tert-octyloxy group, 1-methylheptyloxy group, 2-ethylhexyloxy group, 2-propylpentyloxy group, 2,5-dimethylhexyloxy group, 2,5, 5-trimethylhexyloxy group, n-nonyloxy group, 2,2-dimethylheptyloxy group, 2,6-dimethyl-4-heptyloxy group, 3,5,5-trimethylhexyloxy group, n-decyloxy group, 4 -Ethyloctyloxy group, n-undecyloxy group, 1-methyldecyloxy group, n-dodecyloxy group, 1,3,5,7-tetramethyloctyloxy group, n-tridecyloxy group, 1-hexyl Heptyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group Group, n-heptadecyloxy group, n-octadecyloxy group, n-eicosyloxy group, cyclopentyloxy group, cyclohexyloxy group, 4-methylcyclohexyloxy group, 4-tert-butylcyclohexyloxy group, cycloheptyloxy group And a straight-chain, branched or cyclic alkoxy group such as a cyclooctyloxy group.

In the general formula (1), specific examples of the substituted or unsubstituted aryl group represented by X _{1 to} X ₂₀ include, for example, the substituents exemplified as specific examples of R _{1 to} R ₄ in the general formula (1). Or an unsubstituted aryl group can be mentioned.

In the general formula (1), specific examples of the substituted or unsubstituted aryloxy group represented by X _{1 to} X ₂₀ include, for example, a phenyloxy group, a 2-methylphenyloxy group, a 3-methylphenyloxy group, 4-methylphenyloxy group, 2-ethylphenyloxy group, 3-ethylphenyloxy group, 4-ethylphenyloxy group, 4-n-propylphenyloxy group, 4-isopropylphenyloxy group, 4-n-butylphenyl Oxy group, 4-isobutylphenyloxy group, 4-tert-butylphenyloxy group, 4-n-pentylphenyloxy group, 4-isopentylphenyloxy group, 4-tert-pentylphenyloxy group, 4-n-hexyl Phenyloxy group, 4-cyclohexylphenyloxy group, 4-n-heptylphenyl ester Si group, 4-n-octylphenyloxy group, 4-n-nonylphenyloxy group, 4-n-decylphenyloxy group, 4-n-undecylphenyloxy group, 4-n-dodecylphenyloxy group, 4 -N-tetradecylphenyloxy group, 4-n-hexadecylphenyloxy group, 4-n-octadecylphenyloxy group, 2,3-dimethylphenyloxy group, 2,4-dimethylphenyloxy group, 2,5- Dimethylphenyloxy group, 2,6-dimethylphenyloxy group, 3,4-dimethylphenyloxy group, 3,5-dimethylphenyloxy group, 3,4,5-trimethylphenyloxy group, 2,3,5,6 -Tetramethylphenyloxy group,
2,6-diethylphenyloxy group, 3,5-di-tert-butylphenyloxy group,
5-indanyloxy group, 1,2,3,4-tetrahydro-5-naphthyloxy group, 1,2,3,4-tetrahydro-6-naphthyloxy group, 2-methoxyphenyloxy group, 3-methoxyphenyl Oxy group, 4-methoxyphenyloxy group, 3-ethoxyphenyloxy group, 4-ethoxyphenyloxy group, 4-n-propoxyphenyloxy group, 4-isopropoxyphenyloxy group, 4-n-butoxyphenyloxy group, 4-isobutoxyphenyloxy group, 4-n-pentyloxyphenyloxy group, 4-n-hexyloxyphenyloxy group, 4-cyclohexyloxyphenyloxy group, 4-n-heptyloxyphenyloxy group, 4-n- Octyloxyphenyloxy group, 4-n-nonyloxyphenyloxy group, 4-n- Siloxyphenyloxy group, 4-n-undecyloxyphenyloxy group, 4-n-dodecyloxyphenyloxy group, 4-n-tetradecyloxyphenyloxy group, 4-n-hexadecyloxyphenyloxy group, 4 -N-octadecyloxyphenyloxy group, 2,3-dimethoxyphenyloxy group, 2,4-dimethoxyphenyloxy group, 2,5-dimethoxyphenyloxy group, 3,4-dimethoxyphenyloxy group, 3,5-dimethoxy Phenyloxy group, 3,5-diethoxyphenyloxy group,
3,4-methylenedioxyphenyloxy group, 3-trifluoromethoxyphenyloxy group, 4-trifluoromethoxyphenyloxy group,

2-methoxy-4-methylphenyloxy group, 2-methoxy-5-methylphenyloxy group, 3-methoxy-4-methylphenyloxy group, 2-methyl-4-methoxyphenyloxy group, 3-methyl-4- Methoxyphenyloxy group, 3-methyl-5-methoxyphenyloxy group, 2-fluorophenyloxy group, 3-fluorophenyloxy group, 4-fluorophenyloxy group, 2-chlorophenyloxy group, 3-chlorophenyloxy group, 4 -Chlorophenyloxy group, 4-bromophenyloxy group, 2,4-difluorophenyloxy group, 3,5-difluorophenyloxy group, 2,4-dichlorophenyloxy group, 2,5-dichlorophenyloxy group, 3,4- Dichlorophenyloxy group, 3,5-dichlorophenyloxy group, 2- Tyl-4-chlorophenyloxy group, 2-chloro-4-methylphenyloxy group, 3-chloro-4-methylphenyloxy group, 2-chloro-4-methoxyphenyloxy group, 3-methoxy-4-fluorophenyloxy Group, 3-methoxy-4-chlorophenyloxy group, 3-fluoro-4-methoxyphenyloxy group, 3-trifluoromethylphenyloxy group, 4-trifluoromethylphenyloxy group, 3,5-bis (trifluoromethyl) ) Phenyloxy group, 4-phenylphenyloxy group, 3-phenylphenyloxy group, 2-phenylphenyloxy group, 4- (4′-methylphenyl) phenyloxy group, 4- (4′-methoxyphenyl) phenyloxy Group, 3,5-diphenylphenyloxy group, 1-naphthyloxy group, 2- Futyloxy group, 4-methyl-1-naphthyloxy group, 4-ethoxy-1-naphthyloxy group, 6-n-butyl-2-naphthyloxy group, 6-methoxy-2-naphthyloxy group, 7-ethoxy-2 -Naphtyloxy group, 2-furyloxy group, 2-thienyloxy group, 5-ethyl-2-thienyloxy group, 5-n-pentyl-2-thienyloxy group, 5-n-decyl-2-thienyloxy group 5-phenyl-2-thienyloxy group, 5- (2′-thienyl) -2-thienyloxy group, 3-thienyloxy group, 2-pyridyloxy group, 3-pyridyloxy group, 4-pyridyloxy group, etc. And substituted or unsubstituted aryloxy groups.

  In the general formula (1), M represents two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or a metal oxide atom. It is preferably a divalent metal atom or a metal oxide atom.

Examples of the monovalent metal atom represented by M include Na, K, and Li.
Examples of the divalent metal atom represented by M include Cu, Zn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn, Mg, Ti, Be, Ca, Ba, Cd, Hg, and Pb. , Sn and the like.
Examples of the trivalent substituted metal atom represented by M include Al-F, Al-Cl, Al-Br, Al-I, Ga-F, Ga-Cl, Ga-Br, Ga-I, and In-. F, In-Cl, In- Br, In-I, Tl-F, Tl-Cl, Tl-Br, Tl-I, Al-C 6 H 5, Al-C 6 H 4 (CH 3), In- _{C 6 H 5, In-C} 6 H 4 (CH 3), Mn (OH), Mn (OC 6 H 5) , Mn [OSi (CH ₃ ) ₃ ], Fe—Cl, Ru—Cl, and the like.

The tetravalent substituted metal atom represented by M, for _{example, CrCl 2, SiCl 2, SiBr} 2, SiF 2, SiI 2, ZrCl 2, ZrI 2, GeCl 2, GeBr 2, GeF 2, GeI 2, SnCl ₂ , SnF ₂ , SnBr ₂ , TiF ₂ , TiCl ₂ , TiBr ₂ , Si (OH) ₂ , Ge (OH) ₂ , Zr (OH) ₂ , Mn (OH) ₂ , Sn (OH) ₂ , Ti (R) ₁₀ ) ₂ , Cr (R ₁₀ ) ₂ , Si (R ₁₀ ) ₂ , Sn (R ₁₀ ) ₂ , Ge (R ₁₀ ) ₂ [wherein R ₁₀ is an alkyl group, a phenyl group, a naphthyl group, or its Represents a derivative], Si (OR ₂₀ ) ₂ , Sn (OR ₂₀ ) ₂ , Ge (OR ₂₀ ) ₂ , Ti (OR ₂₀ ) ₂ , Cr (OR ₂₀ ) ₂ [wherein R ₂₀ is an alkyl group, Phenyl group, naphthyl group, trialkyl A silyl group, a dialkylalkoxysilyl group, or a derivative thereof], Sn (SR ₃₀ ) ₂ , Ge (SR ₃₀ ) ₂ [wherein R ₃₀ represents an alkyl group, a phenyl group, a naphthyl group, or a derivative thereof. And the like.
Examples of the metal oxide atom represented by M include VO, MnO, TiO and the like.
In the general formula (1), M is more preferably Cu, Zn, Fe, Co, Ni, Pd, Mg, VO, TiO, still more preferably Cu, Zn, Ni, VO, and particularly preferably. Are Cu and VO.

  Specific examples of the naphthalocyanine compound represented by the general formula (1) include the following compounds, but the present invention is not limited thereto.

The naphthalocyanine compound represented by the general formula (1) can be produced with reference to a method known per se.
That is, the naphthalocyanine compound represented by the general formula (1) includes, for example, a compound represented by the general formula (2) to the general formula (5) and a metal or a metal salt (for example, a metal halide or a metal carboxylate). ) In the presence of an organic solvent and optionally a base (eg ammonium molybdate, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0]- 5-nonene, trialkylamine, ammonia) (for example, JP-A-50-85630, JP-A-1-45474, JP-A-1-60660). Can be produced according to the method described in 1).

  The naphthalocyanine compound represented by the general formula (1) includes, for example, a compound represented by the general formula (2) to the general formula (5) and a metal or a metal salt (for example, a metal halide or a metal carboxylate). ) In the presence of an optionally halogenated hydrocarbon-based solvent and a nitrile-based solvent [for example, manufactured according to the method described in JP-A-2008-231153] Can do it.]

[Wherein R _{1 to} R ₄ and X _{1 to} X ₂₀ represent the same meaning as in the general formula (1)]

The compounds represented by the general formulas (2) to (5) can be produced by referring to a method known per se. For example, when the compound represented by the general formula (2) is described as an example, the compound in which R ₁ is a substituted or unsubstituted aryl group includes, for example, the compound represented by the general formula (6) and the general formula (7). )
Alternatively, the compound represented by the general formula (8) and the compound represented by the general formula (9)
As a catalyst, for example, a palladium catalyst [for example, bis (triphenylphosphine) palladium dichloride, tetrakis (triphenylphosphine) palladium, palladium acetate, palladium / carbon], and if necessary, act in the presence of a base [For example, Chem. Lett., 1200 (2000), Chem. Rev., 95, 2457 (1995), Chem.
Rev., 102, 1359 (2002), Chem. Rev., 107, 133 (2007), Tetrahedron, 54, 263 (1998) can be referred to].

[Wherein, X _{1 to} X ₅ represent the same meaning as in the general formula (1), R ₁ represents a substituted or unsubstituted aryl group, Z ₁ and Z ₂ represent a halogen atom or —OSO ₂ —R And M ₁ and M ₂ each represent a boron metal-containing group or a zinc metal-containing group.

In general formula (6) and general formula (9), the halogen atom represented by Z ₁ and Z ₂ preferably represents a chlorine atom, a bromine atom or an iodine atom, more preferably a bromine atom or iodine. Represents an atom.

In General Formula (6) and General Formula (9), in the —OSO ₂ —R group represented by Z ₁ and Z ₂ , R may be substituted with a substituted or unsubstituted aryl group, or a halogen atom. Represents a linear, branched or cyclic alkyl group, more preferably a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or a linear or branched chain having 1 to 10 carbon atoms which may be substituted with a halogen atom. Alternatively, it represents a cyclic alkyl group, and more preferably represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom.

As specific examples of the substituted or unsubstituted aryl group represented by R of -OSO 2 _-R group, and examples thereof include a phenyl group, a 4-methylphenyl group, a 4-chlorophenyl group and. In addition, specific examples of the linear, branched or cyclic alkyl group which may be substituted with the halogen atom represented by R of the —OSO ₂ —R group include, for example, a methyl group, an ethyl group, and an n-propyl group. Alkyl groups such as isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, cyclopentyl group, cyclohexyl group, n-octyl group, n-decyl group, trifluoromethyl group, chlorodifluoromethyl And alkyl groups substituted with halogen atoms such as a group, a dichlorofluoromethyl group, a pentafluoroethyl group, and an n-nonafluorobutyl group.
In General Formula (6) and General Formula (9), the —OSO ₂ —R group represented by Z ₁ and Z ₂ is more preferably a benzenesulfonyloxy group, a p-toluenesulfonyloxy group, or methanesulfonyloxy. Group, a trifluoromethanesulfonyloxy group.

In General Formula (7) and General Formula (8), the boron metal-containing group represented by M ₁ and M ₂ is preferably a group represented by General Formula (M−1).
_{-B (OR 0) (OR 00} ) (M-1)
(In the formula, R ₀ and R ₀₀ represent a hydrogen atom or an alkyl group, and R ₀ and R ₀₀ may be bonded to each other to form a cyclic alkylene group or an arylene group)
In General Formula (M-1), R ₀ and R ₀₀ each represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
When R ₀ and R ₀₀ are bonded to each other to represent a cyclic alkylene group, it preferably represents a cyclic alkylene group having 2 to 10 carbon atoms.
In addition, when R ₀ and R ₀₀ are bonded to each other to represent an arylene group, it preferably represents a 1,2-phenylene group having 6 to 10 carbon atoms which may be substituted with an alkyl group.

In General Formula (7) and General Formula (8), the zinc metal-containing group represented by M ₁ and M ₂ is preferably a group represented by General Formula (M-2).
-ZnZ ₀₀ (M-2)
(In the formula, Z ₀₀ represents a halogen atom)
In General Formula (M-2), Z ₀₀ represents a halogen atom, preferably a chlorine atom, a bromine atom, or an iodine atom.

Further, when the compound represented by the general formula (2) is described as an example, the compound in which R ₁ is a halogen atom is, for example, a compound represented by the general formula (10) and a base (for example, tert-butyllithium). , Lithium diisopropylamide, lithium-2,2,6,6-tetramethylpiperidide) to produce a compound of general formula (11), and then a halogenating agent (for example, N-fluorobenzenesulfonimide) , Chlorine, N-chlorosuccinimide, bromine, N-bromosuccinimide, iodine, perfluoroalkyliodine).

[Wherein X _{1 to} X ₅ represent the same meaning as in the general formula (1)]

In addition, when a compound represented by the general formula (2) to the general formula (5) is reacted with, for example, a metal or a metal salt to produce a naphthalocyanine compound represented by the general formula (1), Multiple isomers are formed during cyclization.
In the present specification, the naphthalocyanine compound represented by the general formula (1) is one compound selected from compounds represented by the general formula (1-A) to the general formula (1-D), or It represents a mixture of two or more isomers [eg Angew. Chem. Int. Ed. Eng., 32, 1422 (1993)].
In describing the structure of such a mixture of a plurality of isomers, for the sake of convenience, in this specification, for example, one structural formula represented by the general formula (1-A) is described. .

[Wherein R _{1 to} R ₄ , X _{1 to} X ₂₀ , and M represent the same meaning as in the general formula (1)]

As a specific example, for example, the compound having the structure described as the compound of Exemplified Compound No. 3 is one compound selected from the compounds represented by formula (3-a) to formula (3-d), or two or more compounds Represents a mixture of the following isomers.

The present invention is a filter comprising at least one naphthalocyanine compound represented by the general formula (1). In the filter of the present invention, the naphthalocyanine compound represented by the general formula (1) may be used alone or in combination.
Of course, as the naphthalocyanine compound represented by the general formula (1), for example, one compound selected from the compounds represented by the general formula (1-A) to the general formula (1-D), or two kinds Mixtures of the above isomers can be used. Further, if desired, each isomer can be separated from the mixture, and one of the isomers can be used, and a plurality of isomers having an arbitrary ratio can be used in combination. Incidentally, the naphthalocyanine compound represented by the general formula (1) includes not only crystals but also amorphous (amorphous).
Considering the preferable characteristics of the filter of the present invention, the naphthalocyanine compound represented by the general formula (1) is preferably a compound having an absorption maximum at 650 to 780 nm, and more preferably absorbed at 670 to 750 nm. It is a compound having a maximum.

As a filter of the present invention, for example, a heat ray shielding filter that shields sunlight or light in the near infrared region (near infrared) emitted from various displays,
For example, an optical filter for imaging such as a camera,
For example, it is a filter for various displays such as plasma display, liquid crystal display, organic electroluminescence display, FED (Field Emission Display), CRT (Cathode Ray Tube), for example, house window, car, airplane, train, spaceship, etc. It is used by being mounted on various transport aircraft, various image sensors, and various displays.
In addition, in a liquid crystal display, it can apply to various aspects, such as a transmission type and a reflection type, for example.

The configuration of the filter of the present invention is not particularly limited, but generally comprises a substrate (A), a transparent adhesive layer (B), a functional transparent layer (C) and / or a transparent conductive layer (D). It is a filter.
The configuration of the filter of the present invention is generally
(1) Filter comprising the substrate (A) (FIG. 1)
(2) A filter comprising a substrate (A) and a transparent adhesive layer (B) (FIG. 2)
(3) Filter comprising the substrate (A), the transparent adhesive layer (B) and the substrate (A) (FIG. 3)
(4) Filter comprising a functional transparent layer (C), a substrate (A), and a functional transparent layer (C) (FIG. 4)
(5) Filter comprising a transparent adhesive layer (B) (FIG. 5)
(6) Filter comprising the substrate (A) and the functional transparent layer (C) (FIG. 6)
(7) Filter comprising the substrate (A), the transparent adhesive layer (B) and the functional transparent layer (C) (FIG. 7)
(8) The filter (FIG. 8 and FIG. 9) which consists of a base | substrate (A), a transparent adhesion layer (B), a functional transparent layer (C), and a transparent conductive layer (D) can be mentioned.

As a structure of the filter of this invention, More preferably, it has the structure of said (1)-(7), More preferably, it has the structure of (1)-(4).
The filter of the present invention contains at least one naphthalocyanine compound represented by the general formula (1) in at least one layer or member constituting the substrate, the transparent adhesive layer, the functional transparent layer, and the transparent conductive layer. It consists of.
For example, in the filter having the configuration (2), the naphthalocyanine compound represented by the general formula (1) may be contained in the substrate or / and the transparent adhesive layer.
For example, in the filter having the configuration of (3), the naphthalocyanine compound represented by the general formula (1) may be contained in the substrate or / and the transparent adhesive layer, and more preferably, the general formula ( The compound represented by 1) is contained in the transparent adhesive layer.
For example, in the filter having the configuration of the above (4), the naphthalocyanine compound represented by the general formula (1) may be contained in the substrate or / and the functional transparent layer, and more preferably, the general formula The naphthalocyanine compound represented by (1) is contained in the substrate.

Of course, when configuring the filter of the present invention, various other configurations can be made in consideration of desired required characteristics. For example, the filter of the present invention can be provided with a plurality of transparent adhesive layers as desired. The filter of the present invention can be provided with a plurality of functional transparent layers. These layers may also contain a naphthalocyanine compound represented by the general formula (1).

Hereinafter, the substrate (A) will be described.
The substrate functions as a filter support, and transparent glass, green glass, and a transparent polymer film are generally used in the visible light range. As the transparent polymer film, for example, polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, polystyrene, polyarylate, polyether, polyether ether ketone, fluorinated aromatic polymer, polycarbonate, polyethylene, polypropylene, cyclic polyolefin, polyamide, Cellulose resins such as polyimide, polyamideimide, triacetyl cellulose, fluorine resins such as polyurethane and polytetrafluoroethylene, vinyl compounds such as polyvinyl chloride, polyacrylic acid, polyacrylic acid esters, polyacrylonitrile, vinyl compounds Polymers, polymethacrylic acid, polymethacrylic acid ester, vinylidene compounds such as polyvinylidene chloride, vinylidene fluoride / trifluoroe Examples thereof include, but are not limited to, a vinyl compound such as a len copolymer, an ethylene / vinyl acetate copolymer, a copolymer of a fluorine compound, a polyether such as polyethylene oxide, an epoxy resin, polyvinyl alcohol, and polyvinyl butyral. It is not something. The thickness of the substrate is not limited, but generally the thickness is 10 μm to 20 mm, preferably 20 μm to 10 mm.

From the viewpoint of production efficiency, the substrate is preferably a flexible transparent polymer film. Further, for example, the optical material of the present invention using the transparent polymer film directly bonded to the surface of glass or the like as the substrate. The filter has an advantage that when the glass is broken, the glass can be prevented from scattering.
In the present invention, the surface of the substrate may be subjected to etching treatment such as sputtering treatment, corona treatment, flame treatment, ultraviolet ray irradiation and electron beam irradiation, or undercoating treatment. A hard coat layer may be formed on at least one main surface of the substrate. Examples of the hard coat film that becomes the hard coat layer include thermosetting resins such as acrylic resins, silicon resins, melamine resins, urethane resins, alkyd resins, and fluorine resins, or photocurable resins. Can be mentioned. The thickness of the hard coat layer is about 1 to 100 μm. Moreover, the hard coat layer may contain one or more naphthalocyanine compounds represented by the general formula (1).

Hereinafter, the transparent adhesive layer (B) will be described.
In the present invention, the transparent adhesive layer is a layer made of any transparent adhesive material (adhesive, adhesive). The transparent adhesive layer is, for example, an acrylic adhesive, a silicon adhesive, a urethane adhesive, a polyvinyl butyral adhesive (PVB), an ethylene-vinyl acetate adhesive (EVA), a polyvinyl ether, a saturated polyester, a melamine resin. Formed from. In addition, as an adhesive material, a sheet form or a liquid form can be used.
For example, when using a sheet-like pressure-sensitive adhesive material as the adhesive material, the sheet-like adhesive material is laminated or laminated after the adhesive is applied. For example, when a liquid adhesive is used as the adhesive, it is cured and bonded by treatment at room temperature or high temperature after application and bonding, or by ultraviolet irradiation. Examples of the coating method include known methods such as a screen printing method, a bar coating method, a reverse coating method, a gravure coating method, a die coating method, a roll coating method, and a comma coating method. Although the thickness of a transparent adhesion layer is not specifically limited, Generally, it is 0.5-500 micrometers. The surface on which the transparent adhesive layer is formed and the surface to be bonded are preferably subjected to an easy adhesion treatment such as an easy adhesion coat or a corona discharge treatment in advance. Furthermore, after bonding through the transparent adhesive layer, the air mixed between the members at the time of bonding is defoamed or dissolved in the adhesive material to further improve the adhesion between the members. It is preferable to perform the treatment under pressure and heating conditions.
The transparent adhesive layer can also contain a plasticizer.
Examples of such plasticizers include glycol ester compounds such as triethylene glycol ester compounds, tetraethylene glycol ester compounds and tripropylene glycol ester compounds, and also organic phosphoric acid compounds and organic phosphorous acid compounds. Can do.
The transparent adhesive layer is generally provided on at least one surface of the base, and is used by being bonded to another base, for example.
In the filter of the present invention, the transparent adhesive layer may be a single layer or a plurality of layers.
The naphthalocyanine compound represented by the general formula (1) can be contained in at least one layer of the transparent adhesive layer.

Hereinafter, the functional transparent layer (C) will be described.
The filter of the present invention has a visible light reflection prevention function, an antiglare function, an antireflection antiglare function, a near infrared reflection function, a hard coat function (friction resistance function), depending on the installation method for the filter and the required function. In addition, a functional transparent layer having at least one of an antistatic function, an antifouling function, a gas barrier function, and an ultraviolet cut function and transmitting visible light is provided.
The functional transparent layer is a functional film itself having one or more of the above functions, or a support formed by applying a functional film to the coating method, printing method, or various conventionally known film forming methods, and further having each function. Supports can be used.

The support is preferably a transparent support, and is generally transparent glass, green glass, or a transparent polymer film. In addition, as a transparent polymer film, the transparent polymer film illustrated by the base | substrate (A) can be mentioned, for example. The thickness of the support is not particularly limited. Further, for example, a naphthalocyanine compound represented by the general formula (1) can be contained in a support composed of a transparent polymer film.
Even when the functional transparent layer is the functional film itself, the naphthalocyanine compound represented by the general formula (1) can be contained in the film. The functional transparent layer has an anti-reflection / anti-glare (ARAG) function that has a visible-light anti-reflection (AR: anti-reflection) function, an anti-glare (AG: anti-glare) function, or both functions to suppress visible light reflection. It is preferable to have any of the functions.
The functional transparent layer having a visible light reflection preventing function can determine the thickness of each component of the antireflection film and each component by optical design in consideration of the optical characteristics of the support for forming the antireflection film. it can. As a functional transparent layer having a visible light reflection preventing function, for example, a thin film such as a fluorine-based transparent polymer resin having a refractive index of 1.6 or less in the visible light region, magnesium fluoride, silicon-based resin, silicon oxide, For example, a single layer formed with an optical film thickness of ¼ wavelength, or an inorganic compound thin film made of metal oxide, fluoride, silicide, boride, carbide, nitride, sulfide, etc. having a different refractive index, or When an organic compound thin film made of a silicon-based resin, an acrylic resin, a fluorine-based resin, or the like is viewed from the support, there are those in which two or more layers are laminated in the order of a high refractive index layer and a low refractive index layer.

The functional transparent layer having a near infrared reflection function has a function of reflecting near infrared rays.
Examples of such a film having a near-infrared reflecting function include an aluminum vapor-deposited film, a noble metal thin film, a resin film in which metal oxide fine particles containing indium oxide as a main component and containing a small amount of tin oxide are dispersed, or a high refractive index material layer And a dielectric multilayer film in which low refractive index material layers are alternately laminated.
When the functional transparent layer having such a near-infrared reflecting function is provided, near-infrared rays can be more effectively shielded.
In the present invention, the layer having a near infrared reflection function may be provided on one side of the support or on both sides.

The functional transparent layer having a near infrared reflection function is more preferably a dielectric multilayer film in which high refractive index material layers and low refractive index material layers are alternately laminated.
As a material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index range of usually 1.7 to 2.5 is selected. Examples of such materials include titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, or indium oxide, and the like, and titanium oxide, tin oxide. And / or a material containing a small amount of cerium oxide or the like (for example, 0 to 10% by mass relative to the main component).

As a material constituting the low refractive index material layer, a material having a refractive index of 1.6 or less can be used, and more preferably, a material having a refractive index of 1.2 to 1.6 is selected. Examples of such materials include silicon oxide, aluminum oxide, lanthanum fluoride, magnesium fluoride, and sodium hexafluoride sodium.

The thickness of each of the high refractive index material layer and the low refractive index material layer is preferably 0.1λ to 0.5λ, where λ (nm) is the near infrared wavelength to be blocked.
Moreover, the total number of laminated layers of the high refractive index material layer and the low refractive index material layer in the dielectric multilayer film is 5 to 60 layers, and more preferably 6 to 50 layers.

As a method for forming the inorganic compound thin film, for example, a known method such as a sputtering method, an ion plating method, a vacuum deposition method, or a wet coating method can be applied. As a method for forming the organic compound thin film, for example, a known method such as a bar coating method, a reverse coating method, a gravure coating method, a die coating method, a roll coating method, or a comma coating method can be applied.

The visible light reflectance of the surface of the functional transparent layer having a visible light reflection preventing function is generally 2% or less, preferably 1.3% or less, and more preferably 0.8% or less. .
The functional transparent layer having an antiglare function is generally a transparent layer with respect to a visible light region having a minute uneven surface state of about 0.1 to 10 μm. The functional transparent layer having an antiglare function is, for example, an acrylic resin, a silicon resin, a melamine resin, a urethane resin, an alkyd resin, a fluorine resin, or a thermosetting resin, or a photocurable resin. Inorganic particles such as silica and organic silicon compounds, or inks formed by dispersing organic compound particles such as melamine and acrylic, for example, bar coating method, reverse coating method, gravure coating method, die coating method, roll coating method It can be formed by coating and curing on a support by a method such as a comma coating method. The average particle diameter of the inorganic compound particles and the organic compound particles is generally 1 to 40 μm.
The functional transparent layer having an antiglare function is, for example, a thermosetting resin such as an acrylic resin, a silicon resin, a melamine resin, a urethane resin, an alkyd resin, a fluorine resin, or a photocurable resin. Can be formed by pressing a mold having a desired haze or surface state and curing the surface to irregularities. The haze value that serves as an index of the antiglare function is generally 0.5 to 20%.

The functional transparent layer having an antireflection antiglare function can be prepared by forming an antireflection film on a film having an antiglare function or a support having an antiglare function. The visible light reflectance of the surface of the functional transparent layer having an antireflection antiglare function is generally adjusted to 1.5% or less, preferably 1.0% or less. For the purpose of adding scratch resistance to the filter of the present invention, it is preferable that the functional transparent layer has a hard coat function (friction resistance function). The functional transparent layer having a hard coat function can be prepared by forming a film having a hard coat function or a hard coat film on a support. Examples of the hard coat film include thermosetting resins such as acrylic resins, silicon resins, melamine resins, urethane resins, alkyd resins, and fluorine resins, or photocurable resins. The thickness of the hard coat film is generally about 1 to 100 μm.

The hard coat film can also be used for a high refractive index layer or a low refractive index layer of a transparent functional layer having an antireflection function. Further, an antireflection film may be formed on the hard coat film, and the functional transparent layer may have both an antireflection function and a hard coat function. Similarly, the functional transparent layer may have both functions of an antiglare function and a hard coat function. A functional transparent layer having both an antiglare function and a hard coat function can be prepared, for example, by forming an antireflection film on a hard coat film having irregularities by dispersing particles or the like. As for the surface hardness of the functional transparent layer having a hard coat function, the pencil hardness according to JISK5600 is at least H or more, preferably 2H or more. In addition, the filter of the present invention may require an antistatic function in consideration of prevention of dust adhesion and prevention of adverse effects on the human body. In this case, in order to provide an antistatic function, the functional transparent layer may have a certain conductivity. In general, the conductivity may be about 10 ¹¹ Ω / □ or less in terms of surface resistance. Examples of the conductive material include known transparent conductive films such as ITO (Indium Tin Oxide), and conductive films in which conductive ultrafine particles such as ITO ultrafine particles and tin oxide ultrafine particles are dispersed. In addition, the layer constituting the functional transparent layer having at least one of the antireflection function, the antiglare function, the antireflection antiglare function, the near infrared reflection function, and the hard coat function has conductivity. It is preferable. It is preferable that the functional transparent film has a gas barrier function with respect to, for example, environmental substances or moisture.

The required gas barrier function is generally 10 g / m ² · day or less in terms of moisture permeability. Examples of the film having a gas barrier function include silicon oxide, aluminum oxide, tin oxide, indium oxide, yttrium oxide, magnesium oxide, or a mixture thereof, or a metal oxide thin film obtained by adding other elements to these, Examples thereof include films made of various resins such as vinylidene chloride, acrylic resin, silicon resin, melamine resin, urethane resin, and fluorine resin. The thickness of the film having a gas barrier function is generally 10 to 200 nm in the case of a metal oxide thin film, and is generally 1 to 100 μm in the case of a resin. The film having a gas barrier function may have a single layer structure or a multilayer structure. Examples of the film having a gas barrier function against moisture include, for example, polyethylene, polypropylene, nylon, polyvinylidene chloride, vinylidene chloride and vinyl chloride, vinylidene chloride and acrylonitrile copolymers, and various resins such as fluorine resins. Mention may be made of membranes.

In addition, a layer constituting a functional transparent layer having any one or more of a visible light antireflection function, an antiglare function, an antireflection antiglare function, a near infrared reflection function, an antistatic function, and a hard coat function. Furthermore, the layer can also serve as a gas barrier function. Furthermore, an antifouling function can be imparted to the surface of the functional transparent layer so that fingerprints and the like can be easily prevented or removed. Those having an antifouling function are compounds having non-wetting properties with respect to water and / or fats and oils, and examples thereof include fluorine compounds and silicon compounds. In addition, by forming, for example, an inorganic thin film single layer that absorbs ultraviolet rays, or an antireflection film composed of an inorganic thin film multilayer, or a transparent film containing an ultraviolet absorbing compound, on the functional transparent layer, Furthermore, an ultraviolet cut function can be imparted.

It is preferable that the filter of the present invention, for example, the filter for plasma display, which is a display filter, functions as an electromagnetic wave shield having the property of shielding electromagnetic waves from the display screen. In addition to the substrate and the transparent adhesive layer, a transparent conductive layer (D) is preferably provided.

Hereinafter, the transparent conductive layer (D) will be described.
When the display filter is in the form of an electromagnetic wave shield, a transparent conductive layer is formed on one main surface of the substrate. The transparent conductive layer in the present invention is a transparent conductive layer composed of a single layer or a multilayer thin film. In addition, in the electromagnetic wave shield, electrical connection between the transparent conductive layer and the outside is necessary. For example, the functional transparent layer, the transparent adhesive layer, and the like secure the conduction portion while leaving the peripheral portion of the transparent conductive layer. It will be necessary. As a single transparent conductive layer, there are a conductive mesh such as a metal mesh and a conductive grid pattern film, and a transparent conductive thin film such as a metal thin film and an oxide semiconductor thin film. As the transparent conductive layer composed of a multilayer thin film, there is a multilayer thin film in which a metal thin film and a high refractive index transparent thin film are laminated. Multi-layer thin film composed of metal thin film and high refractive index transparent thin film prevents the reflection of metal in the specific wavelength region by the high-refractive index transparent thin film, the conductivity of silver and other metals and the near-infrared reflection characteristics due to free electrons. Since it can be performed, it has preferable characteristics with respect to conductivity, near-infrared cut function, and visible light transmittance. In order to obtain a display filter having an electromagnetic wave shielding function and a near-infrared cut function, a metal thin film having a high conductivity for electromagnetic wave absorption and a reflective interface for electromagnetic wave reflection and a high refractive index transparent thin film were laminated. A transparent conductive layer comprising a multilayer thin film is preferred. In order to have an electromagnetic wave shielding function necessary for a plasma display in addition to a high visible light transmittance and a low visible light reflectance, the transparent conductive layer generally has a surface resistance of 0.01 to 30Ω / □, more preferably 0.1 to 15Ω / □, and more preferably 0.1 to 5Ω / □. Also, the transparent conductive layer itself can have a near-infrared cut function, and the light transmittance minimum in the near-infrared wavelength region, for example, 800 to 1100 nm, can be 20% or less.

A preferred transparent conductive layer in the present invention is a high refractive index transparent thin film layer on one main surface of the substrate.
In the order of (Dt) and metal thin film layer (Dm), (Dt) / (Dm) is used as a repeating unit, and is repeatedly laminated 2 to 4 times, and at least a high refractive index transparent thin film layer is further laminated thereon. The sheet resistance of the transparent conductive layer is 0.1 to 5Ω / □. The material for the metal thin film layer is preferably silver, gold, platinum, palladium, copper, indium, tin, or an alloy of silver and gold, platinum, palladium, copper, indium or tin. Although the content rate of the silver in the alloy containing silver is not specifically limited, Generally, it is 50 to less than 100 mass%. In the case of a metal thin film composed of a plurality of layers, at least one layer should be used without alloying silver, or when viewed from the substrate, only the metal thin film layer in the first layer and / or the outermost layer is a silver alloy. It can be. The metal thin film layer is required to be in a continuous state rather than a discontinuous island structure from the viewpoint of conductivity, and the thickness is preferably 4 to 30 nm. In the case of a metal thin film composed of a plurality of layers, it is not necessary that all the layers have the same thickness, and further, all the layers may not be silver or a silver alloy having the same composition. Examples of the method for forming the metal thin film layer include known methods such as sputtering, ion plating, vacuum deposition, and plating.

  The transparent thin film forming the high refractive index transparent thin film layer is not particularly limited as long as it has transparency in the visible light region and has a function of preventing light reflection in the visible light region of the metal thin film layer. In general, a material having a refractive index with respect to visible light of 1.6 or more, preferably 1.8 or more is used. Examples of the material for forming such a transparent thin film include oxides such as indium, titanium, zirconium, bismuth, tin, zinc, antimony, tantalum, cerium, neodymium, lanthanum, thorium, magnesium, gallium, and the like. And zinc sulfide, and more preferably zinc oxide, titanium oxide, indium oxide, and a mixture of indium oxide and tin oxide (ITO). The thickness of the high refractive index transparent thin film layer is not particularly limited, but is generally 5 to 200 nm. Examples of the method for forming the high refractive index transparent thin film layer include known methods such as sputtering, ion plating, ion beam assist, vacuum deposition, and wet coating. For the purpose of improving the environmental resistance of the transparent conductive layer, a protective layer made of an organic or inorganic material can be provided on the surface of the transparent conductive layer to such an extent that various properties such as conductivity and optical properties are not significantly impaired. In addition, in order to improve the environmental resistance of the metal thin film layer and the adhesion between the metal thin film layer and the high refractive index transparent thin film layer, conductivity, optical characteristics, etc. are provided between the metal thin film layer and the high refractive index transparent thin film layer. An inorganic layer can be provided to such an extent that these properties are not impaired. In addition, as a material which forms an inorganic substance layer, copper, nickel, chromium, gold | metal | money, platinum, zinc, zirconium, titanium, tungsten, tin, palladium etc. or the alloy which consists of 2 or more types of these materials is mentioned, for example. . The thickness of the inorganic layer is preferably about 0.2 to 2 nm. As a method for forming the transparent conductive layer, there is a method using a conductive mesh in addition to a method using a transparent conductive thin film. A single-layer metal mesh will be described as an example of the conductive mesh. As a single-layer metal mesh, for example, there is one in which a copper mesh layer is formed on a base. Generally, a single layer of metal mesh is formed by bonding a copper foil on a base and then processing it into a mesh. As the copper foil, rolled copper or electrolytic copper is used, and a porous copper foil having a pore diameter of 0.5 to 5 μm is preferable. The porosity of the copper foil is preferably 0.01 to 20%, more preferably 0.02 to 5%. The porosity is a value defined by P / R where R is the volume and P is the pore volume. The copper foil may be subjected to various surface treatments (for example, chromate treatment, roughening treatment, pickling, zinc / chromate treatment). The thickness of the copper foil is generally 3 to 30 μm. The aperture ratio of the light transmission portion of the metal mesh is generally 60 to 95%. The shape of the opening is not particularly limited, but it is preferably in the form of a regular triangle, a regular square, a regular hexagon, a circle, a rectangle, a rhombus, and the like, and is arranged in the plane. In general, it is preferable that one side or diameter of the opening of the light transmitting portion is 5 to 200 μm. Further, the width of the metal in the portion where the opening is not formed is preferably 5 to 50 μm. The substantial sheet resistance of the metal layer having the light transmitting portion is preferably 0.01 to 0.5Ω / □. In order to electrically connect the transparent conductive layer and the ground portion (ground conductor) of the display device, a conductive adhesive layer is provided.

Examples of the conductive adhesive and conductive adhesive used for the conductive adhesive layer include acrylic adhesives, silicon adhesives, urethane adhesives, polyvinyl butyral adhesives (PVB), and ethylene-vinyl acetate adhesives. There are materials in which metal particles such as carbon, Cu, Ni, Ag, and Fe are dispersed as conductive particles in a base material such as (EVA), polyvinyl ether, saturated polyester, and melamine resin. The volume resistivity of the conductive adhesive and the conductive adhesive is generally 1 × 10 ⁻⁴ to 1 × 10 ³ Ω · cm. Examples of the conductive adhesive and the conductive pressure-sensitive adhesive include a sheet form and a liquid form. As the conductive adhesive material, a sheet-like pressure sensitive adhesive material can be suitably used. After pasting the sheet-like adhesive material, or after applying the adhesive, it is laminated and pasted. The liquid conductive adhesive can be cured by treatment at room temperature or high temperature after application and bonding, or by irradiation with ultraviolet rays. Examples of the method for applying the liquid conductive adhesive include a screen printing method, a bar coating method, a reverse coating method, a gravure coating method, a die coating method, a roll coating method, and a comma coating method. The thickness of the conductive adhesive layer is set in consideration of the volume resistivity and necessary conductivity, and is generally 0.5 to 50 μm, preferably 1 to 30 μm. A double-sided adhesive type conductive tape having conductivity on both sides can also be used.

The filter of the present invention contains at least one naphthalocyanine compound represented by the general formula (1). In addition, in this specification, content includes not only those contained in each layer consisting of various members or films, or the transparent adhesive material, but also the state of being applied to the surface of each member or each layer. is there.
Examples of the method for containing the naphthalocyanine compound represented by the general formula (1) in the filter of the present invention include the following methods (a) to (d).
(A) A method of adding to the transparent adhesive material and including it in the transparent adhesive layer,
(A) a method of kneading and containing the polymer resin,
(C) A method in which a naphthalocyanine compound represented by the general formula (1) is dispersed or dissolved in an organic solvent containing a polymer resin or a resin monomer, and various members are cast on each layer, for example,
(D) There is a method in which a naphthalocyanine compound represented by the general formula (1) is added to an organic solvent containing a binder resin, and coating is performed on various members and each layer as a paint.

  The naphthalocyanine compound represented by the general formula (1) is excellent in heat resistance. For example, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polybutyral is used at 200 to 350 ° C., and injection molding or extrusion molding. It can also be formed by such a method.

The amount of the naphthalocyanine compound represented by the general formula (1) contained in the filter of the present invention is not particularly limited, and a desired amount can be used depending on the purpose of use of the filter. .
For example, in the method (a), the content of the naphthalocyanine compound represented by the general formula (1) is not particularly limited, but is generally 10 ppm to 30% by mass with respect to the transparent adhesive material. Preferably, it is 10 ppm to 20% by mass.
In the methods (a) and (c), the content of the naphthalocyanine compound represented by the general formula (1) is not particularly limited. It is 10 ppm to 30% by mass, preferably 10 ppm to 20% by mass.
In the method (d), the content of the naphthalocyanine compound represented by the general formula (1) is not particularly limited, but is generally 10 ppm to 30% by mass with respect to the binder resin, preferably Is from 10 ppm to 20 mass%. Moreover, generally binder resin density | concentration is 1-50 mass% with respect to the whole coating material.
The shape of the filter of the present invention is not particularly limited, and includes various shapes such as a flat plate shape, a film shape, a corrugated plate shape, a spherical shape, and a dome shape.

In the filter of the present invention, in addition to the naphthalocyanine compound represented by the general formula (1), one or more light absorbing compounds can be used in combination as long as the desired effects of the present invention are not impaired.
The light absorbing compound is not particularly limited, and examples thereof include a compound having a desired absorption in the visible region or the near infrared region,
For example, known anthraquinone compounds, methine compounds, azomethine compounds, oxazine compounds, azo compounds, styryl compounds, coumarin compounds, porphyrin compounds, tetraazaporphyrin compounds, dibenzofuranone compounds, diketopyrrolopyrrole compounds, rhodamine compounds, xanthene compounds, pyromethenes Compounds having absorption in the visible region, such as compounds,
For example, known phthalocyanine compounds (for example, metal phthalocyanine complexes), naphthalocyanine compounds (for example, metal naphthalocyanine complexes), cyanine compounds, anthraquinone compounds, dithiol compounds (for example, nickel dithiol complexes), diimonium compounds, and further, for example, oxidation Examples thereof include compounds having absorption in the near infrared region other than the naphthalocyanine compound represented by the general formula (1) such as a metal oxide such as a tungsten-based compound (for example, cesium tungsten oxide).

The amount of the light-absorbing compound used can be arbitrarily set in consideration of the absorption wavelength and extinction coefficient of the compound and desired optical characteristics (for example, color, transmission characteristics, visual field, and contrast). For example, the amount of other compounds having absorption in the near infrared region is not particularly limited, but is preferably 80% by mass or less with respect to the naphthalocyanine compound represented by the general formula (1). Yes, more preferably 60% by mass or less, and still more preferably 40% by mass or less.
The filter of the present invention may further contain an ultraviolet absorber and an antioxidant as desired. The ultraviolet absorber is not particularly limited, and examples thereof include salicylic acid-based, benzophenone-based, benzotriazole-based, triazine-based, and cyanoacrylate-based ultraviolet absorbers. The antioxidant is not particularly limited, and examples thereof include phenolic antioxidants.

Since the filter of the present invention contains at least one naphthalocyanine compound represented by the general formula (1), it shields light in the near-infrared region and has excellent transmission characteristics in the visible region. Functions as a heat ray shielding (near infrared shielding) filter.
Such a heat ray shielding filter can be used by being mounted on a window (outside air side or inside air side) of a transport aircraft such as a building window, a car, an airplane, or a train, for example.
The filter of the present invention functions as an optical filter for an imaging device and an optical filter for a display by containing at least one naphthalocyanine compound represented by the general formula (1).
Such an optical filter can be used by being mounted on, for example, a camera module, various sensors, and various displays (liquid crystal display, plasma display).
Moreover, the optical filter of the present invention functions as an electromagnetic wave shield having a characteristic of blocking electromagnetic waves from the display screen, for example.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these. Hereinafter, the spectral characteristics were measured and evaluated as follows using a spectrophotometer (U-4100) manufactured by Hitachi High-Technology Corporation.

<Evaluation of incident angle dependency>
In the wavelength range of 560 to 800 nm, the wavelength (Xa) at which the transmittance measured from the vertical direction of the filter is 50%, and the transmittance measured from an angle of 30 ° with respect to the vertical direction of the filter is 50%. The wavelength (Xb) was measured, and the absolute value | Xa−Xb | of the difference between Xa and Xb was determined.
The smaller the value of | Xa−Xb |, the smaller the incident angle dependency of the absorption wavelength, and the wider the viewing angle. In practice, the value of | Xa−Xb | is preferably 20 nm or less.

<Evaluation of steep absorption>
When the absorbance at the absorption maximum wavelength (L) was normalized to 1.0, the difference (LM) of the wavelength (M) at which the absorbance was 0.3 was determined.
A smaller value of | LM | indicates that the absorption spectrum is steeper.
Practically, the value of | LM | is preferably 40 nm or less, and more preferably 30 nm or less.

Example 1
Add 100 g of cyclic olefin-based resin (Zeonor 1020R, manufactured by Nippon Zeon Co., Ltd.), 0.1 g of compound of Exemplified Compound No. 3, and 3: 7 (mass ratio) mixed solution of cyclohexane and xylene, and the resin concentration is 20% by mass. Solution was obtained.
Next, the obtained solution was cast on a smooth glass plate, dried at 60 ° C. for 8 hours, and at 80 ° C. for 8 hours, and then peeled from the glass plate.
The peeled coating film was further dried under reduced pressure at 100 ° C. for 24 hours to produce a substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.
The spectral transmittance of this substrate was measured, and the absorption maximum wavelength, the transmittance in the visible light wavelength region, and | LM− were determined. The results are shown in Table 1.

Subsequently, a dielectric multilayer film [silica layer (SiO ₂ : film thickness 83 to 199 nm) and titania layer (TiO ₂ : film thickness 101 to 101 nm) reflecting near infrared rays at a deposition temperature of 100 ° C. on one side of the obtained substrate. A dielectric multilayer film [silica layer (SiO ₂ : film thickness) reflecting near infrared rays at a deposition temperature of 100 ° C. on the other surface of the substrate. 77 to 189 nm) and titania layers (TiO ₂ : film thickness 84 to 118 nm) are formed alternately to form a filter having a thickness of 0.105 mm. The spectral transmittance of this filter was measured, and the optical characteristics in the infrared wavelength region and | Xa−Xb | were determined. The average value of transmittance at a wavelength of 430 to 580 nm was 90%, and the average value of transmittance at a wavelength of 800 to 1000 nm was 1% or less. The results are shown in Table 1.

(Example 2)
By adding 100 g of cyclic olefin-based resin (APEL6015T, manufactured by Mitsui Chemicals, Inc.), 0.1 g of compound of Exemplified Compound No. 7, and 7: 3 (mass ratio) mixed solution of cyclohexane and methylene chloride, the resin concentration is 20 mass. % Solution was obtained.
Subsequently, the obtained solution was cast on a smooth glass plate, dried at 40 ° C. for 4 hours, and at 60 ° C. for 4 hours, and then peeled from the glass plate. The peeled coating film was further dried at 100 ° C. under reduced pressure for 8 hours to produce a substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.
Using this substrate, a filter having a dielectric multilayer film having a thickness of 0.105 mm was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Examples 3 to 8)
Instead of using the compound of Example Compound No. 7 in Example 2, the compound of Example Compound No. 12 (Example 3), the compound of Example Compound No. 16 (Example 4), the compound of Example Compound No. 21 (Example) 5), described in Example 2 except that the compound of Exemplified Compound No. 25 (Example 6), the compound of Exemplified Compound No. 36 (Example 7), and the compound of Exemplified Compound No. 41 (Example 8) were used. A substrate was produced by the method, and a filter having a dielectric multilayer film was produced and evaluated.
The results are shown in Table 1.

Example 9
100 g of polycarbonate resin (Pure Ace, manufactured by Teijin Ltd.), 0.05 g of Compound of Exemplified Compound No. 14, 0.05 g of Compound of Exemplified Compound No. 15, and methylene chloride are added to obtain a solution having a resin concentration of 20% by mass. It was. Subsequently, the obtained solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 100 ° C. for 6 hours under reduced pressure to produce a substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm. Using this substrate, a filter having a dielectric multilayer film having a thickness of 0.105 mm was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Examples 10 to 12)
In Example 9, instead of using the compound of Exemplified Compound No. 14 and the compound of Exemplified Compound No. 15, in (Example 10), the compound of Example Compound No. 8 is represented by 0.06 g and the formula (a) Using 0.04 g of naphthalocyanine compound,
In (Example 11), 0.07 g of the compound of Exemplified Compound No. 20 and 0.03 g of the cyanine compound represented by the formula (b) are used.
In Example 12, a dielectric multilayer film was formed by the method described in Example 9, except that 0.05 g of Compound No. 44 of Exemplified Compound No. and 0.05 of the diimonium compound represented by the formula (c) were used. A filter having a thickness of 0.105 mm was prepared and evaluated. These results are shown in Table 1.

(Example 13)
100 g of polyethersulfone (Sumilite FS-1300, manufactured by Sumitomo Bakelite Co., Ltd.), 0.05 g of compound of exemplified compound number 6, 0.05 g of compound of exemplified compound number 13, and N-methyl-2-pyrrolidone A solution having a concentration of 20% by mass was obtained. Subsequently, the obtained solution was cast on a smooth glass plate, dried at 60 ° C. for 4 hours, and at 80 ° C. for 4 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 120 ° C. under reduced pressure for 8 hours to produce a substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.
Using this substrate, a filter having a thickness of 0.105 mm was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 1)
In Example 1, a substrate was prepared by the method described in Example 1 except that the compound of Exemplified Compound No. 3 was not used. Further, using this substrate, a 0.105 mm thick filter having a dielectric multilayer film was produced and evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 2)
In Example 1, a substrate was prepared by the method described in Example 1 except that the phthalocyanine compound represented by the formula (d) was used instead of the compound of Exemplified Compound No. 3. Further, a filter having a thickness of 0.105 mm having a dielectric multilayer film was produced and evaluated using this substrate in the same manner as in Example 1. The results are shown in Table 1.

(Example 14)
12 kg of the compound of Exemplified Compound No. 29 is added to 100 kg of molten polycarbonate resin (Teijin Chemicals Ltd., Panlite 1285, trade name), and the outer diameter is 75 mm and the center thickness is 2 mm at 250 to 300 ° C. using an injection molding machine. Molded into a lens.
The light transmittance value at 700 nm at the center of this lens was 9.0%, and the visible light transmittance was 89%. Moreover, when this lens was worn and a laser cutter was used, no irritation or fatigue was felt in the eyes, and there was no problem in confirming the object in the field of view.

(Example 15)
Preparation of transparent adhesive layer 40 g of triethylene glycol-di-2-ethylhexanoate, [2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chloro as an ultraviolet absorber 1 g of benzotriazole], 1 g of (2,6-di-tert-butyl-4-methylphenol) as an antioxidant and 0.004 g of the compound of Exemplified Compound No. 7 are mixed, and a phosphate compound as a dispersant. After adding 0.001 g, the mixture was mixed in a horizontal microbead mill to obtain a dispersion.
This dispersion and 100 g of polyvinyl butyral resin were sufficiently kneaded with a mixing roll to obtain a transparent adhesive composition.
This transparent adhesive composition is sandwiched between two fluororesin sheets via a clearance plate (760 μm) and press-molded at 150 ° C. for 30 minutes to produce a transparent adhesive layer having a thickness of 760 μm. It was cut and processed into a size of 30 cm.

-Production of filter (laminated glass) Next, the obtained transparent adhesive layer is sandwiched between two green glasses [conforms to JIS R3208 (1998), length 30 cm x width 30 cm x thickness 2 mm], using a vacuum laminator The laminate was obtained by holding at 90 ° C. for 30 minutes and vacuum pressing. In the laminated body, the intermediate film portion protruding from the glass plate was cut off to produce a laminated glass.

・ Evaluation of the filter This laminated glass is fully bonded to the outside air side of the window glass of the room (length 2m x width 2m x height 2m), and the temperature of the room between 12pm and 3pm in midsummer is measured. As a result, the maximum temperature was 31 ° C. This filter was used in the same environment for three months from July to September, but it was found that the heat ray shielding effect was not changed and had excellent weather resistance.

(Comparative Example 3)
In Example 15, except that the compound of Exemplified Compound No. 7 was not used, a laminated glass was produced by the method described in Example 15, and this laminated glass was placed in a room (2 m long × 2 m wide × 2 m high). ) Was measured on the room temperature between 12 pm and 3 pm in midsummer, and the maximum temperature was 37 ° C.

(Comparative Example 4)
In Example 15, instead of using the compound of Exemplified Compound No. 7, a laminated glass was produced by the method described in Example 15 except that the compound represented by the formula (e) was used. Was pasted on the entire window glass of the room (length 2m x width 2m x height 2m), and the temperature of the room between 12pm and 3pm in midsummer was measured. The maximum temperature was 35 ° C. .
In addition, when this filter was used in the same environment for 1 month in July, absorption of the compound represented by the formula (e) was lost, and the weather resistance (light resistance) was inferior. found.

(Comparative Example 5)
In Example 15, instead of using the compound of Example Compound No. 7, a laminated glass was produced by the method described in Example 15 except that the compound represented by the formula (f) was used. Was pasted on the entire window glass of the room (length 2m x width 2m x height 2m), and the temperature of the room between 12pm and 3pm in midsummer was measured. The maximum temperature was 35 ° C. .
In addition, when this filter was used in the same environment for one month in July, absorption of the compound represented by the formula (f) was lost, and the weather resistance (light resistance) was inferior. found.

(Example 16)
A biaxially stretched polyethylene terephthalate film (PET) (thickness: 188 μm) is used as a base, and an ITO thin film (film thickness: 40 nm), a silver thin film (film thickness: 11 nm), an ITO thin film are sequentially formed on one side of the PET film. (Film thickness: 95 nm), silver thin film (film thickness: 14 nm), ITO thin film (film thickness: 90 nm), silver thin film (film thickness: 12 nm), ITO thin film (film thickness: 40 nm), a total of 7 transparent conductive layers And a transparent laminate having a transparent conductive layer having a surface resistance of 2.2Ω / □ was produced.
The compound of Exemplified Compound No. 38 and the tetraazaporphyrin compound represented by the formula (g) were dissolved in an ethyl acetate / toluene (50: 50% by mass) solvent to prepare a diluted solution.

Acrylic adhesive (80% by mass) and this dilute solution (20% by mass) are mixed, applied to the surface of the substrate side of the transparent laminate with a comma coater to a dry film thickness of 25 μm, dried and adhesive A release film was laminated on the surface to form a transparent adhesive layer sandwiched between the release film and the substrate of the transparent laminate.
The adhesive material had a refractive index of 1.51 and an extinction coefficient of 0.
The compound of Exemplified Compound No. 38 and the tetraazaporphyrin compound represented by the formula (g) were prepared so as to contain 1150 (mass) ppm and 1050 (mass) ppm, respectively, in the dried adhesive material.

On the other hand, a gravure coater is applied to one surface of a triacetylcellulose film (thickness: 80 μm) by adding a photopolymerization initiator to a polyfunctional methacrylate resin and further dispersing ITO fine particles (average particle size: 10 nm). Was applied and cured with UV to form a conductive hard coat film (film thickness: 3 μm).
A fluorine-containing organic compound solution is coated on the microgravure coater, dried at 90 ° C and thermally cured to form an antireflective film (film thickness: 100 nm) with a refractive index of 1.4. Hard coat function (Pencil hardness: 2H), gas barrier function (moisture permeability: 1.8 g / m ² · day), antireflection function (visible surface light reflectance: 1.0%), antistatic function (surface resistance: 7 × 10 ⁹ Ω / □), an antireflection film was produced as a functional transparent layer having an antifouling function.
On the other main surface of the antireflection film, an acrylic pressure-sensitive adhesive and a diluent [ethyl acetate / toluene (50: 50% by mass)] are applied and dried to form a transparent pressure-sensitive adhesive layer having a thickness of 25 μm and further separated. A mold film was laminated. The roll-shaped transparent laminate / adhesive / release film was cut into a size of 970 mm × 570 mm and fixed on a glass support plate with the transparent conductive layer surface facing up. Furthermore, using a laminator, the antireflection film was laminated only on the inner side, leaving the conductive portion so that the peripheral portion 20 mm of the transparent conductive layer was exposed.

Further, a silver paste was screen-printed in a range of a width of 22 mm at the peripheral edge so as to cover the exposed conductive portion of the transparent conductive layer, and dried to form an electrode having a thickness of 15 μm.
A display filter having an electromagnetic wave shielding function having a release film on the transparent adhesive layer surface was prepared by removing from the glass support plate.

Furthermore, the release film of the display filter is peeled off and bonded to the front surface of the plasma display panel (display unit 920 mm × 520 mm) using a single wafer laminator, and then at 60 ° C. and 2 × 10 ⁵ Pa. Autoclaved.
The electrode part of the display filter and the ground part of the plasma display panel were connected using a conductive copper foil adhesive tape to obtain a display device equipped with the display filter.

In the plasma display equipped with this display filter, the transmittance at 595 nm was 37% with respect to the transmittance at 610 nm.
In the plasma display equipped with the display filter, the bright place contrast ratio under the condition of the ambient illuminance of 100 lx was improved to 44, compared with 20 before the display filter was formed.
Further, as an electronic device using an infrared remote controller, even when a home VTR was brought close to a plasma display at 0.5 m, the VTR did not malfunction. When the display filter was not attached, the VTR malfunctioned even when the VTR was moved 5 m away from the plasma display.

The filter of the present invention is a filter excellent in optical characteristics and weather resistance, comprising at least one naphthalocyanine compound having a specific structure. Taking advantage of such excellent filter characteristics, for example, a heat ray shielding filter, for imaging It can be used for applications such as optical filters and filters for various displays.

11: Substrate (A)

21: Substrate (A)
22: Transparent adhesive layer (B)

31: Substrate (A)
32: Transparent adhesive layer (B)

41: Substrate (A)
43: Functional transparent layer (C)

52: Transparent adhesive layer (B)

61: Substrate (A)
63: Functional transparent layer (C)

71: Substrate (A)
72: Transparent adhesive layer (B)
73: Functional transparent layer (C)

81: Substrate (A)
82: Transparent adhesive layer (B)
83: Functional transparent layer (C)
84: Transparent conductive layer (D)

91: Substrate (A)
92: Transparent adhesive layer (B)
93: Functional transparent layer (C)
94: Transparent conductive layer (D)

Claims (3)

A filter comprising at least one naphthalocyanine compound represented by the general formula (1).
(Wherein R _{1 to} R ₄ each independently represents a halogen atom or a substituted or unsubstituted aryl group, and X _{1 to} X ₂₀ each independently represent a hydrogen atom, a halogen atom, a straight chain, a branched chain or a cyclic group) An alkyl group, a linear, branched or cyclic alkoxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aryloxy group,
M represents two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or a metal oxide atom) The filter according to claim 1, comprising a substrate and a transparent adhesive layer. The filter according to claim 1, comprising a substrate and a functional transparent layer.